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WO2018186002A1 - Resin composition and method for producing resin composition - Google Patents

Resin composition and method for producing resin composition Download PDF

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Publication number
WO2018186002A1
WO2018186002A1 PCT/JP2018/002183 JP2018002183W WO2018186002A1 WO 2018186002 A1 WO2018186002 A1 WO 2018186002A1 JP 2018002183 W JP2018002183 W JP 2018002183W WO 2018186002 A1 WO2018186002 A1 WO 2018186002A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
resin composition
aromatic polycarbonate
mass
polycarbonate resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/002183
Other languages
French (fr)
Japanese (ja)
Inventor
晃人 栗山
貴裕 大江
上田 賢司
浩平 清水
稲垣 靖史
靖俊 川手
新吾 一瀬
澤田 真一
尚人 森永
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sony Corp
Original Assignee
Sony Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sony Corp filed Critical Sony Corp
Priority to JP2019511070A priority Critical patent/JP7060013B2/en
Priority to CN202210249663.1A priority patent/CN114634695A/en
Priority to CN201880023460.2A priority patent/CN110506078B/en
Publication of WO2018186002A1 publication Critical patent/WO2018186002A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41Compounds containing sulfur bound to oxygen
    • C08K5/42Sulfonic acids; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • C08L75/06Polyurethanes from polyesters

Definitions

  • the present technology relates to a resin composition and a method for producing the resin composition.
  • Resin compositions containing polycarbonate resin are used in various fields such as exterior, electronic / electrical applications, optical disk substrates and the like.
  • the present situation is that further improvement in the performance of the resin composition containing the polycarbonate resin is desired as the application is expanded in the OA / copier field, the automobile field, the medical material field, and the like.
  • a glycol containing a dicarboxylic acid polycondensation component composed of one or more terephthalic acid components selected from the group consisting of terephthalic acid and terephthalic acid derivatives, and 40 mol% or more of 1,4-cyclohexanedimethanol
  • a transparent face plate for outdoor use characterized by comprising 60 to 80 parts by weight of a polyester resin obtained by polycondensation with a system polycondensation component and 40 to 20 parts by weight of a polycarbonate resin has been proposed (Patent Document 1). See).
  • a curable paint for polycarbonate resin containing a compound (A) having two or more (meth) acryloyl groups in the molecule, conductive fine particles (B) and an organic solvent (C), wherein the organic Proposed curable coating for polycarbonate resin, containing at least a compound (C-1) having a solubility parameter of 8.0 to 10.0 (cal / cm 3 ) 1/2 as solvent (C) (See Patent Document 2).
  • Patent Documents 1 and 2 may not be able to further improve the resin physical properties.
  • the main object of the present technology is to provide a resin composition having excellent resin properties and a method for producing a resin composition having excellent resin properties.
  • the present technology provides a resin composition comprising 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, wherein the polyurethane resin is a cured resin.
  • the average particle size of the polyurethane resin powder having the crosslinked structure may be 0.5 mm to 1.5 mm.
  • the ratio of the particle diameter of the polyurethane resin powder having the crosslinked structure to 0.5 mm to 1.5 mm may be 70% or more with respect to the total powder of the polyurethane resin having the crosslinked structure.
  • the polyurethane resin having the crosslinked structure may be obtained from a reaction between a polyester polyol and a polyisocyanate.
  • the mass ratio of the polyester polyol and the polyisocyanate may be 100: 50 to 100: 200.
  • the polyester polyol may have a hydroxyl value of 30 to 300.
  • the polyester polyol may have a polystyrene-equivalent weight average molecular weight of 10,000 or more and 500,000 or less.
  • the polyisocyanate may have two or more isocyanate groups.
  • An organic sulfonic acid and / or an organic sulfonic acid metal salt compound may further be included in an amount of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin.
  • the organic sulfonic acid metal salt compound may have a polystyrene equivalent weight average molecular weight of 30,000 or more.
  • the organic sulfonic acid metal salt compound may contain a sulfonic acid metal base, and the content of the sulfonic acid metal base may be 0.1 to 10 mol%.
  • the aromatic polycarbonate resin may contain a recycled polycarbonate resin, and the content of the recycled polycarbonate resin may be 1 to less than 100% by mass with respect to the total mass of the aromatic polycarbonate resin.
  • the polyurethane resin having the crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the crosslinked structure are added. It may be obtained by kneading with a polyurethane resin.
  • a polyurethane resin having a crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the polyurethane resin having the crosslinked structure are added.
  • a method for producing a resin composition comprising kneading.
  • the method for producing a resin composition according to the present technology may include producing a polyurethane resin having the crosslinked structure by reacting a polyester polyol and a polyisocyanate.
  • the physical properties of the resin can be improved.
  • the effect described here is not necessarily limited, and may be any effect described in the present technology.
  • the present technology relates to a resin composition including an aromatic polycarbonate resin and a polyurethane resin having a crosslinked structure, which have improved resin physical properties. More specifically, the present technology improves surface physical properties such as solvent resistance, chemical resistance, and scratch resistance without coating the surface with a coating material, and is excellent in the inherent resistance of an aromatic polycarbonate resin.
  • the present invention relates to a resin composition having improved fluidity without impairing mechanical properties such as impact properties.
  • the present technology also relates to a method for producing the resin composition.
  • a resin composition containing a polycarbonate resin is excellent in heat resistance, impact resistance, transparency, and the like.
  • a resin composition containing a polycarbonate resin for example, an aromatic polycarbonate resin
  • improvement of surface properties such as fluidity, solvent resistance, and chemical resistance of a resin composition containing a polycarbonate resin is desired.
  • PET polyethylene terephthalate resin
  • PBT polybutylene terephthalate resin
  • the present technology provides a resin composition comprising 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, wherein the polyurethane resin is a cured resin.
  • 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the polyurethane resin having a crosslinked structure are mixed.
  • a method for producing a resin composition is provided.
  • the present technology provides a resin molded body obtained by molding the resin composition according to the present technology.
  • a resin composition in which surface properties such as fluidity, solvent resistance, chemical resistance, and scratch resistance are improved without reducing mechanical properties such as impact resistance.
  • a flame retardant for example, organic sulfonic acid, an organic sulfonic acid metal salt compound, etc.
  • the resin composition which provided the flame retardance further is provided.
  • this technique may use an aromatic polycarbonate resin containing a recovered polycarbonate resin such as a waste optical disk, the recovered polycarbonate resin such as a waste optical disk can be effectively used as a raw material. Can contribute to resource saving.
  • the resin composition of the first embodiment according to the present technology includes 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, and the polyurethane resin is a cured resin.
  • the polyurethane resin having a crosslinked structure may be a photocurable resin obtained by curing a curable polyurethane resin composition with light (for example, ultraviolet light) or a thermosetting resin cured with heat.
  • the improvement in fluidity improves the processability (moldability, etc.) of the resin composition.
  • the content of the polyurethane resin having a crosslinked structure in the resin composition is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. From the viewpoint of further improving the mechanical properties. 0.05 to 3.0 parts by mass is preferable.
  • the resin composition of the first embodiment according to the present technology includes an aromatic polycarbonate resin.
  • the content of the aromatic polycarbonate resin may be any amount, but is preferably 94.5 to 99.5% by mass, and preferably 96 to 98% by mass with respect to the total mass of the resin composition. More preferred.
  • the aromatic polycarbonate resin is used as a raw material for producing a molded part of the resin composition of the first embodiment according to the present technology, and is used for applications such as optical discs and housing materials for home appliances.
  • an aromatic polycarbonate resin produced by a reaction between a dihydric phenol and a carbonate precursor can be used.
  • the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
  • the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
  • the aromatic polycarbonate resin may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof within a range that does not impair the gist of the present technology.
  • an aromatic dicarboxylic acid for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof within a range that does not impair the gist of the present technology.
  • other thermoplastic resins other than an aromatic polycarbonate resin can be mix
  • the amount of other thermoplastic resin blended varies depending on the type and purpose, but is usually preferably 1 to 30 parts by weight and more preferably 2 to 20 parts by weight per 100 parts by weight of the aromatic polycarbonate resin.
  • thermoplastic resins include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, polyamide resin, cyclic polyolefin resin, polyarylate resin (non-crystalline) And so-called super engineering plastics such as engineering plastics typified by polyarylate and liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylene sulfide. .
  • thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.
  • the aromatic polycarbonate resin contained in the resin composition of the first embodiment according to the present technology may include an aromatic polycarbonate resin having a branched structure (sometimes referred to as a branched aromatic polycarbonate resin).
  • the branched aromatic polycarbonate (PC) resin is not particularly limited as long as it is a branched aromatic polycarbonate resin.
  • PC branched aromatic polycarbonate resin
  • it has a branched nucleus structure derived from a branching agent represented by the following general formula (I).
  • the viscosity average molecular weight is 15,000 to 40,000, preferably 17,000 to 30,000, more preferably 17,000 to 27,000, and the amount of branching agent used is
  • the branched aromatic polycarbonate resin is preferably in the range of 0.01 to 3 mol%, more preferably 0.1 to 2.0 mol% with respect to the dihydric phenol compound.
  • R is hydrogen or an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an n-pentyl group.
  • R1 to R6 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc.) or a halogen atom (for example, chlorine Atoms, bromine atoms, fluorine atoms, etc.).
  • the branching agent represented by the general formula (I) is more specifically 1,1,1-tris (4-hydroxyphenyl) -methane; 1,1,1-tris (4-hydroxyphenyl) -ethane; 1,1,1-tris (4-hydroxyphenyl) -propane; 1,1,1-tris (2-methyl-4-hydroxyphenyl) -methane; 1,1,1-tris (2-methyl-4- 1,1,1-tris (3-methyl-4-hydroxyphenyl) -methane; 1,1,1-tris (3-methyl-4-hydroxyphenyl) -ethane; 1-tris (3,5-dimethyl-4-hydroxyphenyl) -methane; 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) -ethane; 1,1,1-tris (3- Chloro-4-hydroxy Phenyl) -methane; 1,1,1-tris (3-chloro-4-hydroxyphenyl) ethane; 1,1,1-tris (3,
  • branching agents may be used alone or in combination of two or more.
  • 1,1,1-tris (4-hydroxyphenyl) ethane is used as the branching agent
  • the amount used is 0.2 to 2.0 mol% with respect to the dihydric phenol compound.
  • it is 0.3 to 2.0 mol%, more preferably 0.4 to 1.9 mol%.
  • the amount is 0.2 mol% or more, the degree of freedom of blending is widened, and when the amount is 2.0 mol% or less, gelation is difficult during polymerization, and the production of an aromatic polycarbonate resin is easy.
  • the branched aromatic polycarbonate resin has a branched nucleus structure derived from the branching agent represented by the general formula (I), and is specifically represented by the following formula.
  • a, b and c are integers, and PC represents a polycarbonate portion.
  • PC represents a repeating unit represented by the following formula, for example, when bisphenol A is used as a raw material component.
  • the amount (ratio) of the branched aromatic polycarbonate resin in 100 parts by mass of the aromatic polycarbonate resin is preferably 10 to 100 parts by mass, and more preferably 50 to 100 parts by mass. If the amount of the branched aromatic polycarbonate resin is not 10 parts by mass or more, for example, a thin flame retardant effect may not be obtained.
  • the aromatic polycarbonate resin may include an unbranched polycarbonate resin that does not contain halogen in the molecular structure.
  • the unbranched polycarbonate resin is preferably a polymer having a structural unit represented by the following formula (II).
  • X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, etc.) And when X is plural, they may be the same or different, and a and b are each an integer of 1 to 4.
  • Y represents a single bond, an alkylene group having 1 to 8 carbon atoms or an alkylidene group having 2 to 8 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylene group).
  • a cycloalkylene group having 5 to 15 carbon atoms or a cycloalkylidene group having 5 to 15 carbon atoms for example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, etc.
  • X is preferably a hydrogen atom
  • Y is preferably an ethylene group or a propylene group.
  • This aromatic polycarbonate resin can be easily produced by reacting a dihydric phenol represented by the following formula (IV) with phosgene or a carbonic acid diester compound. That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or viscosity average molecular weight regulator, by reaction of a dihydric phenol with a carbonate precursor such as phosgene, or dihydric phenol and diphenyl carbonate. Is produced by a transesterification reaction with a carbonate precursor.
  • dihydric phenols represented by the formula (IV).
  • dihydric phenols other than the dihydric phenols represented by the formula (IV) include dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone, 1,5-dihydroxynaphthalene; and dihydroxynaphthalene such as 2,6-dihydroxynaphthalene. And the like. These dihydric phenols may be used alone or in combination of two or more.
  • the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
  • polymerization of a polycarbonate may be used, and various things can be used.
  • the monohydric phenol include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, and nonylphenol.
  • the aromatic polycarbonate used in the present invention may be a mixture of two or more aromatic polycarbonates.
  • the aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 to 100,000, particularly preferably 20,000 to 40,000, from the viewpoint of mechanical strength and moldability. .
  • the aromatic polycarbonate resin contained in the transmissive resin composition of the first embodiment according to the present technology may include an aromatic polycarbonate-polyorganosiloxane copolymer.
  • the aromatic polycarbonate-polyorganosiloxane copolymer comprises an aromatic polycarbonate part and a polyorganosiloxane part, and includes an aromatic polycarbonate structural unit represented by the following general formula (V) and a polysiloxane represented by the general formula (VI). It contains an organosiloxane structural unit.
  • R 5 and R 6 each represent a halogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) or an optionally substituted phenyl group, and R When there are a plurality of 5 and R 6 , they may be the same or different.
  • Y is a single bond, an alkylene group or alkylidene group having 1 to 20 carbon atoms (preferably 2 to 10 carbon atoms), a cycloalkylene group or cycloalkylidene group having 5 to 20 carbon atoms (preferably 5 to 12 carbon atoms),- O—, —S—, —SO—, —SO 2 — or —CO— is shown, and an isopropylidene group is preferred.
  • p and q are each an integer of 0 to 4 (preferably 0), and when there are a plurality of p and q, they may be the same or different.
  • m represents an integer of 1 to 100 (preferably an integer of 5 to 90). When m is from 1 to 100, an appropriate viscosity average molecular weight can be obtained in the aromatic polycarbonate-polyorganosiloxane copolymer.
  • R 7 to R 10 each represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may have a substituent, and they may be the same or different.
  • Specific examples of R 7 to R 10 include methyl groups, ethyl groups, propyl groups, n-butyl groups, isobutyl groups, amyl groups, isoamyl groups, hexyl groups and other alkyl groups, phenyl groups, tolyl groups, xylyl groups, and the like. Mention may be made of phenyl aryls such as naphthyl groups.
  • R 11 represents an aliphatic or aromatic organic residue, and is preferably a divalent organic compound residue such as an o-allylphenol residue, a p-hydroxystyrene residue, and an eugenol residue.
  • the method for producing the aromatic polycarbonate-polyorganosiloxane copolymer includes, for example, using an aromatic polycarbonate oligomer and a polyorganosiloxane having a reactive group at the end constituting the polyorganosiloxane part in a solvent such as methylene chloride. It can be produced by dissolving and adding a dihydric phenol such as bisphenol A using a catalyst such as triethylamine and interfacial polycondensation reaction.
  • This aromatic polycarbonate-polyorganosiloxane copolymer is, for example, disclosed in JP-A-3-292359, JP-A-4-202465, JP-A-8-81620, JP-A-8-302178, and JP-A-10-302. -7897 and the like.
  • the degree of polymerization of the aromatic polycarbonate structural unit of the aromatic polycarbonate-polyorganosiloxane copolymer is preferably 3 to 100, and the degree of polymerization of the polyorganosiloxane structural unit is preferably about 2 to 500, more preferably about 2 to 300. More preferably, about 2 to 140 is used.
  • the polyorganosiloxane content of the aromatic polycarbonate-polyorganosiloxane copolymer is usually about 0.1 to 10% by mass, preferably 0.3 to 6% by mass.
  • the viscosity-average molecular weight of the aromatic polycarbonate-polyorganosiloxane copolymer used in the transmission resin composition of the first embodiment according to the present technology is usually about 5,000 to 100,000, preferably 10,000 to 30,000, particularly preferably 12,000 to 30,000.
  • these viscosity average molecular weights (Mv) can be obtained in the same manner as the above polycarbonate resin.
  • the aromatic polycarbonate resin shown above may be a newly manufactured virgin material, waste material, end material, sprue material, waste, etc. generated in the manufacturing process, or a product (for example, a digital versatile disc (DVD), It may be a recovered material or a waste material of an optical disc (substrate) such as a compact disc (CD), MO, MD, or Blu-ray disc (BD) (recycled polycarbonate resin).
  • the recycled polycarbonate resin is preferably a recycled polycarbonate resin recovered from the market.
  • the aromatic polycarbonate resin may contain a recycled polycarbonate resin or may be composed of a recycled polycarbonate resin.
  • the content of the recycled polycarbonate resin is preferably 1 to less than 100% by mass with respect to the total mass of the aromatic polycarbonate resin.
  • the recovered optical disc there are various deposits such as a metal reflection layer, a plating layer, a recording material layer, an adhesive layer, a label, etc., but in the present invention, these may be used as provided.
  • Such impurities and sub-materials may be used after being separated and removed by a conventionally known method.
  • a metal reflection layer such as Al, Au, Ag, Si, an organic dye containing a cyanine dye, Te, Se, S, Ge, In, Sb, Fe, Tb, Co, Ag, Ce, Bi, etc.
  • Recording material layers acrylic acrylates, ether acrylates, vinyl monomers and oligomers, adhesive layers comprising at least one polymer, UV curable monomers, oligomers, at least one polymer and polymerization initiators and pigments, Examples include label ink layers in which an auxiliary agent is mixed, but are not limited thereto, and may include a film forming material and a coating material that are usually used in an optical disk.
  • an optical disk can be finely crushed and used as a PC resin raw material as it is, or kneaded and melted with a predetermined additive and pelletized.
  • the recovery disk may be directly put into a hopper or the like of the injection molding machine together with various additives described later to obtain a molded body made of the resin composition.
  • deposits such as a metal reflection layer, a recording material layer, an adhesive layer, a surface hardened layer, and a label are, for example, It can be removed by a mechanical or chemical method proposed in JP-A-6-223416, JP-A-10-269634, JP-A-10-249315, or the like.
  • the weight average molecular weight of the aromatic polycarbonate resin can be measured in terms of polystyrene based on a polystyrene molecular weight standard substance (sample) by GPC (Gel Permeation Chromatography) measurement using a chloroform solvent.
  • the molecular weight of the aromatic polycarbonate resin may be any value, but the molecular weight is preferably 36000 to 63,000 in terms of weight average molecular weight (polystyrene conversion). The reason is that if the weight average molecular weight of the aromatic polycarbonate resin is larger than 63,000, the flowability (workability) at the time of melting of the resin composition as the final target product tends to be deteriorated. On the other hand, when it is smaller than 36000, the solvent resistance tends to decrease and solvent cracks (cracks due to chemicals) tend to occur, and the impact resistance tends to decrease.
  • the aromatic polycarbonate resin contained in the resin composition preferably has a weight average molecular weight of 40,000 to 59,000, and more preferably 44,000 to 54,000, from the viewpoint of mechanical strength and moldability.
  • the resin composition according to the first embodiment of the present technology includes 0.01 to 5.0 parts by mass of a cured polyurethane resin having a crosslinked structure with respect to 100 parts by mass of the aromatic polycarbonate resin. Below, the polyurethane resin which has a crosslinked structure is demonstrated in detail.
  • the polyurethane resin is not particularly limited as long as the polyurethane resin is a cured resin polyurethane resin having a crosslinked structure, but it has excellent surface physical properties such as chemical resistance.
  • a polyurethane resin having a cross-linked structure in which a polyester polyol and polyisocyanate are reacted to cross-link three-dimensionally is preferable.
  • the mass ratio of the polyester polyol to be reacted and the polyisocyanate may be any ratio, but is preferably 100: 50 to 100: 200.
  • a polyurethane resin contains the structural unit derived from a polyester polyol and the structural unit derived from polyisocyanate.
  • the polyurethane resin having a crosslinked structure can be obtained, for example, by mixing two liquids of a polyester polyol and a polyisocyanate, and then producing by a thermosetting reaction. Using a pellet-like aromatic polycarbonate resin, two liquids of polyester polyol and polyisocyanate are mixed and heated in the range of 60 to 200 ° C. for several seconds to 10 minutes. To form a polyurethane resin coating. Thereafter, for example, by kneading with a twin-screw extruder, the resin composition of the first embodiment according to the present technology including an aromatic polycarbonate resin and a polyurethane having a crosslinked structure can be produced.
  • the present technology can also be obtained by applying a polyurethane resin-coated resin composition by heating after applying two liquids of polyester polyol and polyisocyanate on a color plate made of an aromatic polycarbonate resin and re-pelletizing.
  • the resin composition of 1st Embodiment which concerns on can be manufactured.
  • a coated product obtained by coating a polyurethane resin on a carbonate resin is not particularly limited, and may be a conventionally known method.
  • a method may be used in which a polyurethane resin is applied to a carbonate resin (for example, aromatic carbonate resin) substrate, and then the obtained two-layer film is baked at the same time.
  • the method for coating may be appropriately selected from conventionally known methods in consideration of the form of the polyurethane resin to be used and the surface shape of the base material of the carbonate resin (for example, aromatic carbonate resin), and is particularly limited.
  • it can be applied by air spray, airless spray, shower, carte coater, bell, or other ordinary electrostatic coating.
  • the obtained coated product may be subjected to natural drying or forced drying (for example, hot air drying, near infrared drying, electromagnetic wave drying, etc.).
  • the method for baking is not particularly limited, but the baking temperature is 70 to 110 ° C. in consideration of the possibility that the baking may cause deterioration of the base material of the carbonate resin (for example, aromatic carbonate resin).
  • the baking time at that time depends on the baking temperature and may be appropriately set in consideration of energy efficiency, but it is 10 to 60 minutes. It is preferable to set it for 15 to 40 minutes.
  • the average particle diameter of the polyurethane resin powder having a crosslinked structure may be any average particle diameter, but is preferably 0.5 mm to 1.5 mm.
  • the average particle size of the polyurethane resin having a crosslinked structure is 0.5 mm to 1.5 mm, the dispersibility and mixing properties of the polyurethane resin are improved in the aromatic polycarbonate resin.
  • the surface properties (chemical resistance, etc.) and fluidity will be further improved while the mechanical properties of the resin composition are better maintained.
  • the ratio of the particle size of the polyurethane resin powder to 0.5 mm to 1.5 mm may be any ratio to the total polyurethane resin powder, but is 70% or more. It is preferable.
  • the content is 70% or more, the dispersibility and mixing properties of the polyurethane resin become better in the aromatic polycarbonate resin.
  • the surface properties (chemical resistance, etc.) and fluidity will be further improved while the mechanical properties of the resin composition are better maintained.
  • the particle size distribution of the polyurethane resin powder can be measured as follows.
  • low tap measurement was used.
  • the low-tap method is a method for sorting by sieve eyes, and is a measurement method for measuring the mass of a sample remaining on each sieve and describing the cumulative distribution on a graph to obtain an average particle size distribution.
  • the particle size of the polyurethane resin powder having a crosslinked structure can be changed by adjusting the pulverization conditions.
  • a polyurethane resin having a particle size of 0.5 mm to 1.5 mm and a ratio of 70% or more with respect to the total powder of the polyurethane resin can be produced by pulverizing the polyurethane resin by a freeze pulverization method.
  • the ratio of the polyester polyol and the polyisocyanate is such that the ratio of the number of hydroxyl equivalents in the polyester polyol to the number of isocyanate equivalents in the polyisocyanate (number of hydroxyl equivalents in the polyester polyol component: number of isocyanate equivalents in the polyisocyanate) is 100: 50 to 100. Is preferably set to be in the range of 200, more preferably in the range of 100: 80 to 100: 180. When the number of hydroxyl group equivalents in the polyester polyol is 100 and the number of equivalents of isocyanate in the polyisocyanate is less than 50, the crosslinking reaction between the polyester polyol and the polyisocyanate becomes slightly insufficient, and the coating speed is reduced.
  • the curability is slightly lowered and the physical properties of the coating film such as abrasion resistance, hardness, weather resistance, water resistance, solvent resistance, chemical resistance and the like are slightly lowered.
  • the number of equivalents of hydroxyl group in the polyester polyol is set to 100 and the number of equivalents of isocyanate in the polyisocyanate exceeds 200, the physical properties may be slightly lowered due to the presence of excess polyisocyanate.
  • the curable polyurethane resin composition may appropriately contain a solvent for dissolving or dispersing the polyester polyol and / or polyisocyanate.
  • the solvent may be contained in one or both of the polyester polyol and polyisocyanate.
  • a solvent can also be used in order to dilute so that it may become a suitable viscosity.
  • the solvent examples include hydrocarbon solvents such as toluene, xylene, solvent naphtha, methylcyclohexane, and ethylcyclohexane; ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, And ketone solvents such as diisobutyl ketone.
  • hydrocarbon solvents such as toluene, xylene, solvent naphtha, methylcyclohexane, and ethylcyclohexane
  • ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monomethyl ether
  • acetone methyl ethyl ketone
  • methyl isobutyl ketone methyl isobutyl ketone
  • ketone solvents such as diisobut
  • the curable polyurethane resin composition may be a natural dye, an organic synthetic dye, a pigment, an inorganic pigment, or a bright material (a flake pigment that imparts a glittery feeling or light interference to the coating film).
  • a coloring component such as can be contained. These coloring components may be contained in either polyester polyol or polyisocyanate, but are preferably contained in polyester polyol. Only 1 type may be sufficient as a coloring component, and 2 or more types may be sufficient as it. Needless to say, the polyurethane resin having a crosslinked structure may be a clear coating containing no coloring component.
  • natural pigments include carotenoid pigments such as carotene, carotenal, capsanthin, lycopene, bixin, crocin, canthaxanthin and anato; anthocyanidins such as shisonin, raphanin and enocyanin, chalcones such as safrole yellow and safflower, Flavonols such as rutin and quercetin, flavonoids such as flavones such as cacao pigments, flavin pigments such as riboflavin; anthraquinones such as lacaic acid, carminic acid (cochineal), kermesic acid, alizarin, shikonin Quinone dyes such as naphthoquinones such as alkanin and echinochrome; polyphyrin dyes such as chlorophyll and hemoglobin; diketone dyes such as curcumin (turmeric); Tashianijin based dyes; and the like.
  • organic synthetic dyes or pigments include those defined by Ordinance No. 30 of the Ministry of Health and Welfare.
  • Red 202 (Risor Rubin BCA), Red 203 (Rake Red C), Red 204 (Rake Red CBA), Red 205 (Risor Red), Red 206 (Risor Red CA), Red 207 (Risole) Red BA), Red 208 (Risor Red SR), Red 219 (Brilliant Lake Red R), Red 220 (Deep Maroon), Red 221 (Toluidine Red), Red 228 (Parmaton Red), orange No. 203 (Permanent Orange), Orange No. 204 (Bench Gin Orange G), Yellow 205 (Bench Gin Yellow G), Red No. 404 (Brilliant Fast Scarlet), Red No. 405 (Permanent Red F5R), Orange No. 401 ( Hansa Orange), Yellow No. 401 ( Nzaero), Blue No. 404 (phthalocyanine blue), and the like.
  • inorganic pigments include silicic anhydride, magnesium silicate, talc, kaolin, bentonite, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, light calcium carbonate, heavy calcium carbonate, light magnesium carbonate, and heavy magnesium carbonate.
  • the bright material include flaky aluminum, vapor-deposited aluminum, aluminum oxide, oxybismuth chloride, mica, titanium oxide-coated mica, iron oxide-coated mica, mica-like iron oxide, titanium oxide-coated silica, and titanium oxide-coated alumina.
  • Examples thereof include iron oxide-coated silica, iron oxide-coated alumina, glass flakes, colored glass flakes, vapor-deposited glass flakes, and hologram films.
  • the size of these glitter materials is not particularly limited, but is preferably 1-30 ⁇ m in the longitudinal direction and 0.001-1 ⁇ m in thickness.
  • the curable polyurethane resin composition may contain other natural product-derived resins as necessary.
  • other natural product-derived resins may be contained in either polyester polyol or polyisocyanate, but are preferably contained in polyester polyol.
  • One type of other natural product-derived resins may be used, or two or more types may be used.
  • natural product-derived resins are not particularly limited, but include, for example, plant fibers, cellulose resins, polyhydroxycarboxylic acids typified by polylactic acid, polycaprolactam, modified polyvinyl alcohol, and the like, as well as typified by polycaprolactone. Examples include biodegradable aliphatic polyester. As other natural product-derived resins, those that are soluble in the above-mentioned solvents are particularly preferable, and cellulose-derived resins are particularly preferable. For example, physical properties such as surface hardness of the obtained cured coating film can be further improved by containing a small amount of one or more selected from cellulose, nitrocellulose, and cellulose acetate butyrate.
  • Examples of other commercially available products that can be used as other natural product-derived resins include nitrocellulose, industrial nitrified cotton “BNC-HIG-2” manufactured by Bergerac NC, France, and industrial nitrified cotton manufactured by Korea CNC.
  • RS1-4 “Swancell HM1-4” manufactured by Kyosei Yoko Co., Ltd., “Selnova BTH1-4” manufactured by Asahi Kasei Chemicals Co., Ltd.), etc.
  • a conventionally known surface conditioner wax, repellency inhibitor, antifoaming agent, etc.
  • plasticizer plasticizer
  • UV stabilizer antioxidant
  • fluidity modifier e.g., ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol, ethylene glycol dimethoxysulfate, etc.
  • additives such as an anti-sagging agent, a matting agent, a polishing agent, and an antiseptic can be appropriately contained.
  • additives may be contained in either polyester polyol or polyisocyanate, but are preferably contained in polyester polyol.
  • the polyurethane resin having a crosslinked structure is a cured product obtained by curing a curable polyurethane resin composition containing at least a polyester polyol and a polyisocyanate, and is a resin obtained by curing a polyester polyol with a polyisocyanate.
  • the polyurethane resin having a crosslinked structure can be obtained, for example, by mixing polyester polyol and polyisocyanate as described above.
  • the resin composition of 1st Embodiment which concerns on this technique can be obtained by adding the polyurethane resin which has the obtained crosslinked structure to polycarbonate resin (dry blending), and kneading
  • polyester polyol as a raw material for the polyurethane resin having a crosslinked structure will be described.
  • the hydroxyl value of the polyester polyol may have any value, but is preferably 30 to 300.
  • the resulting polyurethane resin may have a slightly lower crosslink density.
  • the chemical resistance and resistance of the resin composition added and kneaded to the aromatic polycarbonate resin may be reduced. Abrasion, weather resistance, water resistance, and solvent resistance may be slightly insufficient.
  • the hydroxyl value of the polyester polyol exceeds 300, on the contrary, since the crosslinking is slightly advanced, the compatibility with the aromatic polycarbonate resin is slightly deteriorated, and the mechanical properties and chemical resistance are slightly decreased. There is.
  • the hydroxyl value can be obtained by measurement by the method described in JIS K-1557-1.
  • the weight average molecular weight of the polyester polyol may have any value, but is preferably 10,000 to 500,000. If the weight average molecular weight of the polyester polyol is less than 10,000, a polyurethane structure having a crosslinked structure is formed, and the chemical resistance of the resin composition added to and kneaded with the polycarbonate resin may be slightly insufficient. . On the other hand, when the weight average molecular weight of the polyester polyol exceeds 500,000, the viscosity becomes high, and when added to the polycarbonate resin and kneaded, the dispersibility tends to be slightly deteriorated, leading to a decrease in physical properties.
  • Polyester polyol can be produced by, for example, a method of reacting a low molecular weight polyol and a polycarboxylic acid, a method of ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone, and the like.
  • low molecular weight polyol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo Pentyl glycol, 1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6000), dipropylene glycol, tripropylene glycol Bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts be able to.
  • polycarboxylic acid examples include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid.
  • Isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acids, and anhydrides or ester-forming derivatives thereof can be used.
  • the polyester polyol may be a polyester polyol obtained using a vegetable oil-derived raw material.
  • the vegetable oil-derived raw material is preferably at least one selected from the group consisting of vegetable oil or fatty acids thereof, carboxylic acids produced using vegetable oil as a raw material, and raw materials having a hydroxyl group derived from vegetable oil.
  • vegetable oil or vegetable oil fatty acid include Chinese tung oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil fatty acid, cottonseed oil (fatty acid), soybean oil (fatty acid), olive oil (fatty acid), safflower oil (Fatty acid), castor oil (fatty acid) rice bran oil (fatty acid), hydrogenated coconut oil (fatty acid), coconut oil (fatty acid), palm oil (fatty acid) and the like.
  • carboxylic acids produced from vegetable oils include, for example, 12-hydroxystearic acid, heptyl acid, undecylenic acid, sebacic acid produced from castor oil; rosin purified from pine ani, and hydrogenated rosin that is a hydride thereof.
  • dimer acid produced from a dry vegetable oil fatty acid such as polymerized rosin tall oil fatty acid which is a polymer thereof, and hydrogenated dimer acid which is a hydride thereof; isostearic acid produced as a by-product during dimer acid production, and the like.
  • Examples of the raw material having a hydroxyl group derived from vegetable oil include heptanal, octanol, 1,10-decanediol produced from castor oil; glycerin purified from each vegetable oil; and the like.
  • the polyester polyol may be obtained using the above-described vegetable oil-derived raw material, and its production method is not particularly limited. For example, it is generally used for the above-mentioned vegetable oil-derived raw material and, if necessary, the esterification reaction.
  • the acid component and / or alcohol component to be obtained can be obtained by an esterification reaction.
  • Examples of the acid component that can be used in obtaining the polyester polyol include benzoic acid, p-tert-butylbenzoic acid, isophthalic acid, phthalic anhydride, terephthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, and azelain.
  • Acid sebacic acid, isosebacic acid, oxalic acid, trimellitic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, dodecanoic acid, tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) Phthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tetrachloro (anhydride) phthalic acid, hexachloro (anhydride) phthalic acid, tetrabromo (anhydride) phthalic acid, glutaric acid, adipic acid, pimelic acid, uberic acid, hydrogenated phthalate Acid, 1,4-cyclohexanedicarboxylic acid, etc. And the like. In addition, only 1 type may be sufficient as an acid component, and 2 or more types may be sufficient as it.
  • Examples of the alcohol component that can be used for obtaining the polyester polyol include ethylene glycol, neopentyl glycol, diethylene glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and 2,3,4-trimethyl-1 , 3-pentanediol, 3-methylpentene-1,5-diol, 1,4-cyclohexanedimethanol, ethylene oxide or propylenoxide of bisphenol A or hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene Glycol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-ethyl-1,3-propanediol, trisic Divalent alcohol components such as decanedimethanol, cyclohexanedicarboxylic acid, cyclohexanedimethanol, cyclohexaned
  • the amount of the vegetable oil-derived raw material used is preferably set so as to be 30 to 100% by mass, although the content of the vegetable oil-derived raw material in the obtained polyester polyol may be optional.
  • the content ratio of the vegetable oil-derived raw material in the polyester polyol is less than 30% by mass, the effect of preventing global warming obtained by using a carbon neutral material tends to be slightly reduced.
  • what is necessary is just to employ
  • the polyisocyanate has at least one isocyanate group and preferably has two or more isocyanate groups.
  • polyisocyanate examples include aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, alicyclic polyisocyanates, or reaction products of these polyisocyanates and polyols.
  • tolylene diisocyanate TDI
  • diphenylmethane diisocyanate MDI
  • polyphenylmethane polyisocyanate CAde MDI
  • modified MDI modified diphenylmethane diisocyanate
  • XDI xylylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • Aromatic polyisocyanates or trimer compounds of these polyisocyanates, reaction products of these polyisocyanates and polyols, and the like are preferable.
  • the polyisocyanate only one type of polyisocyanate may be used, or two or more types of polyisocyanate may be used.
  • Organic sulfonic acid and organic sulfonic acid metal salt compound In the resin composition of the first embodiment according to the present technology, the organic sulfonic acid and / or the organic sulfonic acid metal salt compound is further added in an amount of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. May be included.
  • the organic sulfonic acid and the organic sulfonic acid metal salt compound will be described in detail.
  • the organic sulfonic acid is not particularly limited, but is preferably an aromatic organic sulfonic acid.
  • the organic sulfonic acid metal salt compound is not particularly limited, but is preferably an aromatic sulfonic acid metal salt compound.
  • the aromatic sulfonic acid metal salt compound contains a sulfonic acid metal base, and the content of the sulfonic acid metal base may be arbitrarily adjusted and may be any amount, but is preferably 0.1 to 10 mol%.
  • examples of the low molecular weight compound include perfluoroalkanesulfonic acid, alkylbenzene sulfonic acid, halogenated alkylbenzene sulfonic acid, alkyl sulfonic acid, naphthalene sulfonic acid and the like, or alkali metals thereof.
  • examples of the salt or the alkaline earth metal salt and the high molecular weight compound include, for example, a polymer having an aromatic ring and a predetermined amount of sulfonic acid and / or a metal salt thereof described in Patent 4196862 and Patent 4196661. Are listed.
  • polystyrene (PS) sulfonic acid or polystyrene (PS) sulfonic acid metal salt examples include polystyrene (PS) sulfonic acid or polystyrene (PS) sulfonic acid metal salt, high impact polystyrene (HIPS) sulfonic acid or high impact polystyrene (HIPS) sulfonic acid metal salt, or sulfonic acid.
  • HIPS high impact polystyrene
  • HIPS high impact polystyrene
  • AS Styrene / acrylonitrile copolymer resin
  • organic sulfonic acid or organic sulfonic acid metal salt compounds ranging from low molecular weight to high molecular weight, but in general, dispersion when high molecular weight is kneaded into aromatic polycarbonate resin It is preferable because of its good properties and excellent storage stability under high temperature and high humidity conditions.
  • an alkali metal salt or alkaline earth metal salt thereof specifically, for example, polystyrene sulfonic acid or potassium thereof.
  • salt One or more selected from these may be mixed and used at an appropriate ratio, but when using polystyrene sulfonic acid or its potassium salt, a high flame retardant effect can be obtained with a very small amount of addition, preferable.
  • those weight average molecular weights are 30000 or more, and when it is 40000 or more and 300000 or less, since the balance of solvent resistance and compatibility is further maintained, it is more preferable.
  • the content of the organic sulfonic acid or the organic sulfonic acid metal salt compound is 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin.
  • the flame retardant effect is further enhanced, and in the case of 0.05 to 1 mass part, a stronger flame retardant effect can be obtained. If it is less than 0.05 parts by mass, it may be difficult to obtain a flame retardant effect. If it exceeds 1.5 parts by mass, the compatibility with the aromatic polycarbonate resin may be reduced, and negative flame retardant.
  • the flame retardant level may be lower than the effect, that is, the case of not containing.
  • the resin composition of the first embodiment according to the present technology may further include an anti-drip agent.
  • the content of the anti-drip agent may be 0.8 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin.
  • an anti-drip agent is included. The drip phenomenon during combustion can be suppressed.
  • the anti-drip agent include a fluoroolefin resin.
  • fluoroolefin resin capable of suppressing the drip phenomenon
  • examples of the fluoroolefin resin capable of suppressing the drip phenomenon include a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a copolymer with a tetrafluoroethylene-ethylene monomer. Any one of them or a mixture of two or more of them can be used.
  • fluoroolefin resins it is particularly preferable to use a tetrafluoroethylene polymer or the like, and the average molecular weight is 50,000 or more, and preferably in the range of 100,000 to 20,000,000.
  • fluoroolefin resin what has fibril formation ability is more preferable.
  • the content of the anti-drip agent such as fluoroolefin resin may be 0.8 parts by mass or less, preferably in the range of 0.001 to 0.8 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin.
  • the range of 0.01 to 0.5 parts by mass is more preferable, and the range of 0.05 to 0.3 parts by mass is even more preferable.
  • the content of the anti-drip agent such as fluoroolefin resin is less than 0.001 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin, it may be difficult to suppress the drip phenomenon.
  • the content of the anti-drip agent such as fluoroolefin resin is more than 0.8 parts by mass, the molded product may be slightly whitened and transparency may be slightly impaired.
  • the resin composition of the first embodiment according to the present technology includes, as other components (other additives), for example, an antioxidant (hindered phenol-based, phosphorus-based, sulfur-based), antistatic Agent, UV absorber (benzophenone, benzotriazole, hydroxyphenyltriazine, cyclic imino ester, cyanoacrylate), light stabilizer, plasticizer, compatibilizer, colorant (pigment, dye), light stability Agents, crystal nucleating agents, antibacterial agents, flow modifiers, infrared absorbers, phosphors, hydrolysis inhibitors, mold release agents, silicone flame retardants or surface treatment agents may be contained.
  • an antioxidant hinderephthalate, hydroxyphenyltriazine, cyclic imino ester, cyanoacrylate
  • light stabilizer plasticizer
  • compatibilizer colorant (pigment, dye)
  • colorant pigment
  • light stability Agents crystal nucleating agents, antibacterial agents, flow modifiers, infrared absorbers, phosphors, hydrolysis inhibitors,
  • the silicone compound is used to impart flame retardancy to the resin composition of the first embodiment according to the present technology.
  • the addition amount of the silicone-based flame retardant in the resin composition is preferably 0.001 to 0.02 (0.1 to 2% by mass) as a mass ratio with respect to the resin composition.
  • the addition amount of the silicone-based flame retardant is less than 0.001 (0.1% by mass) in terms of mass ratio with respect to the resin composition, the effect of imparting flame retardancy to the resin composition may not be sufficient.
  • the addition amount is more than 0.02 (2% by mass)
  • the economy may be deteriorated due to the decrease in efficiency, and the effect of imparting flame retardancy may be saturated and the efficiency may be decreased.
  • Second Embodiment (Example of Manufacturing Method of Resin Composition)> [3-1. Method for producing resin composition]
  • the manufacturing method of the resin composition of 2nd Embodiment (example of a resin composition) which concerns on this technique is demonstrated in detail.
  • a polyurethane resin having a crosslinked structure is added to 100 parts by weight of an aromatic polycarbonate resin. It is a manufacturing method of the resin composition including adding and knead
  • the polyurethane resin having a crosslinked structure is preferably a curable resin, and may be a photocurable resin or a thermosetting resin.
  • the aromatic polycarbonate resin and the polyurethane resin having a cross-linked structure used in the method for producing the resin composition of the second embodiment according to the present technology are the first operations according to the present technology, except as described below.
  • the content of the aromatic polycarbonate resin and the polyurethane resin having a crosslinked structure contained in the resin composition in the form is the same as the aromatic polycarbonate resin and the crosslinked structure used in the method for producing the resin composition of the second embodiment according to the present technology. It can be applied as it is to the polyurethane resin it has.
  • the resin composition produced by the method for producing a resin composition of the second embodiment according to the present technology while maintaining the performance of mechanical properties such as impact resistance, fluidity, solvent resistance, Surface properties such as chemical resistance and scratch resistance can be improved.
  • the improvement in fluidity improves the processability of the resin composition.
  • the amount of the polyurethane resin having a crosslinked structure added to 100 parts by mass of the aromatic polycarbonate resin is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. From the viewpoint of improvement, the amount is preferably 0.05 to 3.0 parts by mass.
  • the manufacturing method of the resin composition of 2nd Embodiment which concerns on this technique is as follows, for example.
  • First embodiment (example of resin composition)>
  • the organic sulfonic acid and / or organic sulfonic acid metal salt compound, the anti-drip agent, other components and / or the silicone compound are added in predetermined amounts. And mix. After mixing, for example, it is dispersed substantially uniformly with a Henschel mixer or a tumbler.
  • the resin composition is obtained by melt-kneading with a single screw or twin screw extruder and cutting the resulting strand with a pelletizer to produce pellets.
  • the resin composition manufactured by the manufacturing method of the resin composition of 2nd Embodiment which concerns on this technique is not restricted to what was processed into the pellet form, The state (powder state or fluid state) which mixed each component And those processed into a form different from the pellet (such as a sheet).
  • a method of adding a component of a polyurethane resin having a cross-linked structure of 0.01 to 5.0 parts by mass to a component of 100 parts by mass of an aromatic polycarbonate resin includes, for example, pellets of 100 parts by mass of an aromatic polycarbonate resin
  • a method of adding 0.01 to 5.0 parts by mass of a polyurethane resin component or the like so that a coating film is formed on the surface, 0.01% on a color plate made of 100 parts by mass of an aromatic polycarbonate resin An example is a method of adding a component of polyurethane resin of up to 5.0 parts by mass so as to coat it.
  • the method for producing the resin composition of the second embodiment according to the present technology includes producing a polyurethane resin having a crosslinked structure by reacting a polyester polyol and a polyisocyanate.
  • a method for producing a polyurethane resin having a crosslinked structure by reacting a polyester polyol and a polyisocyanate is, for example, mixing two liquids of a polyester polyol and a polyisocyanate, and then performing a thermosetting reaction or photocuring. This is a manufacturing method.
  • the resin molded body of the third embodiment according to the present technology is a resin molded body obtained by molding the resin composition of the first embodiment according to the present technology.
  • the resin molded body of the third embodiment according to the present technology may be a resin molded body including the resin composition of the first embodiment according to the present technology.
  • the resin composition of the first embodiment according to the present technology improves processability by improving fluidity without lowering mechanical properties, and further improves surface properties such as chemical resistance. It is possible to obtain a resin molded article suitable for equipment / copiers, in-vehicle use, and medical use.
  • the resin molded body of the third embodiment according to the present technology can be manufactured as follows, for example. Injection molding of pellets made of the resin composition of the first embodiment according to the present technology, or pellets made of the resin composition manufactured from the method for producing the resin composition of the second embodiment according to the present technology , Injection compression molding, extrusion molding, blow molding, vacuum molding, press molding, foam molding, or supercritical molding, etc. to a predetermined shape (for example, home appliances, automobiles, information equipment, office equipment, telephones, stationery, furniture) Or molded into housings or parts of various products such as fibers) to obtain a resin molded body.
  • a predetermined shape for example, home appliances, automobiles, information equipment, office equipment, telephones, stationery, furniture
  • molded into housings or parts of various products such as fibers to obtain a resin molded body.
  • the present technology is not limited to the above embodiments, and can be changed without departing from the gist of the present technology.
  • the present technology may have the following configurations.
  • [1] Including 100 parts by weight of an aromatic polycarbonate resin and 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure, A resin composition, wherein the polyurethane resin is a cured resin.
  • the ratio of the particle size of the polyurethane resin powder having the crosslinked structure to 0.5 mm to 1.5 mm is 70% or more with respect to the total powder of the polyurethane resin having the crosslinked structure, [1] or The resin composition as described in [2].
  • Comparative Example 1-5 was a coated product, and was manufactured as follows. In Comparative Example 1-5 (coated product), the coating material was applied to the surface of the substrate by a roll coater method, a spray method, or a dipping method. After coating, a desired coating film was formed on the substrate surface by heating and drying at 60 to 120 ° C. for several seconds to 10 minutes as necessary.
  • the number of isocyanate equivalents of the polyester polyol (Placcel PCL305 (manufactured by Daicel Chemical Industries)) and the polyisocyanate curing agent (Duranate TPA-100 (manufactured by Asahi Kasei Kogyo)) is 100: 100.
  • a two-component curable coating composition was obtained.
  • compositions (parts by mass) of each component of the resin compositions of Examples 1-1 to 1-10 and the evaluation results of fluidity (g / 10 min), tensile strength (%), chemical resistance and bending strength are shown below. Table 1 shows. Further, the composition (parts by mass) of each component of the resin compositions of Comparative Examples 1-1 to 1-5, and evaluation results of fluidity (g / 10 min), tensile strength (%), chemical resistance, and bending strength Is shown in Table 2 below.
  • composition (parts by mass) of each component of the resin compositions of Examples 2-1 to 2-10, fluidity (g / 10 min), tensile strength (%), chemical resistance, flame resistance (UL94, 1. 6 mm) and the evaluation results of the bending strength are shown in Table 3 below. Further, the composition (parts by mass) of each component of the resin compositions of Comparative Examples 2-1 to 2-4, fluidity (g / 10 min), tensile strength (%), chemical resistance, flame resistance (UL94, 1.6 mm) and the evaluation results of the bending strength are shown in Table 4 below.
  • each component to be described is the aromatic polycarbonate resin described in the resin composition of 1st Embodiment which concerns on said this technique, bridge
  • Component A aromatic polycarbonate resin
  • the following components A-1 to A-4 were used as the aromatic polycarbonate resin as the component A.
  • A-1 Commercially available medium molecular weight PC resin (L-1225L: Teijin Chemicals, PS converted Mw 45000).
  • A-2 Commercially available low molecular weight PC resin (L-1225LLL: Teijin Chemicals, Mw 33000 in terms of PS).
  • A-3 PC resin (Mw in PS conversion: 46000) obtained by roughly pulverizing used building material sheets, melting and kneading with a twin screw extruder, and then pelletizing.
  • A-4 Used CD is pulverized (2 to 20 mm) and treated with an alkaline hot water solution to form a coating film (recording material layer, label, adhesive layer, cured layer, metal reflective layer, etc.) After removing, PC resin (Mw in PS conversion: 32000) pelletized after melting and kneading with a twin screw extruder.
  • B component polyurethane resin having a crosslinked structure
  • B-1 to B-3 which are thermosetting resins, were used as the polyurethane resin having a crosslinked structure as the B component.
  • the C-1 component and D-1 component used in the B-3 component are shown below.
  • B-1 Neolabasan N781 (Musashi Paint Co., Ltd.)
  • B-2 Neo Rabasan Soft NS781 (Musashi Paint Co., Ltd.)
  • B-3 having a cross-linked structure obtained by mixing C-1 and D-1 with 100 parts by mass: 100 parts by mass (C-1: D-1) and then reacting by heating at 80 ° C. for 10 minutes. Polyurethane resin.
  • component C polyester polyol
  • component C-1 was used as the polyester polyol as component C.
  • component D polyisocyanate
  • component D-1 The following component D-1 was used as the polyisocyanate as component D.
  • D-1 Duranate TPA-100 (manufactured by Asahi Kasei Corporation).
  • E component organic sulfonic acid and organic sulfonic acid metal salt compound
  • the following components E-1 to E-2 were used as the organic sulfonic acid and organic sulfonic acid metal salt compound as the E component.
  • E-1 organic sulfonic acid metal salt compound, in which potassium sulfonate is introduced into the surface layer of polystyrene (manufactured by Sony Corporation: PSS-K).
  • E-2 Organic sulfonic acid, one obtained by introducing sulfonic acid into the surface layer of polystyrene (manufactured by Sony Corporation: PSS-H).
  • F component anti-drip agent
  • F-1 PTFE commercially available as polytetrafluoroethylene having fibril-forming ability (manufactured by Daikin Industries, Ltd .: Polyflon FA500H).
  • Example 1-1 to Example 1-10 Table 2 (Comparative Example 1-1 to Comparative Example 1-5), Table 3 (Example 2-1 to Example 2-10) and Table 4 (Comparative Example 2) -1 to Comparative Example 2-4)
  • a twin-screw co-rotating extruder Toyo Seiki Seisakusho: Labo Plast Mill, twin-screw
  • Extrusion conditions were a discharge rate of 4 kg / h, a screw rotation speed of 48 rpm, and an extrusion temperature of 270 ° C. from the first supply port to the die part.
  • the obtained pellets were dried in a hot air circulating dryer at 120 ° C. for 8 hours, and then used in the test method shown below at a cylinder temperature of 290 ° C. and a mold temperature of 70 ° C. using an injection molding machine. A test piece was molded.
  • Test method for tensile strength (%)
  • the test piece was subjected to a tensile test according to JIS K7162 method, and the tensile strength was measured.
  • the evaluation results of tensile strength (%) are shown in Tables 1 to 4 below.
  • the bending test is a kind of test for qualitatively evaluating impact resistance by bending a prepared test piece (length: 110 mm, width: 13 mm, thickness: 1.0 mm) and measuring a broken angle. In this evaluation, when the destroyed angle was 90 ° C. or more, it was evaluated as “ ⁇ ”, and when it was within 90 ° C., it was evaluated as “X”.
  • Table 1 shows the results of Examples 1-1 to 1-10, and Table 2 shows the results of Comparative Examples 1-1 to 1-5.
  • the resin compositions according to Examples 1-1 to 1-10 were compatible with thin molded products.
  • the resin compositions according to Examples 1-1 to 1-10 have moldability (fluidity), mechanical properties (tensile strength and tensile strength) as compared with the resin compositions according to Comparative Examples 1-1 to 1-5.
  • the resin composition had excellent bending strength and surface properties (chemical resistance).
  • Examples and Comparative Examples are compared with the same molecular weight of the aromatic polycarbonate resin, that is, Examples 1-1 to 1-3, Examples 1-7 to 1-8, and Comparative Example 1-1 are compared.
  • Examples 1-1 and Comparative Example 1-2 When comparing 1-4 and comparative example 1-2, comparing example 1-5 and comparative example 1-3, and comparing example 1-6 and comparative example 1-4, the example was compared to the comparative example.
  • the mechanical properties tensile strength and bending strength
  • Examples 1-1 to 1-10 were compared with Comparative Example 1-5.
  • Comparative Example 1-5 is a coated product in which a carbonate resin is coated with a polyurethane resin for the purpose of improving chemical resistance.
  • the resin compositions according to Examples 1-1 to 1-10 compared with the resin composition according to Comparative Example 1-5, have a surface physical property (anti-resistance) without reducing mechanical properties (tensile strength and bending strength). Since chemical properties can be imparted, it was excellent.
  • the resin compositions according to Examples 1-1 to 1-10 were very excellent in that the degree of freedom of molding (fluidity) was improved as compared with the resin composition according to Comparative Example 1-5. .
  • Table 3 below shows the results of Examples 2-1 to 2-10, and Table 4 shows the results of Comparative Examples 2-1 to 2-4.
  • the resin compositions according to Examples 2-1 to 2-10 were compatible with thin molded products.
  • the resin compositions according to Examples 2-1 to 2-10 to which organic sulfonic acid or organic sulfonic acid metal salt compound (flame retardant) was added are the same as the resin compositions according to Comparative Examples 2-1 to 2-4.
  • the resin composition was excellent in moldability (fluidity), mechanical properties (tensile strength and bending strength), surface properties (chemical resistance) and flame retardancy.

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Abstract

Provided is a resin composition having excellent resin properties. The resin composition comprises 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, and the polyurethane resin is a cured resin.

Description

樹脂組成物、及び樹脂組成物の製造方法Resin composition and method for producing resin composition

 本技術は、樹脂組成物、及び樹脂組成物の製造方法に関する。 The present technology relates to a resin composition and a method for producing the resin composition.

 ポリカーボネート樹脂を含有する樹脂組成物は、エクステリア、電子電気用途、光ディスク基板等など様々な分野で使用されている。 Resin compositions containing polycarbonate resin are used in various fields such as exterior, electronic / electrical applications, optical disk substrates and the like.

 しかしながら、今後、OA・複写機分野、自動車分野、医療材料分野等に用途を広げるに伴って、ポリカーボネート樹脂を含有する樹脂組成物の更なる性能改良が望まれているのが現状である。 However, the present situation is that further improvement in the performance of the resin composition containing the polycarbonate resin is desired as the application is expanded in the OA / copier field, the automobile field, the medical material field, and the like.

 例えば、テレフタル酸およびテレフタル酸誘導体からなる群より選ばれる1種または2種以上のテレフタル酸系成分からなるジカルボン酸系重縮合成分と、1,4-シクロヘキサンジメタノールを40モル%以上含有するグリコール系重縮合成分とを重縮合させて得られるポリエステル樹脂60~80重量部と、ポリカーボネート樹脂40~20重量部とからなることを特徴とする屋外用途用透明面板が提案されている(特許文献1を参照)。 For example, a glycol containing a dicarboxylic acid polycondensation component composed of one or more terephthalic acid components selected from the group consisting of terephthalic acid and terephthalic acid derivatives, and 40 mol% or more of 1,4-cyclohexanedimethanol A transparent face plate for outdoor use characterized by comprising 60 to 80 parts by weight of a polyester resin obtained by polycondensation with a system polycondensation component and 40 to 20 parts by weight of a polycarbonate resin has been proposed (Patent Document 1). See).

 また、例えば、分子中に2個以上の(メタ)アクリロイル基を有する化合物(A)、導電性微粒子(B)及び有機溶媒(C)を含有するポリカーボネート樹脂用硬化性塗料であって、前記有機溶媒(C)として、少なくとも溶解度パラメーターが8.0~10.0(cal/cm1/2である化合物(C-1)を含有することを特徴とするポリカーボネート樹脂用硬化性塗料が提案されている(特許文献2を参照)。 Further, for example, a curable paint for polycarbonate resin containing a compound (A) having two or more (meth) acryloyl groups in the molecule, conductive fine particles (B) and an organic solvent (C), wherein the organic Proposed curable coating for polycarbonate resin, containing at least a compound (C-1) having a solubility parameter of 8.0 to 10.0 (cal / cm 3 ) 1/2 as solvent (C) (See Patent Document 2).

特開2000-63641号公報JP 2000-63641 A 特開2011-74228号公報JP 2011-74228 A

 しかしながら、特許文献1~2で提案された技術では、樹脂物性の更なる向上が図れないおそれがある。 However, the techniques proposed in Patent Documents 1 and 2 may not be able to further improve the resin physical properties.

 そこで、本技術では、優れた樹脂物性を有する樹脂組成物、及び優れた樹脂物性を有する樹脂組成物の製造方法を提供することを主目的とする。 Therefore, the main object of the present technology is to provide a resin composition having excellent resin properties and a method for producing a resin composition having excellent resin properties.

 本発明者らは、上述の目的を解決するために鋭意研究を重ねた結果、芳香族ポリカーボネート樹脂と、架橋構造を有するポリウレタン樹脂とを所定の組成比で用いることによって、驚くべきことに、樹脂物性を飛躍的に向上させることに成功し、本技術を完成するに至った。 As a result of intensive studies to solve the above-mentioned object, the present inventors have surprisingly found that resin is used by using an aromatic polycarbonate resin and a polyurethane resin having a crosslinked structure at a predetermined composition ratio. We succeeded in dramatically improving the physical properties and completed this technology.

 すなわち、本技術では、芳香族ポリカーボネート樹脂100質量部と、架橋構造を有するポリウレタン樹脂0.01~5.0質量部とを含み、該ポリウレタン樹脂が硬化樹脂である、樹脂組成物を提供する。 That is, the present technology provides a resin composition comprising 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, wherein the polyurethane resin is a cured resin.

 前記架橋構造を有するポリウレタン樹脂の粉体の平均粒径が0.5mm~1.5mmでよい。 The average particle size of the polyurethane resin powder having the crosslinked structure may be 0.5 mm to 1.5 mm.

 前記架橋構造を有するポリウレタン樹脂の全粉体に対して、前記架橋構造を有するポリウレタン樹脂の粉体の粒径が0.5mm~1.5mmである割合が70%以上でよい。 The ratio of the particle diameter of the polyurethane resin powder having the crosslinked structure to 0.5 mm to 1.5 mm may be 70% or more with respect to the total powder of the polyurethane resin having the crosslinked structure.

 前記架橋構造を有するポリウレタン樹脂が、ポリエステルポリオールとポリイソシアネートとの反応から得られてよい。
 前記ポリエステルポリオールと前記ポリイソシアネートとの質量比が、100:50~100:200でよい。
 前記ポリエステルポリオールの水酸基価が30~300でよい。
 前記ポリエステルポリオールのポリスチレン換算の重量平均分子量が、10,000以上500,000以下でよい。
 前記ポリイソシアネートが2つ以上のイソシアネート基を有してよい。
The polyurethane resin having the crosslinked structure may be obtained from a reaction between a polyester polyol and a polyisocyanate.
The mass ratio of the polyester polyol and the polyisocyanate may be 100: 50 to 100: 200.
The polyester polyol may have a hydroxyl value of 30 to 300.
The polyester polyol may have a polystyrene-equivalent weight average molecular weight of 10,000 or more and 500,000 or less.
The polyisocyanate may have two or more isocyanate groups.

 前記芳香族ポリカーボネート樹脂100質量部に対して、有機スルホン酸及び/又は有機スルホン酸金属塩化合物0.01~3.0質量部を更に含んでよい。
 前記有機スルホン酸金属塩化合物のポリスチレン換算の重量平均分子量が、30,000以上でよい。
 前記有機スルホン酸金属塩化合物がスルホン酸金属塩基を含有してよく、該スルホン酸金属塩基の含有量が0.1~10モル%でよい。
An organic sulfonic acid and / or an organic sulfonic acid metal salt compound may further be included in an amount of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin.
The organic sulfonic acid metal salt compound may have a polystyrene equivalent weight average molecular weight of 30,000 or more.
The organic sulfonic acid metal salt compound may contain a sulfonic acid metal base, and the content of the sulfonic acid metal base may be 0.1 to 10 mol%.

 前記芳香族ポリカーボネート樹脂が、再生ポリカーボネート樹脂を含んでよく、該再生ポリカーボネート樹脂の含有量が、前記芳香族ポリカーボネート樹脂の全質量に対して1~100質量%未満でよい。 The aromatic polycarbonate resin may contain a recycled polycarbonate resin, and the content of the recycled polycarbonate resin may be 1 to less than 100% by mass with respect to the total mass of the aromatic polycarbonate resin.

 本技術に係る樹脂組成物が、前記芳香族ポリカーボネート樹脂100質量部に、前記架橋構造を有するポリウレタン樹脂0.01~5.0重量部を添加して、前記芳香族ポリカーボネート樹脂と前記架橋構造を有するポリウレタン樹脂とを混錬して得られてよい。 In the resin composition according to the present technology, 0.01 to 5.0 parts by weight of the polyurethane resin having the crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the crosslinked structure are added. It may be obtained by kneading with a polyurethane resin.

 また、本技術では、芳香族ポリカーボネート樹脂100質量部に、架橋構造を有するポリウレタン樹脂0.01~5.0重量部を添加することと、該芳香族ポリカーボネート樹脂と該架橋構造を有するポリウレタン樹脂とを混錬することとを含む、樹脂組成物の製造方法を提供する。 In the present technology, 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the polyurethane resin having the crosslinked structure are added. And a method for producing a resin composition, comprising kneading.

 本技術に係る樹脂組成物の製造方法が、ポリエステルポリオールとポリイソシアネートとを反応させて前記架橋構造を有するポリウレタン樹脂を製造することを含んでよい。 The method for producing a resin composition according to the present technology may include producing a polyurethane resin having the crosslinked structure by reacting a polyester polyol and a polyisocyanate.

 本技術によれば、樹脂物性を向上させることができる。なお、ここに記載された効果は、必ずしも限定されるものではなく、本技術中に記載されたいずれかの効果であってもよい。 According to the present technology, the physical properties of the resin can be improved. In addition, the effect described here is not necessarily limited, and may be any effect described in the present technology.

 以下、本技術を実施するための好適な形態について説明する。以下に説明する実施形態は、本技術の代表的な実施形態の一例を示したものであり、これにより本技術の範囲が狭く解釈されることはない。 Hereinafter, preferred embodiments for implementing the present technology will be described. The embodiment described below shows an example of a typical embodiment of the present technology, and the scope of the present technology is not interpreted narrowly.

 なお、説明は以下の順序で行う。
 1.本技術の概要
 2.第1の実施形態(樹脂組成物の例)
  2-1.樹脂組成物
  2-2.芳香族ポリカーボネート樹脂
  2-3.ポリウレタン樹脂
  2-4.ポリエステルポリオール
  2-5.ポリイソシアネート
  2-6.有機スルホン酸及び有機スルホン酸金属塩化合物
  2-7.ドリップ防止剤
  2-8.その他成分
 3.第2の実施形態(樹脂組成物の製造方法の例)
  3-1.樹脂組成物の製造方法
 4.第3の実施形態(樹脂成形体の例)
  4-1.樹脂成形体
  4-2.樹脂成形体の製造方法
The description will be given in the following order.
1. Overview of this technology First embodiment (example of resin composition)
2-1. Resin composition 2-2. Aromatic polycarbonate resin 2-3. Polyurethane resin 2-4. Polyester polyol 2-5. Polyisocyanate 2-6. Organic sulfonic acid and organic sulfonic acid metal salt compound 2-7. Anti-drip agent 2-8. Other components Second Embodiment (Example of Manufacturing Method of Resin Composition)
3-1. 3. Production method of resin composition Third embodiment (example of resin molded body)
4-1. Resin molding 4-2. Manufacturing method of resin molding

 <1.本技術の概要>
 まず、本技術の概要について説明をする。
 本技術は、樹脂物性を向上させた、芳香族ポリカーボネート樹脂と架橋構造を有するポリウレタン樹脂とを含む樹脂組成物に関する。さらに、詳しくは、本技術は、表面にコーティング材をコートすることなく、耐溶剤性、耐薬品性、耐擦傷性等の表面物性を向上させ、かつ、芳香族ポリカーボネート樹脂が本来有する優れた耐衝撃性等の機械的物性などの性能を損なうことなく、流動性を向上させた樹脂組成物に関する。また、本技術は、その樹脂組成物の製造方法に関する。
<1. Overview of this technology>
First, an outline of the present technology will be described.
The present technology relates to a resin composition including an aromatic polycarbonate resin and a polyurethane resin having a crosslinked structure, which have improved resin physical properties. More specifically, the present technology improves surface physical properties such as solvent resistance, chemical resistance, and scratch resistance without coating the surface with a coating material, and is excellent in the inherent resistance of an aromatic polycarbonate resin. The present invention relates to a resin composition having improved fluidity without impairing mechanical properties such as impact properties. The present technology also relates to a method for producing the resin composition.

 ポリカーボネート樹脂(例えば、芳香族ポリカーボネート樹脂)を含有する樹脂組成物は、耐熱性、耐衝撃性、透明性等に優れる。しかしながら、ポリカーボネート樹脂(例えば、芳香族ポリカーボネート樹脂)を含有する樹脂組成物は、流動性が低く成形性が悪くなることがあり、また、耐溶剤性、耐薬品性等の表面物性が悪化することがある。ポリカーボネート樹脂(例えば、芳香族ポリカーボネート樹脂)を含有する樹脂組成物の流動性、耐溶剤性、耐薬品性等の表面物性の改良が望まれているのが現状である。 A resin composition containing a polycarbonate resin (for example, an aromatic polycarbonate resin) is excellent in heat resistance, impact resistance, transparency, and the like. However, a resin composition containing a polycarbonate resin (for example, an aromatic polycarbonate resin) has low fluidity and may deteriorate moldability, and surface properties such as solvent resistance and chemical resistance may deteriorate. There is. At present, improvement of surface properties such as fluidity, solvent resistance, and chemical resistance of a resin composition containing a polycarbonate resin (for example, an aromatic polycarbonate resin) is desired.

 ポリカーボネート樹脂の流動性、耐薬品性を向上させる方法としては、ポリカーボネート樹脂にポリエチレンテレフタレート樹脂(PET)やポリブチレンテレフタレート樹脂(PBT)といったポリエステル系樹脂を溶融混練するという技術がある。しかし、ポリエチレンテレフタレート樹脂(PET)やポリブチレンテレフタレート樹脂(PBT)はポリカーボネート樹脂との相溶性に劣るため、溶融混練するとポリカーボネート樹脂の特徴である機械的物性が著しく損なわれ、さらに、ポリエチレンテレフタレート樹脂(PET)やポリブチレンテレフタレート樹脂(PBT)はガラス転移温度が低いため耐熱性も大幅に低下するということがある。 As a method for improving the fluidity and chemical resistance of a polycarbonate resin, there is a technique in which a polyester resin such as polyethylene terephthalate resin (PET) or polybutylene terephthalate resin (PBT) is melt-kneaded with the polycarbonate resin. However, since polyethylene terephthalate resin (PET) and polybutylene terephthalate resin (PBT) have poor compatibility with polycarbonate resin, mechanical properties that are characteristic of polycarbonate resin are remarkably impaired when melt kneaded. PET) and polybutylene terephthalate resin (PBT) have a low glass transition temperature, so that the heat resistance may be greatly reduced.

 また、耐薬品性、耐擦傷性等を向上させる方法の技術として、成形後のポリカーボネート樹脂にコーティング材をコートして耐薬品性を向上させる方法がある。しかしながら、溶剤や材料の浸食によりポリカーボネート樹脂の機械的物性が著しく低下することがある。このため、コーティング方式においても、表面物性と機械的物性との両立は困難である。 Also, as a technique for improving chemical resistance, scratch resistance, etc., there is a method of improving chemical resistance by coating a polycarbonate resin after molding with a coating material. However, the mechanical properties of the polycarbonate resin may be significantly reduced by erosion of solvents and materials. For this reason, it is difficult to achieve both surface properties and mechanical properties even in the coating method.

 本技術は、以上のような状況下に鑑みて、本発明者らが鋭意研究を重ねた結果の末になされたものである。本技術では、芳香族ポリカーボネート樹脂100質量部と、架橋構造を有するポリウレタン樹脂0.01~5.0質量部とを含み、ポリウレタン樹脂が硬化樹脂である、樹脂組成物を提供する。また、本技術では、芳香族ポリカーボネート樹脂100質量部に、架橋構造を有するポリウレタン樹脂0.01~5.0重量部を添加することと、芳香族ポリカーボネート樹脂と架橋構造を有するポリウレタン樹脂とを混錬することとを含む、樹脂組成物の製造方法を提供する。さらに、本技術では、本技術に係る樹脂組成物を成形加工して得られる樹脂成形体を提供する。 This technology has been made as a result of repeated studies by the present inventors in view of the above situation. The present technology provides a resin composition comprising 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, wherein the polyurethane resin is a cured resin. In the present technology, 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the polyurethane resin having a crosslinked structure are mixed. A method for producing a resin composition is provided. Furthermore, the present technology provides a resin molded body obtained by molding the resin composition according to the present technology.

 本技術によれば、耐衝撃性等の機械的物性を低下させることなく、流動性や、耐溶剤性、耐薬品性、耐擦傷性等の表面物性を向上させた樹脂組成物が提供される。また、本技術によれば、難燃剤(例えば有機スルホン酸、有機スルホン酸金属塩化合物等)を更に含むときは、難燃性を更に付与した樹脂組成物が提供される。 According to the present technology, there is provided a resin composition in which surface properties such as fluidity, solvent resistance, chemical resistance, and scratch resistance are improved without reducing mechanical properties such as impact resistance. . Moreover, according to this technique, when a flame retardant (for example, organic sulfonic acid, an organic sulfonic acid metal salt compound, etc.) is further included, the resin composition which provided the flame retardance further is provided.

 さらに、本技術は、廃光学ディスク等の回収ポリカーボネート樹脂を含む芳香族ポリカーボネート樹脂を用いてもよいので、廃光学ディスク等の回収ポリカーボネート樹脂を原料として有効利用することができるため、芳香族ポリカーボネート樹脂の省資源化に貢献することができる。 Furthermore, since this technique may use an aromatic polycarbonate resin containing a recovered polycarbonate resin such as a waste optical disk, the recovered polycarbonate resin such as a waste optical disk can be effectively used as a raw material. Can contribute to resource saving.

 <2.第1の実施形態(樹脂組成物の例)>
 [2-1.樹脂組成物]
 以下、本技術に係る第1の実施形態(樹脂組成物の例)の樹脂組成物について詳細に説明をする。
<2. First Embodiment (Example of Resin Composition)>
[2-1. Resin composition]
Hereinafter, the resin composition of the first embodiment (example of resin composition) according to the present technology will be described in detail.

 本技術に係る第1の実施形態の樹脂組成物は、芳香族ポリカーボネート樹脂100質量部と、架橋構造を有するポリウレタン樹脂0.01~5.0質量部とを含み、ポリウレタン樹脂が硬化樹脂である、樹脂組成物である。架橋構造を有するポリウレタン樹脂は、硬化性ポリウレタン系樹脂組成物を、光(例えば紫外光)で硬化した光硬化樹脂でもよいし、熱で硬化した熱硬化樹脂でもよい。 The resin composition of the first embodiment according to the present technology includes 100 parts by mass of an aromatic polycarbonate resin and 0.01 to 5.0 parts by mass of a polyurethane resin having a crosslinked structure, and the polyurethane resin is a cured resin. The resin composition. The polyurethane resin having a crosslinked structure may be a photocurable resin obtained by curing a curable polyurethane resin composition with light (for example, ultraviolet light) or a thermosetting resin cured with heat.

 本技術に係る第1の実施形態の樹脂組成物によれば、耐衝撃性等の機械的物性の性能は維持されながら、流動性や、耐溶剤性、耐薬品性、耐擦傷性等の表面物性は向上する。なお、流動性の向上は、樹脂組成物の加工適性(成形性等)を良化させる。 According to the resin composition of the first embodiment of the present technology, the surface of fluidity, solvent resistance, chemical resistance, scratch resistance, etc., while maintaining the performance of mechanical properties such as impact resistance. Physical properties are improved. The improvement in fluidity improves the processability (moldability, etc.) of the resin composition.

 樹脂組成物中の、架橋構造を有するポリウレタン樹脂の含有量は、芳香族ポリカーボネート樹脂100質量部に対して0.01~5.0質量部であるが、機械的物性の更なる向上の観点から、0.05~3.0質量部であることが好ましい。 The content of the polyurethane resin having a crosslinked structure in the resin composition is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. From the viewpoint of further improving the mechanical properties. 0.05 to 3.0 parts by mass is preferable.

 [2-2.芳香族ポリカーボネート樹脂]
 本技術に係る第1の実施形態の樹脂組成物は芳香族ポリカーボネート樹脂を含む。芳香族ポリカーボネート樹脂の含有量は、任意の量でよいが、樹脂組成物の全質量に対して、94.5~99.5質量%であることが好ましく、96~98質量%であることがより好ましい。
[2-2. Aromatic polycarbonate resin]
The resin composition of the first embodiment according to the present technology includes an aromatic polycarbonate resin. The content of the aromatic polycarbonate resin may be any amount, but is preferably 94.5 to 99.5% by mass, and preferably 96 to 98% by mass with respect to the total mass of the resin composition. More preferred.

 芳香族ポリカーボネート樹脂は、本技術に係る第1の実施形態の樹脂組成物の成形加工部品を製造するための原料として使用され、光学ディスクや家電の筐体用材料などの用途に使用される。通常、二価フェノールとカーボネート前駆体との反応により製造される芳香族ポリカーボネート樹脂を用いることが出来る。反応方法の一例として界面重合法、溶融エステル交換法、カーボネートプレポリマーの固相エステル交換法、および環状カーボネート化合物の開環重合法などを挙げることができる。これら二価フェノールとカーボネート前駆体については、特に制限は無く種々のものを使用することが出来る。 The aromatic polycarbonate resin is used as a raw material for producing a molded part of the resin composition of the first embodiment according to the present technology, and is used for applications such as optical discs and housing materials for home appliances. Usually, an aromatic polycarbonate resin produced by a reaction between a dihydric phenol and a carbonate precursor can be used. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. About these dihydric phenol and carbonate precursor, there is no restriction | limiting in particular and various things can be used.

 芳香族ポリカーボネート樹脂は、本技術の趣旨を損なわない範囲で、芳香族ジカルボン酸、例えばテレフタル酸、イソフタル酸、ナフタレンジカルボン酸あるいはその誘導体を共重合したポリエステルカーボネートであってもよい。また、本技術に係る第1の実施形態の樹脂組成物の樹脂物性を損なうことがない限り、芳香族ポリカーボネート樹脂以外の他の熱可塑性樹脂を配合することができる。この他の熱可塑性樹脂の配合量は、その種類および目的によって変わるが、通常、芳香族ポリカーボネート樹脂100質量部当たり、1~30質量部が好ましく、2~20質量部がより好ましい。他の熱可塑性樹脂としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアルキルメタクリレート樹脂などに代表される汎用プラスチックス、ポリフェニレンエーテル樹脂、ポリアセタール樹脂、ポリアミド樹脂、環状ポリオレフィン樹脂、ポリアリレート樹脂(非晶性ポリアリレート、液晶性ポリアリレート)等に代表されるエンジニアリングプラスチックス、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリサルフォン、ポリエーテルサルフォン、ポリフェニレンサルファイドなどのいわゆるスーパーエンジニアリングプラスチックスと呼ばれるものを挙げることができる。さらにオレフィン系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマー、ポリウレタン系熱可塑性エラストマーなどの熱可塑性エラストマーも使用することができる。 The aromatic polycarbonate resin may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof within a range that does not impair the gist of the present technology. Moreover, unless the resin physical property of the resin composition of 1st Embodiment which concerns on this technique is impaired, other thermoplastic resins other than an aromatic polycarbonate resin can be mix | blended. The amount of other thermoplastic resin blended varies depending on the type and purpose, but is usually preferably 1 to 30 parts by weight and more preferably 2 to 20 parts by weight per 100 parts by weight of the aromatic polycarbonate resin. Other thermoplastic resins include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, polyamide resin, cyclic polyolefin resin, polyarylate resin (non-crystalline) And so-called super engineering plastics such as engineering plastics typified by polyarylate and liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylene sulfide. . Furthermore, thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.

 以下、芳香族ポリカーボネート樹脂について更に詳細に説明をする。 Hereinafter, the aromatic polycarbonate resin will be described in more detail.

 (分岐構造を有する芳香族ポリカーボネート樹脂)
 本技術に係る第1の実施形態の樹脂組成物に含まれる芳香族ポリカーボネート樹脂は、分岐構造を有する芳香族ポリカーボネート樹脂(分岐状の芳香族ポリカーボネート樹脂ということもある。)を含んでもよい。
(Aromatic polycarbonate resin having a branched structure)
The aromatic polycarbonate resin contained in the resin composition of the first embodiment according to the present technology may include an aromatic polycarbonate resin having a branched structure (sometimes referred to as a branched aromatic polycarbonate resin).

 分岐状の芳香族ポリカーボネート(PC)樹脂は、分岐状の芳香族ポリカーボネート樹脂であれば特に限定されないが、例えば、下記一般式(I)で表される分岐剤から誘導された分岐核構造を有し、かつ粘度平均分子量が15,000~40,000であって、好ましくは17,000~30,000であって、より好ましくは17,000~27,000であり、分岐剤の使用量は、二価フェノール化合物に対して、好ましくは0.01~3モル%、より好ましくは0.1~2.0モル%の範囲である分岐状の芳香族ポリカーボネート樹脂が挙げられる。 The branched aromatic polycarbonate (PC) resin is not particularly limited as long as it is a branched aromatic polycarbonate resin. For example, it has a branched nucleus structure derived from a branching agent represented by the following general formula (I). And the viscosity average molecular weight is 15,000 to 40,000, preferably 17,000 to 30,000, more preferably 17,000 to 27,000, and the amount of branching agent used is The branched aromatic polycarbonate resin is preferably in the range of 0.01 to 3 mol%, more preferably 0.1 to 2.0 mol% with respect to the dihydric phenol compound.

Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001

 Rは水素あるいは炭素数1~5のアルキル基、例えばメチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基などである。また、R1~R6はそれぞれ独立に、水素、炭素数1~5のアルキル基(例えばメチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基など)あるいはハロゲン原子(例えば塩素原子、臭素原子、フッ素原子など)である。 R is hydrogen or an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an n-pentyl group. R1 to R6 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc.) or a halogen atom (for example, chlorine Atoms, bromine atoms, fluorine atoms, etc.).

 一般式(I)で表される分岐剤は、さらに具体的には1,1,1-トリス(4-ヒドロキシフェニル)-メタン;1,1,1-トリス(4-ヒドロキシフェニル)-エタン;1,1,1-トリス(4-ヒドロキシフェニル)-プロパン;1,1,1-トリス(2-メチル-4-ヒドロキシフェニル)-メタン;1,1,1-トリス(2-メチル-4-ヒドロキシフェニル)-エタン;1,1,1-トリス(3-メチル-4-ヒドロキシフェニル)-メタン;1,1,1-トリス(3-メチル-4-ヒドロキシフェニル)-エタン;1,1,1-トリス(3,5-ジメチル-4-ヒドロキシフェニル)-メタン;1,1,1-トリス(3,5-ジメチル-4-ヒドロキシフェニル)-エタン;1,1,1-トリス(3-クロロ-4-ヒドロキシフェニル)-メタン;1,1,1-トリス(3-クロロ-4-ヒドロキシフェニル)エタン;1,1,1-トリス(3,5-ジクロロ-4-ヒドロキシフェニル)-メタン;1,1,1-トリス(3,5-ジクロロ-4-ヒドロキシフェニル)-エタン;1,1,1-トリス(3-ブロモ-4-ヒドロキシフェニル)-メタン;1,1,1-トリス(3-ブロモ-4-ヒドロキシフェニル)-エタン;1,1,1-トリス(3,5-ジブロモ-4-ヒドロキシフェニル)-メタン;1,1,1-トリス(3,5-ジブロモ-4-ヒドロキシフェニル)-エタン、4,4’-[1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エチリデン]ビスフェノール;α,α’,α”-トリス(4-ヒドロキシフェニル)-1,3,5-トリイソプロピルベンゼン;1-[α-メチル-α-(4’-ヒドロキシフェニル)エチル]-4-[α’,α’-ビス(4”-ヒドロキシフェニル)エチル]ベンゼン;フロログリシン、トリメリト酸、イサチンビス(o-クレゾール)等の官能基を3つ以上有する化合物などである。上記のうち、1,1,1-トリス(4-ヒドロキシフェニル)エタンを用いることが入手性、反応性及び経済性の観点から好ましい。 The branching agent represented by the general formula (I) is more specifically 1,1,1-tris (4-hydroxyphenyl) -methane; 1,1,1-tris (4-hydroxyphenyl) -ethane; 1,1,1-tris (4-hydroxyphenyl) -propane; 1,1,1-tris (2-methyl-4-hydroxyphenyl) -methane; 1,1,1-tris (2-methyl-4- 1,1,1-tris (3-methyl-4-hydroxyphenyl) -methane; 1,1,1-tris (3-methyl-4-hydroxyphenyl) -ethane; 1-tris (3,5-dimethyl-4-hydroxyphenyl) -methane; 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) -ethane; 1,1,1-tris (3- Chloro-4-hydroxy Phenyl) -methane; 1,1,1-tris (3-chloro-4-hydroxyphenyl) ethane; 1,1,1-tris (3,5-dichloro-4-hydroxyphenyl) -methane; 1-tris (3,5-dichloro-4-hydroxyphenyl) -ethane; 1,1,1-tris (3-bromo-4-hydroxyphenyl) -methane; 1,1,1-tris (3-bromo- 4-hydroxyphenyl) -ethane; 1,1,1-tris (3,5-dibromo-4-hydroxyphenyl) -methane; 1,1,1-tris (3,5-dibromo-4-hydroxyphenyl)- Ethane, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol; α, α ′, α ″ -tris (4-hydroxyphenyl)- , 3,5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; And compounds having three or more functional groups such as glycine, trimellitic acid, and isatin bis (o-cresol). Of the above, 1,1,1-tris (4-hydroxyphenyl) ethane is preferably used from the viewpoints of availability, reactivity and economy.

 これらの分岐剤はそれぞれ単独で用いてもよいし、2種以上を混合して用いてもよい。また、分岐剤として1,1,1-トリス(4-ヒドロキシフェニル)エタンを用いる場合には、その使用量は、二価フェノール化合物に対して0.2~2.0モル%であることが好ましく、0.3~2.0モル%であることがより好ましく、0.4~1.9モル%であることが更に好ましい。0.2モル%以上であれば、配合の自由度が広くなり、2.0モル%以下であれば、重合中にゲル化しにくく、芳香族ポリカーボネート樹脂の製造が容易である。 These branching agents may be used alone or in combination of two or more. When 1,1,1-tris (4-hydroxyphenyl) ethane is used as the branching agent, the amount used is 0.2 to 2.0 mol% with respect to the dihydric phenol compound. Preferably, it is 0.3 to 2.0 mol%, more preferably 0.4 to 1.9 mol%. When the amount is 0.2 mol% or more, the degree of freedom of blending is widened, and when the amount is 2.0 mol% or less, gelation is difficult during polymerization, and the production of an aromatic polycarbonate resin is easy.

 分岐状の芳香族ポリカーボネート樹脂は、上記一般式(I)で表される分岐剤から誘導された分岐核構造を有し、具体的には下記の式で表されるものである。 The branched aromatic polycarbonate resin has a branched nucleus structure derived from the branching agent represented by the general formula (I), and is specifically represented by the following formula.

Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002

 ここで、上記式中、a,b及びcは整数であり、PCはポリカーボネート部分を示す。 Here, in the above formula, a, b and c are integers, and PC represents a polycarbonate portion.

 PCは、例えば原料成分としてビスフェノールAを使用した場合には、下記の式で表される繰り返し単位を示す。 PC represents a repeating unit represented by the following formula, for example, when bisphenol A is used as a raw material component.

Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003

 芳香族ポリカーボネート樹脂100質量部における、分岐状の芳香族ポリカーボネート樹脂の量(割合)は、10~100質量部であることが好ましく、50~100質量部であることがより好ましい。分岐状の芳香族ポリカーボネート樹脂の量が10質量部以上でないと、例えば、薄肉難燃性の効果が得られない場合がある。 The amount (ratio) of the branched aromatic polycarbonate resin in 100 parts by mass of the aromatic polycarbonate resin is preferably 10 to 100 parts by mass, and more preferably 50 to 100 parts by mass. If the amount of the branched aromatic polycarbonate resin is not 10 parts by mass or more, for example, a thin flame retardant effect may not be obtained.

 (非分岐状ポリカーボネート樹脂)
 芳香族ポリカーボネート樹脂は、分子構造中にハロゲンを含有しない非分岐状ポリカーボネート樹脂を含んでもよい。非分岐状ポリカーボネート樹脂は、好ましくは、下記式(II)で表される構造単位を有する重合体である。
(Unbranched polycarbonate resin)
The aromatic polycarbonate resin may include an unbranched polycarbonate resin that does not contain halogen in the molecular structure. The unbranched polycarbonate resin is preferably a polymer having a structural unit represented by the following formula (II).

Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004

 式(II)中、Xは、それぞれ水素原子又は炭素数1~8のアルキル基(例えば、メチル基、エチル基、プロピル基、n-ブチル基、イソブチル基、アミル基、イソアミル基、ヘキシル基など)であり、このXが複数の場合、それらは同一であってもよいし、異なっていてもよく、a及びbは、それぞれ1~4の整数である。そして、Yは、単結合,炭素数1~8のアルキレン基又は炭素数2~8のアルキリデン基(例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンテリレン基、ヘキシレン基、エチリデン基、イソプロピリデン基など)、炭素数5~15のシクロアルキレン基又は炭素数5~15のシクロアルキリデン基(例えば、シクロペンチレン基、シクロヘキシレン基、シクロペンチリデン基、シクロヘキシリデン基など)、又は-S-、-SO-、-SO-、-O-、-CO-結合もしくは下記式(III)あるいは(III’)で表される結合を示す。このうち、Xは水素原子が好ましく、また、Yはエチレン基,プロピレン基が好ましい。 In the formula (II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, etc.) And when X is plural, they may be the same or different, and a and b are each an integer of 1 to 4. Y represents a single bond, an alkylene group having 1 to 8 carbon atoms or an alkylidene group having 2 to 8 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylene group). A cycloalkylene group having 5 to 15 carbon atoms or a cycloalkylidene group having 5 to 15 carbon atoms (for example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, etc.), or- S—, —SO—, —SO 2 —, —O—, —CO— or a bond represented by the following formula (III) or (III ′) is shown. Among these, X is preferably a hydrogen atom, and Y is preferably an ethylene group or a propylene group.

Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005

 この芳香族ポリカーボネート樹脂は、下記の式(IV)で表される二価フェノールとホスゲン又は炭酸ジエステル化合物とを反応させることによって容易に製造することができるものである。すなわち、例えば、塩化メチレンなどの溶媒中において、公知の酸受容体や粘度平均分子量調節剤の存在下、二価フェノールとホスゲンのようなカーボネート前駆体との反応により、あるいは二価フェノールとジフェニルカーボネートのようなカーボネート前駆体とのエステル交換反応などによって製造される。 This aromatic polycarbonate resin can be easily produced by reacting a dihydric phenol represented by the following formula (IV) with phosgene or a carbonic acid diester compound. That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or viscosity average molecular weight regulator, by reaction of a dihydric phenol with a carbonate precursor such as phosgene, or dihydric phenol and diphenyl carbonate. Is produced by a transesterification reaction with a carbonate precursor.

Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006

 式(IV)中、X、Y、a及びbは、前記と同じである。 In the formula (IV), X, Y, a and b are the same as described above.

 ここで、前記式(IV)で表される二価フェノールとしては、様々なものがある。例えば、ビス(4-ヒドロキシフェニル)メタン;ビス(4-ヒドロキシフェニル)フェニルメタン;ビス(4-ヒドロキシフェニル)ナフチルメタン;ビス(4-ヒドロキシフェニル)-(4-イソプロピルフェニル)メタン;ビス(3,5-ジクロロ-4-ヒドロキシフェニル)メタン;ビス(3,5-ジメチル-4-ヒドロキシフェニル)メタン;1,1-ビス(4-ヒドロキシフェニル)エタン;1-ナフチル-1,1-ビス(4-ヒドロキシフェニル)エタン;1-フェニル-1,1-ビス(4-ヒドロキシフェニル)エタン;1,2-ビス(4-ヒドロキシフェニル)エタン;2,2-ビス(4-ヒドロキシフェニル)プロパン〔通称:ビスフェノールA〕;2-メチル-1,1-ビス(4-ヒドロキシフェニル)プロパン;2,2-ビス(3,5-ジメチル-4-ヒドロキシフェニル)プロパン;1-エチル-1,1-ビス(4-ヒドロキシフェニル)プロパン;2,2-ビス(3-メチル-4-ヒドロキシフェニル)プロパン;1,1-ビス(4-ヒドロキシフェニル)ブタン;2,2-ビス(4-ヒドロキシフェニル)ブタン;1,4-ビス(4-ヒドロキシフェニル)ブタン;2,2-ビス(4-ヒドロキシフェニル)ペンタン;4-メチル-2,2-ビス(4-ヒドロキシフェニル)ペンタン;2,2-ビス(4-ヒドロキシフェニル)ヘキサン;4,4-ビス(4-ヒドロキシフェニル)ヘプタン;2,2-ビス(4-ヒドロキシフェニル)ノナン;1,10-ビス(4-ヒドロキシフェニル)デカン;1,1-ビス(4-ヒドロキシフェニル)-3,3,5-トリメチルシクロヘキサン;などのジヒドロキシジアリールアルカン類、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン;1,1-ビス(4-ヒドロキシフェニル)シクロデカンなどのジヒドロキシジアリールシクロアルカン類、ビス(4-ヒドロキシフェニル)スルホン;ビス(3,5-ジメチル-4-ヒドロキシフェニル)スルホンなどのジヒドロキシジアリールスルホン類、ビス(4-ヒドロキシフェニル)エーテル;ビス(3,5-ジメチル-4-ヒドロキシフェニル)エーテルなどのジヒドロキシジアリールエーテル類、4,4’-ジヒドロキシベンゾフェノン;3,3’,5,5’-テトラメチル-4,4’-ジヒドロキシベンゾフェノンなどのジヒドロキシジアリールケトン類、ビス(4-ヒドロキシフェニル)スルフィド;ビス(3-メチル-4-ヒドロキシフェニル)スルフィド;ビス(3,5-ジメチル-4-ヒドロキシフェニル)スルフィドなどのジヒドロキシジアリールスルフィド類、ビス(4-ヒドロキシフェニル)スルホキシドなどのジヒドロキシジアリールスルホキシド類、4,4’-ジヒロキシジフェニルなどのジヒドロキシジフェニル類、9,9-ビス(4-ヒドロキシフェニル)フルオレンなどのジヒドロキシアリールフルオレン類などが挙げられる。これらの中では、2,2-ビス(4-ヒドロキシフェニル)プロパン〔通称:ビスフェノールA〕が好適である。 Here, there are various types of dihydric phenols represented by the formula (IV). For example, bis (4-hydroxyphenyl) methane; bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3 , 5-dichloro-4-hydroxyphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1-naphthyl-1,1-bis ( 4-hydroxyphenyl) ethane; 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane [ Common name: bisphenol A]; 2-methyl-1,1-bis (4-hydroxyphenyl) propane; 2 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4-hydroxyphenyl) propane 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) butane; 1,4-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl); ) Pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; Bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane; 1,1-bis (4-hydroxyphenyl) -3,3 Dihydroxydiarylalkanes such as 5-trimethylcyclohexane; 1,1-bis (4-hydroxyphenyl) cyclohexane; dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclodecane, bis (4-hydroxy Phenyl) sulfone; dihydroxydiaryl sulfones such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-4-hydroxyphenyl) ether Dihydroxydiaryl ethers, 4,4′-dihydroxybenzophenone; dihydroxydiaryl ketones such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) ) Sulfide; bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxy diaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide; and dihydroxy diaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide , Dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl, and dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. Among these, 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is preferable.

 前記式(IV)で表される二価フェノール類以外の二価フェノールとしては、ヒドロキノン、レゾルシノール、メチルヒドロキノンなどのジヒドロキシベンゼン類、1,5-ジヒドロキシナフタレン;2,6-ジヒドロキシナフタレンなどのジヒドロキシナフタレン類等が挙げられる。これらの二価フェノールは、それぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。また、炭酸ジエステル化合物としては、ジフェニルカーボネート等のジアリールカーボネートやジメチルカーボネート、ジエチルカーボネート等のジアルキルカーボネートが挙げられる。 Examples of dihydric phenols other than the dihydric phenols represented by the formula (IV) include dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone, 1,5-dihydroxynaphthalene; and dihydroxynaphthalene such as 2,6-dihydroxynaphthalene. And the like. These dihydric phenols may be used alone or in combination of two or more. Examples of the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

 そして、分子量調節剤としては、通常、ポリカーボネートの重合に用いられるものでよく、各種のものを用いることができる。具体的には、一価フェノールとして、例えば、フェノール、p-クレゾール、p-tert-ブチルフェノール、p-tert-オクチルフェノール、p-クミルフェノール、ノニルフェノールなどが挙げられる。更に、本発明で用いる芳香族ポリカーボネートは、2種以上の芳香族ポリカーボネートの混合物であってもよい。そして、該芳香族ポリカーボネートは、機械的強度及び成形性の点から、その粘度平均分子量が10,000~100,000のものが好ましく、特に、20,000~40,000のものが好適である。 And as a molecular weight regulator, what is normally used for superposition | polymerization of a polycarbonate may be used, and various things can be used. Specific examples of the monohydric phenol include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, and nonylphenol. Furthermore, the aromatic polycarbonate used in the present invention may be a mixture of two or more aromatic polycarbonates. The aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 to 100,000, particularly preferably 20,000 to 40,000, from the viewpoint of mechanical strength and moldability. .

(芳香族ポリカーボネート-ポリオルガノシロキサン共重合体)
 本技術に係る第1の実施形態の透過型樹脂組成物に含まれる芳香族ポリカーボネート樹脂は、芳香族ポリカーボネート-ポリオルガノシロキサン共重合体を含んでもよい。
(Aromatic polycarbonate-polyorganosiloxane copolymer)
The aromatic polycarbonate resin contained in the transmissive resin composition of the first embodiment according to the present technology may include an aromatic polycarbonate-polyorganosiloxane copolymer.

 芳香族ポリカーボネート-ポリオルガノシロキサン共重合体は、芳香族ポリカーボネート部とポリオルガノシロキサン部とからなり、下記の一般式(V)で示される芳香族ポリカーボネート構造単位及び一般式(VI)で示されるポリオルガノシロキサン構造単位を含むものである。 The aromatic polycarbonate-polyorganosiloxane copolymer comprises an aromatic polycarbonate part and a polyorganosiloxane part, and includes an aromatic polycarbonate structural unit represented by the following general formula (V) and a polysiloxane represented by the general formula (VI). It contains an organosiloxane structural unit.

Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007

 上記式(V)において、R及びRは、それぞれハロゲン原子、炭素数1~6(好ましくは炭素数1~4)のアルキル基又は置換基を有してもよいフェニル基を示し、R及びRが複数個ある場合、それらはたがいに同一でも異なっていてもよい。Yは単結合、炭素数1~20(好ましくは炭素数2~10)のアルキレン基若しくはアルキリデン基、炭素数5~20(好ましくは炭素数5~12)のシクロアルキレン基もしくはシクロアルキリデン基、-O-、-S-、-SO-、-SO2-又は-CO-のいずれかを示し、好ましくはイソプロピリデン基である。p及びqは、それぞれ0~4の整数(好ましくは0)であり、p及びqが複数個ある場合、それらはたがいに同一でも異なっていてもよい。mは1~100の整数(好ましくは5~90の整数)を示す。mが1~100であることにより芳香族ポリカーボネートーポリオルガノシロキサン共重合体において適度な粘度平均分子量が得られる。 In the above formula (V), R 5 and R 6 each represent a halogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) or an optionally substituted phenyl group, and R When there are a plurality of 5 and R 6 , they may be the same or different. Y is a single bond, an alkylene group or alkylidene group having 1 to 20 carbon atoms (preferably 2 to 10 carbon atoms), a cycloalkylene group or cycloalkylidene group having 5 to 20 carbon atoms (preferably 5 to 12 carbon atoms),- O—, —S—, —SO—, —SO 2 — or —CO— is shown, and an isopropylidene group is preferred. p and q are each an integer of 0 to 4 (preferably 0), and when there are a plurality of p and q, they may be the same or different. m represents an integer of 1 to 100 (preferably an integer of 5 to 90). When m is from 1 to 100, an appropriate viscosity average molecular weight can be obtained in the aromatic polycarbonate-polyorganosiloxane copolymer.

Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008

 上記式(VI)において、R~R10はそれぞれ炭素数1~6のアルキル基又は置換基を有してもよいフェニル基を示し、それらはたがいに同一でも異なっていてもよい。R~R10の具体例としては、メチル基、エチル基、プロピル基、n-ブチル基、イソブチル基、アミル基、イソアミル基及びヘキシル基などのアルキル基、フェニル基、トリル基、キシリル基及びナフチル基などのフェニル系アリールを挙げることができる。R11は脂肪族もしくは芳香族を含む有機残基を示し、好ましくはo-アリルフェノール残基、p-ヒドロキシスチレン残基及びオイゲノール残基などの二価の有機化合物残基である。 In the above formula (VI), R 7 to R 10 each represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may have a substituent, and they may be the same or different. Specific examples of R 7 to R 10 include methyl groups, ethyl groups, propyl groups, n-butyl groups, isobutyl groups, amyl groups, isoamyl groups, hexyl groups and other alkyl groups, phenyl groups, tolyl groups, xylyl groups, and the like. Mention may be made of phenyl aryls such as naphthyl groups. R 11 represents an aliphatic or aromatic organic residue, and is preferably a divalent organic compound residue such as an o-allylphenol residue, a p-hydroxystyrene residue, and an eugenol residue.

 上記の芳香族ポリカーボネート-ポリオルガノシロキサン共重合体の製造方法は、例えば、芳香族ポリカーボネートオリゴマーとポリオルガノシロキサン部を構成する末端に反応性基を有するポリオルガノシロキサンとを、塩化メチレン等の溶媒に溶解させ、トリエチルアミン等の触媒を用い、ビスフェノールAなどの二価フェノールを加え、界面重縮合反応することにより製造することができる。この芳香族ポリカーボネート-ポリオルガノシロキサン共重合体は、例えば、特開平3-292359号公報、特開平4-202465号公報、特開平8-81620号公報、特開平8-302178号公報及び特開平10-7897号公報等に開示されている。 The method for producing the aromatic polycarbonate-polyorganosiloxane copolymer includes, for example, using an aromatic polycarbonate oligomer and a polyorganosiloxane having a reactive group at the end constituting the polyorganosiloxane part in a solvent such as methylene chloride. It can be produced by dissolving and adding a dihydric phenol such as bisphenol A using a catalyst such as triethylamine and interfacial polycondensation reaction. This aromatic polycarbonate-polyorganosiloxane copolymer is, for example, disclosed in JP-A-3-292359, JP-A-4-202465, JP-A-8-81620, JP-A-8-302178, and JP-A-10-302. -7897 and the like.

 芳香族ポリカーボネート-ポリオルガノシロキサン共重合体の芳香族ポリカーボネート構造単位の重合度は、3~100、ポリオルガノシロキサン構造単位の重合度は2~500程度のものが好ましく、より好ましくは2~300程度のものであり、さらに好ましくは2~140程度のものが用いられる。また、芳香族ポリカーボネート-ポリオルガノシロキサン共重合体のポリオルガノシロキサンの含有量としては、通常0.1~10質量%程度、好ましくは0.3~6質量%の範囲である。本技術に係る第1の実施形態の透過型樹脂組成物に用いられる芳香族ポリカーボネート-ポリオルガノシロキサン共重合体の粘度平均分子量は、通常5,000~100,000程度、好ましくは10,000~30,000、特に好ましくは12,000~30,000である。ここで、これらの粘度平均分子量(Mv)は、上記のポリカーボネート樹脂と同様に求めることができる。 The degree of polymerization of the aromatic polycarbonate structural unit of the aromatic polycarbonate-polyorganosiloxane copolymer is preferably 3 to 100, and the degree of polymerization of the polyorganosiloxane structural unit is preferably about 2 to 500, more preferably about 2 to 300. More preferably, about 2 to 140 is used. The polyorganosiloxane content of the aromatic polycarbonate-polyorganosiloxane copolymer is usually about 0.1 to 10% by mass, preferably 0.3 to 6% by mass. The viscosity-average molecular weight of the aromatic polycarbonate-polyorganosiloxane copolymer used in the transmission resin composition of the first embodiment according to the present technology is usually about 5,000 to 100,000, preferably 10,000 to 30,000, particularly preferably 12,000 to 30,000. Here, these viscosity average molecular weights (Mv) can be obtained in the same manner as the above polycarbonate resin.

 (再生ポリカーボネート樹脂)
 以上に示した芳香族ポリカーボネート樹脂は、新たに製造されたバージン材でもよいし、製造工程において生じた廃材、端材、スプルー材、屑等、あるいは製品(例えば、デジタル多用途ディスク(DVD)、コンパクトディスク(CD)、MO、MD、ブルーレイディスク(BD)等の光学ディスク(基板))の回収物、廃材であってもよい(再生ポリカーボネート樹脂)。再生ポリカーボネート樹脂は、市場から回収した再生ポリカーボネート樹脂であることが好ましい。
(Recycled polycarbonate resin)
The aromatic polycarbonate resin shown above may be a newly manufactured virgin material, waste material, end material, sprue material, waste, etc. generated in the manufacturing process, or a product (for example, a digital versatile disc (DVD), It may be a recovered material or a waste material of an optical disc (substrate) such as a compact disc (CD), MO, MD, or Blu-ray disc (BD) (recycled polycarbonate resin). The recycled polycarbonate resin is preferably a recycled polycarbonate resin recovered from the market.

 すなわち、芳香族ポリカーボネート樹脂は、再生ポリカーボネート樹脂を含んでもよいし、再生ポリカーボネート樹脂から構成されてもよい。そして、再生ポリカーボネート樹脂の含有量が、芳香族ポリカーボネート樹脂の全質量に対して1~100質量%未満であることが好ましい。 That is, the aromatic polycarbonate resin may contain a recycled polycarbonate resin or may be composed of a recycled polycarbonate resin. The content of the recycled polycarbonate resin is preferably 1 to less than 100% by mass with respect to the total mass of the aromatic polycarbonate resin.

 回収された光学ディスクを使用する場合、金属反射層、メッキ層、記録材料層、接着剤層、レーベル等の各種付着物があるが、本発明においては、これらを具備したまま使用してもよく、このような不純物や副材料を従来公知の方法により分離・除去した後のものを用いてもよい。 When using the recovered optical disc, there are various deposits such as a metal reflection layer, a plating layer, a recording material layer, an adhesive layer, a label, etc., but in the present invention, these may be used as provided. Such impurities and sub-materials may be used after being separated and removed by a conventionally known method.

 具体的には、Al、Au、Ag、Si等の金属反射層、シアニン系色素を含む有機色素、Te、Se、S、Ge、In、Sb、Fe、Tb、Co、Ag、Ce、Bi等の記録材料層、アクリル系アクリレート、エーテル系アクリレート、ビニル系のモノマーやオリゴマー、ポリマーの少なくとも一種以上からなる接着剤層、紫外線硬化型のモノマー、オリゴマー、ポリマーの少なくとも一種及び重合開始剤や顔料、補助剤が混入されているレーベルインキ層等が挙げられるが、これらに限定されるものではなく、光学ディスクにおいて通常使用される膜形成材料、塗装材料を含んでいてもよい。なお、リサイクルという観点においては、原料が低コストであることが望ましいため、樹脂に各種材料による不純物が含まれたまま再利用することが好適である。例えば光学ディスクを細かく破砕し、そのまま、あるいは所定の添加物と混練・溶融し、ペレット化してPC樹脂原料として用いることができる。あるいは、射出成型機の構造によっては、回収ディスクを、後述する各種添加剤と共に射出成型機のホッパー等に直接投入し、樹脂組成物よりなる成形体を得てもよい。なお、ポリカーボネート(PC)樹脂として、上記各種不純物を含まない状態のものを使用する場合には、金属反射層、記録材料層、接着剤層、表面硬化層、レーベル等の付着物は、例えば、特開平6-223416号公報、特開平10-269634公報、特開平10-249315号公報等において提案されている機械的あるいは化学的な方法で除去することができる。 Specifically, a metal reflection layer such as Al, Au, Ag, Si, an organic dye containing a cyanine dye, Te, Se, S, Ge, In, Sb, Fe, Tb, Co, Ag, Ce, Bi, etc. Recording material layers, acrylic acrylates, ether acrylates, vinyl monomers and oligomers, adhesive layers comprising at least one polymer, UV curable monomers, oligomers, at least one polymer and polymerization initiators and pigments, Examples include label ink layers in which an auxiliary agent is mixed, but are not limited thereto, and may include a film forming material and a coating material that are usually used in an optical disk. From the viewpoint of recycling, since it is desirable that the raw material is low-cost, it is preferable to reuse the resin while impurities from various materials are included. For example, an optical disk can be finely crushed and used as a PC resin raw material as it is, or kneaded and melted with a predetermined additive and pelletized. Alternatively, depending on the structure of the injection molding machine, the recovery disk may be directly put into a hopper or the like of the injection molding machine together with various additives described later to obtain a molded body made of the resin composition. In addition, when using a polycarbonate (PC) resin that does not contain the above various impurities, deposits such as a metal reflection layer, a recording material layer, an adhesive layer, a surface hardened layer, and a label are, for example, It can be removed by a mechanical or chemical method proposed in JP-A-6-223416, JP-A-10-269634, JP-A-10-249315, or the like.

 なお、芳香族ポリカーボネート樹脂の重量平均分子量は、クロロホルム溶媒を用いたGPC(Gel Permeation Chromatography)測定にて、ポリスチレン分子量標準物質(サンプル)を基準とした、ポリスチレン換算として測定することができる。 The weight average molecular weight of the aromatic polycarbonate resin can be measured in terms of polystyrene based on a polystyrene molecular weight standard substance (sample) by GPC (Gel Permeation Chromatography) measurement using a chloroform solvent.

 芳香族ポリカーボネート樹脂の分子量は任意の値でよいが、分子量が重量平均分子量(ポリスチレン換算)で36000~63000であることが好ましい。その理由は、芳香族ポリカーボネート樹脂の重量平均分子量が63000より大きい場合は、最終目的物の樹脂組成物の溶融時の流れ性(加工性)が悪くなる傾向になる場合がある。一方、36000よりも小さい場合は、耐溶剤性が低下しソルベントクラック(薬品によるクラック)が発生しやすくなる傾向になる場合があり、耐衝撃性が低下する傾向になる場合がある。 The molecular weight of the aromatic polycarbonate resin may be any value, but the molecular weight is preferably 36000 to 63,000 in terms of weight average molecular weight (polystyrene conversion). The reason is that if the weight average molecular weight of the aromatic polycarbonate resin is larger than 63,000, the flowability (workability) at the time of melting of the resin composition as the final target product tends to be deteriorated. On the other hand, when it is smaller than 36000, the solvent resistance tends to decrease and solvent cracks (cracks due to chemicals) tend to occur, and the impact resistance tends to decrease.

 樹脂組成物中に含有される芳香族ポリカーボネート樹脂は、機械的強度及び成形性の点から、その重量平均分子量が40000~59000であることがより好ましく、44000~54000であることが更に好ましい。 The aromatic polycarbonate resin contained in the resin composition preferably has a weight average molecular weight of 40,000 to 59,000, and more preferably 44,000 to 54,000, from the viewpoint of mechanical strength and moldability.

 [2-3.ポリウレタン樹脂]
 本技術に係る第1の実施形態の樹脂組成物は、架橋構造を有する硬化樹脂のポリウレタン樹脂を、芳香族ポリカーボネート樹脂100質量部に対して0.01~5.0質量部で含む。以下に、架橋構造を有するポリウレタン樹脂について、詳細に説明する。
[2-3. Polyurethane resin]
The resin composition according to the first embodiment of the present technology includes 0.01 to 5.0 parts by mass of a cured polyurethane resin having a crosslinked structure with respect to 100 parts by mass of the aromatic polycarbonate resin. Below, the polyurethane resin which has a crosslinked structure is demonstrated in detail.

 本技術に係る第1の実施形態の樹脂組成物において、ポリウレタン樹脂は、架橋構造を有する硬化樹脂のポリウレタン樹脂であれば、特に限定されることはないが、耐薬品性等の表面物性に優れた塗膜を形成する観点から、ポリエステルポリオールと、ポリイソシアネートとを反応させて3次元的に架橋した架橋構造を有するポリウレタン樹脂であることが好ましい。反応させるポリエステルポリオールとポリイソシアネートとの質量比は任意の比でよいが、100:50~100:200であることが好ましい。また、ポリウレタン樹脂は、ポリエステルポリオール由来の構成単位とポリイソシアネート由来の構成単位とを含むことが好ましい。 In the resin composition of the first embodiment according to the present technology, the polyurethane resin is not particularly limited as long as the polyurethane resin is a cured resin polyurethane resin having a crosslinked structure, but it has excellent surface physical properties such as chemical resistance. From the viewpoint of forming a coated film, a polyurethane resin having a cross-linked structure in which a polyester polyol and polyisocyanate are reacted to cross-link three-dimensionally is preferable. The mass ratio of the polyester polyol to be reacted and the polyisocyanate may be any ratio, but is preferably 100: 50 to 100: 200. Moreover, it is preferable that a polyurethane resin contains the structural unit derived from a polyester polyol and the structural unit derived from polyisocyanate.

 架橋構造を有するポリウレタン樹脂は、例えば、ポリエステルポリオールとポリイソシアネートとの2液を混合し、その後、熱硬化反応によって製造して得ることができる。ペレット状の芳香族ポリカーボネート樹脂を用いて、ポリエステルポリオールとポリイソシアネートとの2液を混合して、60~200℃の範囲で数秒~10分程度加熱することによって、芳香族ポリカーボネートの樹脂のペレット表面にポリウレタン樹脂の塗膜を形成させることができる。その後、例えば、2軸押し出し機によって混錬することにより、芳香族ポリカーボネート樹脂と、架橋構造を有するポリウレタンとを含む、本技術に係る第1の実施形態の樹脂組成物を製造することができる。 The polyurethane resin having a crosslinked structure can be obtained, for example, by mixing two liquids of a polyester polyol and a polyisocyanate, and then producing by a thermosetting reaction. Using a pellet-like aromatic polycarbonate resin, two liquids of polyester polyol and polyisocyanate are mixed and heated in the range of 60 to 200 ° C. for several seconds to 10 minutes. To form a polyurethane resin coating. Thereafter, for example, by kneading with a twin-screw extruder, the resin composition of the first embodiment according to the present technology including an aromatic polycarbonate resin and a polyurethane having a crosslinked structure can be produced.

 また、芳香族ポリカーボネート樹脂からなるカラープレート上に、ポリエステルポリオールとポリイソシアネートとの2液を塗布後、加熱によって作成したポリウレタン樹脂コートをした樹脂組成物を粉砕し、リペレットすることによっても、本技術に係る第1の実施形態の樹脂組成物を製造することができる。 In addition, the present technology can also be obtained by applying a polyurethane resin-coated resin composition by heating after applying two liquids of polyester polyol and polyisocyanate on a color plate made of an aromatic polycarbonate resin and re-pelletizing. The resin composition of 1st Embodiment which concerns on can be manufactured.

 なお、本技術に係る第1の実施形態の樹脂組成物の製造方法の詳細については後述する。 In addition, the detail of the manufacturing method of the resin composition of 1st Embodiment which concerns on this technique is mentioned later.

 一方、ポリウレタン樹脂をカーボネート樹脂(例えば、芳香族カーボネート樹脂)にコートしたコート品は、特に制限はなく、従来公知の方法によればよい。例えば、カーボネート樹脂(例えば、芳香族カーボネート樹脂)の基材にポリウレタン樹脂を塗布した後、得られた2層の膜を同時に焼き付ける方法でよい。塗布するに際の方法は、使用するポリウレタン樹脂の形態やカーボネート樹脂(例えば、芳香族カーボネート樹脂)の基材の表面形状等を考慮して、従来公知の方法から適宜選択すればよく、特に制限はなく、例えば、エアースプレーやエアレススプレー、シャワー、カーテコーター、ベル、そのほか、通常の静電塗装などで塗布することができる。塗布したのち、得られたコート品に自然乾燥もしくは強制乾燥(例えば、温風乾燥、近赤外線乾燥、電磁波乾燥等)を施しておいてもよい。焼き付けを行う際の方法としては、特に制限はないが、焼き付けによりカーボネート樹脂(例えば、芳香族カーボネート樹脂)の基材の劣化が生じる恐れがある場合を考慮すると、焼付温度は、70~110℃とすることが好ましく、80~100℃とすることがより好ましく、そのときの焼付時間は、通常、焼付温度に依存し、エネルギー効率を考慮して適宜設定すればよいが、10~60分間とすることが好ましく、15~40分間とすることがより好ましい。 On the other hand, a coated product obtained by coating a polyurethane resin on a carbonate resin (for example, an aromatic carbonate resin) is not particularly limited, and may be a conventionally known method. For example, a method may be used in which a polyurethane resin is applied to a carbonate resin (for example, aromatic carbonate resin) substrate, and then the obtained two-layer film is baked at the same time. The method for coating may be appropriately selected from conventionally known methods in consideration of the form of the polyurethane resin to be used and the surface shape of the base material of the carbonate resin (for example, aromatic carbonate resin), and is particularly limited. For example, it can be applied by air spray, airless spray, shower, carte coater, bell, or other ordinary electrostatic coating. After coating, the obtained coated product may be subjected to natural drying or forced drying (for example, hot air drying, near infrared drying, electromagnetic wave drying, etc.). The method for baking is not particularly limited, but the baking temperature is 70 to 110 ° C. in consideration of the possibility that the baking may cause deterioration of the base material of the carbonate resin (for example, aromatic carbonate resin). Preferably, the baking time at that time depends on the baking temperature and may be appropriately set in consideration of energy efficiency, but it is 10 to 60 minutes. It is preferable to set it for 15 to 40 minutes.

 架橋構造を有するポリウレタン樹脂の粉体の平均粒径は任意の平均粒径でよいが、0.5mm~1.5mmであることが好ましい。架橋構造を有するポリウレタン樹脂の平均粒径が0.5mm~1.5mmであると、芳香族ポリカーボネート樹脂中で、ポリウレタン樹脂の分散性及び混合性がより良好となる。ポリウレタン樹脂の分散性及び混合性がより良好になると、樹脂組成物の機械的物性はより良好に維持されながら、表面物性(耐薬品性等)及び流動性は更に向上することとなる。 The average particle diameter of the polyurethane resin powder having a crosslinked structure may be any average particle diameter, but is preferably 0.5 mm to 1.5 mm. When the average particle size of the polyurethane resin having a crosslinked structure is 0.5 mm to 1.5 mm, the dispersibility and mixing properties of the polyurethane resin are improved in the aromatic polycarbonate resin. When the dispersibility and mixing properties of the polyurethane resin become better, the surface properties (chemical resistance, etc.) and fluidity will be further improved while the mechanical properties of the resin composition are better maintained.

 架橋構造を有するポリウレタン樹脂は、ポリウレタン樹脂の全粉体に対して、ポリウレタン樹脂の粉体の粒径が0.5mm~1.5mmである割合は任意の割合でよいが、70%以上であることが好ましい。70%以上であると、芳香族ポリカーボネート樹脂中で、ポリウレタン樹脂の分散性及び混合性がより良好となる。ポリウレタン樹脂の分散性及び混合性がより良好になると、樹脂組成物の機械的物性はより良好に維持されながら、表面物性(耐薬品性等)及び流動性は更に向上することとなる。 In the polyurethane resin having a crosslinked structure, the ratio of the particle size of the polyurethane resin powder to 0.5 mm to 1.5 mm may be any ratio to the total polyurethane resin powder, but is 70% or more. It is preferable. When the content is 70% or more, the dispersibility and mixing properties of the polyurethane resin become better in the aromatic polycarbonate resin. When the dispersibility and mixing properties of the polyurethane resin become better, the surface properties (chemical resistance, etc.) and fluidity will be further improved while the mechanical properties of the resin composition are better maintained.

 ポリウレタン樹脂の粉体の粒度分布は以下のように測定することができる。粒度分布の測定は、ロータップ測定を用いた。ロータップ式とは、ふるいの目によって選別する方法であり、それぞれのふるい上に残った試料の質量を計測し、グラフに累積分布を記載して平均粒度分布を求める測定方法である。 The particle size distribution of the polyurethane resin powder can be measured as follows. For the measurement of the particle size distribution, low tap measurement was used. The low-tap method is a method for sorting by sieve eyes, and is a measurement method for measuring the mass of a sample remaining on each sieve and describing the cumulative distribution on a graph to obtain an average particle size distribution.

 架橋構造を有するポリウレタン樹脂の粉体の粒径は、粉砕条件を調節することによって粉体の粒径を変更することができる。ポリウレタン樹脂の全粉体に対して、粒径が0.5mm~1.5mmである割合が70%以上であるポリウレタン樹脂は、凍結粉砕方法によってポリウレタン樹脂を粉砕して製造することができる。 The particle size of the polyurethane resin powder having a crosslinked structure can be changed by adjusting the pulverization conditions. A polyurethane resin having a particle size of 0.5 mm to 1.5 mm and a ratio of 70% or more with respect to the total powder of the polyurethane resin can be produced by pulverizing the polyurethane resin by a freeze pulverization method.

 ポリエステルポリオールとポリイソシアネートとの配合割合は、ポリエステルポリオール中の水酸基当量数とポリイソシアネート中のイソシアネート当量数の比(ポリエステルポリオール成分の水酸基当量数:ポリイソシアネートのイソシアネート当量数)が100:50~100:200の範囲になるように設定するのが好ましく、100:80~100:180の範囲になるように設定するのがより好ましい。ポリエステルポリオール中の水酸基当量数を100としたときに、ポリイソシアネート中のイソシアネートの当量数が50未満であると、ポリエステルポリオールとポリイソシアネートとの架橋反応がやや不充分となって、塗膜の速硬化性がやや低下したり、耐摩耗性、硬度、耐候性、耐水性、耐溶剤性、耐薬品性等の塗膜物性がやや低下したりするおそれがある。一方、ポリエステルポリオール中の水酸基当量数を100としたときに、ポリイソシアネート中のイソシアネートの当量数が200を超えると、余剰のポリイソシアネートが存在することにより物性がやや低下するおそれがある。 The ratio of the polyester polyol and the polyisocyanate is such that the ratio of the number of hydroxyl equivalents in the polyester polyol to the number of isocyanate equivalents in the polyisocyanate (number of hydroxyl equivalents in the polyester polyol component: number of isocyanate equivalents in the polyisocyanate) is 100: 50 to 100. Is preferably set to be in the range of 200, more preferably in the range of 100: 80 to 100: 180. When the number of hydroxyl group equivalents in the polyester polyol is 100 and the number of equivalents of isocyanate in the polyisocyanate is less than 50, the crosslinking reaction between the polyester polyol and the polyisocyanate becomes slightly insufficient, and the coating speed is reduced. There is a possibility that the curability is slightly lowered and the physical properties of the coating film such as abrasion resistance, hardness, weather resistance, water resistance, solvent resistance, chemical resistance and the like are slightly lowered. On the other hand, when the number of equivalents of hydroxyl group in the polyester polyol is set to 100 and the number of equivalents of isocyanate in the polyisocyanate exceeds 200, the physical properties may be slightly lowered due to the presence of excess polyisocyanate.

 硬化性ポリウレタン系樹脂組成物は、ポリエステルポリオール及び/又はポリイソシアネートを溶解もしくは分散させるための溶剤を適宜含有していてもよい。溶剤は、ポリエステルポリオールとポリイソシアネートとのいずれか一方に含有させてもよいし、両方に含有させてもよい。また、溶剤を、ポリエステルポリオールとポリイソシアネートとを混合した後に、適当な粘度になるように希釈する目的で用いることもできる。溶剤としては、例えば、トルエン、キシレン、ソルベントナフサ、メチルシクロヘキサン、エチルシクロヘキサンなどの炭化水素系溶剤;酢酸エチル、酢酸ブチル、酢酸エチレングリコールモノメチルエーテルなどのエステル系溶剤;アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトンなどのケトン系溶剤;等が挙げられる。溶剤は、1種のみであってもよいし、2種以上であってもよい。また、ポリオール成分に用いる溶剤とポリイソシアネート成分に用いる溶剤は、同じであってもよいし、異なっていてもよい。 The curable polyurethane resin composition may appropriately contain a solvent for dissolving or dispersing the polyester polyol and / or polyisocyanate. The solvent may be contained in one or both of the polyester polyol and polyisocyanate. Moreover, after mixing a polyester polyol and polyisocyanate, a solvent can also be used in order to dilute so that it may become a suitable viscosity. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, solvent naphtha, methylcyclohexane, and ethylcyclohexane; ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, And ketone solvents such as diisobutyl ketone. One type of solvent may be sufficient and 2 or more types may be sufficient as it. Moreover, the solvent used for a polyol component and the solvent used for a polyisocyanate component may be the same, and may differ.

 硬化性ポリウレタン系樹脂組成物には、必要に応じて、天然色素、有機合成色素、顔料、無機顔料または光輝材(塗膜にキラキラとした光輝感または光干渉性を付与するりん片状顔料)等の着色成分を含有させることができる。これら着色成分は、ポリエステルポリオールとポリイソシアネートとのどちらに含有させてもよいが、ポリエステルポリオールに含有させるのが好ましい。着色成分は、1種のみであってもよいし、2種以上であってもよい。なお、架橋構造を有するポリウレタン樹脂は、着色成分を含有しないクリヤー塗料であってもよいことは言うまでもない。 If necessary, the curable polyurethane resin composition may be a natural dye, an organic synthetic dye, a pigment, an inorganic pigment, or a bright material (a flake pigment that imparts a glittery feeling or light interference to the coating film). A coloring component such as can be contained. These coloring components may be contained in either polyester polyol or polyisocyanate, but are preferably contained in polyester polyol. Only 1 type may be sufficient as a coloring component, and 2 or more types may be sufficient as it. Needless to say, the polyurethane resin having a crosslinked structure may be a clear coating containing no coloring component.

 天然色素としては、例えば、カロチン、カロチナール、カプサンチン、リコピン、ビキシン、クロシン、カンタキサンチン、アナトーなどのカロチノイド系色素;シソニン、ラファニン、エノシアニンのようなアントシアニジン類、サフロールイエロー、ベニバナのようなカルコン類、ルチン、クエルセチンのようなフラボノール類、カカオ色素のようなフラボン類などのフラボノイド系色素;、リボフラビンなどのフラビン系色素;ラッカイン酸、カルミン酸(コチニール)、ケルメス酸、アリザリンのようなアントラキノン類、シコニン、アルカニン、エキノクロームのようなナフトキノン類などのキノン系色素;クロロフィル、血色素などのポリフィリン系色素;クルクミン(ターメリック)などのジケトン系色素;ベタニンなどのベタシアニジン系色素;等が挙げられる。 Examples of natural pigments include carotenoid pigments such as carotene, carotenal, capsanthin, lycopene, bixin, crocin, canthaxanthin and anato; anthocyanidins such as shisonin, raphanin and enocyanin, chalcones such as safrole yellow and safflower, Flavonols such as rutin and quercetin, flavonoids such as flavones such as cacao pigments, flavin pigments such as riboflavin; anthraquinones such as lacaic acid, carminic acid (cochineal), kermesic acid, alizarin, shikonin Quinone dyes such as naphthoquinones such as alkanin and echinochrome; polyphyrin dyes such as chlorophyll and hemoglobin; diketone dyes such as curcumin (turmeric); Tashianijin based dyes; and the like.

 有機合成色素または顔料としては、厚生省令第30号で定められているものが挙げられる。例えば、赤色202号(リソールルビンBCA)、赤色203号(レーキレッドC)、赤色204号(レーキレッドCBA)、赤色205号(リソールレッド)、赤色206号(リソールレッドCA)、赤色207号(リソールレッドBA)、赤色208号(リソールレッドSR)、赤色219号(ブリリアントレーキレッドR)、赤色220号(ディープマルーン)、赤色221号(トルイジンレッド)、赤色228号(パーマトンレッド)、だいだい色203号(パーマネントオレンジ)、だいだい色204号(ベンチジンオレンジG)、黄色205(ベンチジンエローG)、赤色404号(ブリリアントファストスカーレット)、赤色405号(パーマネントレッドF5R)、だいだい色401号(ハンザオレンジ)、黄色401号(ハンザエロー)、青色404号(フタロシアニンブルー)等が挙げられる。 Examples of organic synthetic dyes or pigments include those defined by Ordinance No. 30 of the Ministry of Health and Welfare. For example, Red 202 (Risor Rubin BCA), Red 203 (Rake Red C), Red 204 (Rake Red CBA), Red 205 (Risor Red), Red 206 (Risor Red CA), Red 207 (Risole) Red BA), Red 208 (Risor Red SR), Red 219 (Brilliant Lake Red R), Red 220 (Deep Maroon), Red 221 (Toluidine Red), Red 228 (Parmaton Red), orange No. 203 (Permanent Orange), Orange No. 204 (Bench Gin Orange G), Yellow 205 (Bench Gin Yellow G), Red No. 404 (Brilliant Fast Scarlet), Red No. 405 (Permanent Red F5R), Orange No. 401 ( Hansa Orange), Yellow No. 401 ( Nzaero), Blue No. 404 (phthalocyanine blue), and the like.

 無機顔料としては、例えば、無水ケイ酸、ケイ酸マグネシウム、タルク、カオリン、ベントナイト、酸化ジルコニウム、酸化マグネシウム、酸化亜鉛、酸化チタン、軽質炭酸カルシウム、重質炭酸カルシウム、軽質炭酸マグネシウム、重質炭酸マグネシウム、硫酸バリウム、黄酸化鉄、ベンガラ、黒酸化鉄、グンジョウ、酸化クロム、水酸化クロム、カーボンブラック、カラミン等が挙げられる。光輝材としては、例えば、りん片状のアルミニウム、蒸着アルミニウム、酸化アルミニウム、塩化オキシビスマス、雲母、酸化チタン被覆雲母、酸化鉄被覆雲母、雲母状酸化鉄、酸化チタン被覆シリカ、酸化チタン被覆アルミナ、酸化鉄被覆シリカ、酸化鉄被覆アルミナ、ガラスフレーク、着色ガラスフレーク、蒸着ガラスフレーク、ホログラムフィルム等が挙げられる。これら光輝材の大きさは、特に制限されないが、長手方向が1~30μm、厚さが0.001~1μmであるのが好ましい。 Examples of inorganic pigments include silicic anhydride, magnesium silicate, talc, kaolin, bentonite, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, light calcium carbonate, heavy calcium carbonate, light magnesium carbonate, and heavy magnesium carbonate. , Barium sulfate, yellow iron oxide, bengara, black iron oxide, gunjou, chromium oxide, chromium hydroxide, carbon black, calamine and the like. Examples of the bright material include flaky aluminum, vapor-deposited aluminum, aluminum oxide, oxybismuth chloride, mica, titanium oxide-coated mica, iron oxide-coated mica, mica-like iron oxide, titanium oxide-coated silica, and titanium oxide-coated alumina. Examples thereof include iron oxide-coated silica, iron oxide-coated alumina, glass flakes, colored glass flakes, vapor-deposited glass flakes, and hologram films. The size of these glitter materials is not particularly limited, but is preferably 1-30 μm in the longitudinal direction and 0.001-1 μm in thickness.

 硬化性ポリウレタン系樹脂組成物には、必要に応じて、その他の天然物由来樹脂が含有されていてもよい。その場合、その他の天然物由来樹脂は、ポリエステルポリオールとポリイソシアネートとのどちらに含有させてもよいが、ポリエステルポリオールに含有させるのが好ましい。その他の天然物由来樹脂は、1種のみであってもよいし、2種以上であってもよい。 The curable polyurethane resin composition may contain other natural product-derived resins as necessary. In that case, other natural product-derived resins may be contained in either polyester polyol or polyisocyanate, but are preferably contained in polyester polyol. One type of other natural product-derived resins may be used, or two or more types may be used.

 その他の天然物由来樹脂としては、特に制限されないが、例えば、植物性繊維、セルロース樹脂、ポリ乳酸に代表されるポリヒドロキシカルボン酸、ポリカプロラクタム、変性ポリビニルアルコールなどのほか、ポリカプロラクトンに代表される生分解性脂肪族ポリエステル等が挙げられる。その他の天然物由来樹脂としては、特に、上述した溶剤に可溶であるものが好ましく、なかでもセルロース由来の樹脂が好適である。例えば、セロース、ニトロセルロース、およびセルロースアセテートブチレートから選ばれる1種以上を少量含有させることにより、得られる硬化塗膜の表面硬度等の物性をより向上させることができる。その他の天然物由来樹脂として用いることのできる好ましい市販品としては、ニトロセルロースでは、仏国ベルジュラックNC社製の工業用硝化綿「BNC-HIG-2」、韓国CNC社製の工業用硝化綿「RS1-4」、(株)協鮮洋行製の「スワンセルHM1-4」、旭化成ケミカルズ(株)製の「セルノバBTH1-4」)等が挙げられ、セルロースアセテートブチレートでは、米国イーストマンケミカルプロダクツ社製の「CAB381-0.1」、「CAB381-0.5」、「CAB381-2」、「CAB531-1」、「CAB551-0.01」、「CAB551-0.2」等が挙げられる。 Other natural product-derived resins are not particularly limited, but include, for example, plant fibers, cellulose resins, polyhydroxycarboxylic acids typified by polylactic acid, polycaprolactam, modified polyvinyl alcohol, and the like, as well as typified by polycaprolactone. Examples include biodegradable aliphatic polyester. As other natural product-derived resins, those that are soluble in the above-mentioned solvents are particularly preferable, and cellulose-derived resins are particularly preferable. For example, physical properties such as surface hardness of the obtained cured coating film can be further improved by containing a small amount of one or more selected from cellulose, nitrocellulose, and cellulose acetate butyrate. Examples of other commercially available products that can be used as other natural product-derived resins include nitrocellulose, industrial nitrified cotton “BNC-HIG-2” manufactured by Bergerac NC, France, and industrial nitrified cotton manufactured by Korea CNC. “RS1-4”, “Swancell HM1-4” manufactured by Kyosei Yoko Co., Ltd., “Selnova BTH1-4” manufactured by Asahi Kasei Chemicals Co., Ltd.), etc. “CAB381-0.1”, “CAB381-0.5”, “CAB381-2”, “CAB531-1”, “CAB551-0.01”, “CAB551-0.2” manufactured by Products It is done.

 硬化性ポリウレタン系樹脂組成物には、必要に応じて、従来公知の表面調整剤(ワックス、ハジキ防止剤、消泡剤など)、可塑剤、紫外線安定剤、酸化防止剤、流動性調整剤、垂れ止め剤、つや消し剤、艶出し剤、防腐剤等の各種添加物を適宜含有させることができる。これら添加物は、ポリエステルポリオールとポリイソシアネートとのどちらに含有させてもよいが、ポリエステルポリオールに含有させるのが好ましい。 In the curable polyurethane resin composition, if necessary, a conventionally known surface conditioner (wax, repellency inhibitor, antifoaming agent, etc.), plasticizer, UV stabilizer, antioxidant, fluidity modifier, Various additives such as an anti-sagging agent, a matting agent, a polishing agent, and an antiseptic can be appropriately contained. These additives may be contained in either polyester polyol or polyisocyanate, but are preferably contained in polyester polyol.

 架橋構造を有するポリウレタン樹脂は、少なくともポリエステルポリオールとポリイソシアネートとを含む硬化性ポリウレタン系樹脂組成物を硬化させた硬化物であり、ポリエステルポリオールをポリイソシアネートで硬化させてなる樹脂ある。架橋構造を有するポリウレタン樹脂は、例えば、上記でも述べたように、ポリエステルポリオールとポリイソシアネートとを混合して得られる。そして、得られた架橋構造を有するポリウレタン樹脂をポリカーボネート樹脂に添加(ドライブレンド)し、その後、混練することにより、本技術に係る第1の実施形態の樹脂組成物を得ることができる。 The polyurethane resin having a crosslinked structure is a cured product obtained by curing a curable polyurethane resin composition containing at least a polyester polyol and a polyisocyanate, and is a resin obtained by curing a polyester polyol with a polyisocyanate. The polyurethane resin having a crosslinked structure can be obtained, for example, by mixing polyester polyol and polyisocyanate as described above. And the resin composition of 1st Embodiment which concerns on this technique can be obtained by adding the polyurethane resin which has the obtained crosslinked structure to polycarbonate resin (dry blending), and kneading | mixing after that.

 [2-4.ポリエステルポリオール]
 架橋構造を有するポリウレタン樹脂の原料となるポリエステルポリオールについて説明する。
[2-4. Polyester polyol]
The polyester polyol as a raw material for the polyurethane resin having a crosslinked structure will be described.

 ポリエステルポリオールの水酸基価は任意の値を有してよいが、30~300であることが好ましい。ポリエステルポリオールの水酸基価が30未満であると、得られるポリウレタン樹脂は、架橋密度がやや低くなる場合があり、結果として、芳香族ポリカーボネート樹脂に添加、混錬した樹脂組成物の耐薬品性、耐摩耗性、耐候性、耐水性、耐溶剤性がやや不充分になる場合がある。一方、ポリエステルポリオールの水酸基価が300を超えると、逆に、架橋がやや進行しすぎることから、芳香族ポリカーボネート樹脂との相溶性がやや悪くなり、機械的物性、耐薬品性がやや低下する場合がある。水酸基価は、JIS K-1557-1に記載の方法により測定を実施して得ることができる。 The hydroxyl value of the polyester polyol may have any value, but is preferably 30 to 300. When the hydroxyl value of the polyester polyol is less than 30, the resulting polyurethane resin may have a slightly lower crosslink density. As a result, the chemical resistance and resistance of the resin composition added and kneaded to the aromatic polycarbonate resin may be reduced. Abrasion, weather resistance, water resistance, and solvent resistance may be slightly insufficient. On the other hand, when the hydroxyl value of the polyester polyol exceeds 300, on the contrary, since the crosslinking is slightly advanced, the compatibility with the aromatic polycarbonate resin is slightly deteriorated, and the mechanical properties and chemical resistance are slightly decreased. There is. The hydroxyl value can be obtained by measurement by the method described in JIS K-1557-1.

 ポリエステルポリオールの重量平均分子量は任意の値を有してよいが、10,000~500,000であることが好ましい。ポリエステルポリオールの重量平均分子量が10,000未満であると、架橋構造を有するポリウレタン構造を形成し、ポリカーボネート樹脂に添加、混錬された樹脂組成物の耐薬品性がやや不充分になるおそれがある。一方、ポリエステルポリオールの重量平均分子量が500,000を超えると、粘度が高くなり、ポリカーボネート樹脂に添加、混錬された時に分散性がやや悪くなり物性低下につながる傾向がある。 The weight average molecular weight of the polyester polyol may have any value, but is preferably 10,000 to 500,000. If the weight average molecular weight of the polyester polyol is less than 10,000, a polyurethane structure having a crosslinked structure is formed, and the chemical resistance of the resin composition added to and kneaded with the polycarbonate resin may be slightly insufficient. . On the other hand, when the weight average molecular weight of the polyester polyol exceeds 500,000, the viscosity becomes high, and when added to the polycarbonate resin and kneaded, the dispersibility tends to be slightly deteriorated, leading to a decrease in physical properties.

 ポリエステルポリオールは、例えば、低分子量ポリオールとポリカルボン酸とを反応させる方法や、ε-カプロラクトン等の環状エステル化合物を開環重合反応する方法等で製造することができる。 Polyester polyol can be produced by, for example, a method of reacting a low molecular weight polyol and a polycarboxylic acid, a method of ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and the like.

 低分子量ポリオールとしては、例えば、エチレングリコール、プロピレングリコ-ル、1,3-プロパンジオ-ル、1,4-ブタンジオ-ル、1,5-ペンタンジオ-ル、1,6-ヘキサンジオ-ル、ネオペンチルグリコ-ル、1,8-オクタンジオ-ル、ジエチレングリコ-ル、トリエチレングリコ-ル、テトラエチレングリコ-ル、ポリエチレングリコ-ル(分子量300~6000)、ジプロピレングリコ-ル、トリプロピレングリコ-ル、ビスヒドロキシエトキシベンゼン、1,4-シクロヘキサンジオ-ル、1,4-シクロヘキサンジメタノ-ル、ビスフェノ-ルA、水素添加ビスフェノ-ルA、ハイドロキノンおよびそれらのアルキレンオキシド付加体等を使用することができる。 Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo Pentyl glycol, 1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6000), dipropylene glycol, tripropylene glycol Bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts be able to.

 また、ポリカルボン酸としては、例えばコハク酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸、マレイン酸、フマル酸、1,3-シクロペンタンジカルボン酸、1,4-シクロヘキサンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、1,4-ナフタレンジカルボン酸、2,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、ナフタル酸、ビフェニルジカルボン酸、1,2-ビス(フェノキシ)エタン-p,p’-ジカルボン酸、及びこれらの無水物またはエステル形成性誘導体などを使用することができる。 Examples of the polycarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid. , Isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acids, and anhydrides or ester-forming derivatives thereof can be used.

 また、ポリエステルポリオールは、植物油由来原料を用いて得られるポリエステルポリオールでもよい。 Further, the polyester polyol may be a polyester polyol obtained using a vegetable oil-derived raw material.

 植物油由来原料は、植物油またはその脂肪酸、植物油を原料として製造されるカルボン酸、および、植物油由来の水酸基を有する原料からなる群より選ばれる1種以上であることが好ましい。植物油または植物油脂肪酸としては、例えば、支那桐油(脂肪酸)、亜麻仁油(脂肪酸)、脱水ひまし油(脂肪酸)、トール油脂肪酸、綿実油(脂肪酸)、大豆油(脂肪酸)、オリーブ油(脂肪酸)、サフラワー油(脂肪酸)、ひまし油(脂肪酸)米糠油(脂肪酸)、水添やし油(脂肪酸)、やし油(脂肪酸)、パーム油(脂肪酸)等が挙げられる。 The vegetable oil-derived raw material is preferably at least one selected from the group consisting of vegetable oil or fatty acids thereof, carboxylic acids produced using vegetable oil as a raw material, and raw materials having a hydroxyl group derived from vegetable oil. Examples of vegetable oil or vegetable oil fatty acid include Chinese tung oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil fatty acid, cottonseed oil (fatty acid), soybean oil (fatty acid), olive oil (fatty acid), safflower oil (Fatty acid), castor oil (fatty acid) rice bran oil (fatty acid), hydrogenated coconut oil (fatty acid), coconut oil (fatty acid), palm oil (fatty acid) and the like.

 植物油を原料として製造されるカルボン酸としては、例えば、ひまし油から製造される12-ヒドロキシステアリン酸、ヘプチル酸、ウンデシレン酸、セバシン酸;松ヤニより精製されるロジン、その水素化物である水添ロジン、およびその重合体である重合ロジントール油脂肪酸等の乾性植物油脂肪酸から製造されるダイマー酸、およびその水素化物である水添ダイマー酸;ダイマー酸製造時に副生されるイソステアリン酸;等が挙げられる。植物油由来の水酸基を有する原料としては、例えば、ひまし油から製造されるヘプタナール、オクタノール、1,10-デカンジオール;各植物油から精製されるグリセリン;等が挙げられる。 Examples of carboxylic acids produced from vegetable oils include, for example, 12-hydroxystearic acid, heptyl acid, undecylenic acid, sebacic acid produced from castor oil; rosin purified from pine ani, and hydrogenated rosin that is a hydride thereof. And dimer acid produced from a dry vegetable oil fatty acid such as polymerized rosin tall oil fatty acid which is a polymer thereof, and hydrogenated dimer acid which is a hydride thereof; isostearic acid produced as a by-product during dimer acid production, and the like. Examples of the raw material having a hydroxyl group derived from vegetable oil include heptanal, octanol, 1,10-decanediol produced from castor oil; glycerin purified from each vegetable oil; and the like.

 ポリエステルポリオールは、上述した植物油由来原料を用いて得られるものであってもよく、その製造方法は特に制限されないが、例えば、前記植物油由来原料と、必要に応じて、エステル化反応に、一般に使用される酸成分および/またはアルコール成分とを、エステル化反応させることにより、得ることができる。 The polyester polyol may be obtained using the above-described vegetable oil-derived raw material, and its production method is not particularly limited. For example, it is generally used for the above-mentioned vegetable oil-derived raw material and, if necessary, the esterification reaction. The acid component and / or alcohol component to be obtained can be obtained by an esterification reaction.

 ポリエステルポリオールを得る際に用いることのできる酸成分としては、例えば、安息香酸、p-tert-ブチル安息香酸、イソフタル酸、無水フタル酸、テレフタル酸、オルソフタル酸、2,6-ナフタレンジカルボン酸、アゼライン酸、セバシン酸、イソセバシン酸、シュウ酸、トリメリット酸、(無水)コハク酸、(無水)マレイン酸、フマル酸、(無水)イタコン酸、ドデカンオン酸、テトラヒドロ(無水)フタル酸、ヘキサヒイドロ(無水)フタル酸、ヘキサハイドロイソフタル酸、ヘキサハイドロテレフタル酸、テトラクロロ(無水)フタル酸、ヘキサクロロ(無水)フタル酸、テトラブロモ(無水)フタル酸、グルタール酸、アジピン酸、ピメリン酸、ユベリン酸、水添フタル酸、1,4-シクロヘキサンジカルボン酸等が挙げられる。なお、酸成分は、1種のみであってもよいし、2種以上であってもよい。 Examples of the acid component that can be used in obtaining the polyester polyol include benzoic acid, p-tert-butylbenzoic acid, isophthalic acid, phthalic anhydride, terephthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, and azelain. Acid, sebacic acid, isosebacic acid, oxalic acid, trimellitic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, dodecanoic acid, tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) Phthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tetrachloro (anhydride) phthalic acid, hexachloro (anhydride) phthalic acid, tetrabromo (anhydride) phthalic acid, glutaric acid, adipic acid, pimelic acid, uberic acid, hydrogenated phthalate Acid, 1,4-cyclohexanedicarboxylic acid, etc. And the like. In addition, only 1 type may be sufficient as an acid component, and 2 or more types may be sufficient as it.

 ポリエステルポリオールを得る際に用いることのできるアルコール成分としては、例えば、エチレングリコール、ネオペンチルグリコール、ジエチレングリコール、テトラメチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、2,3,4-トリメチル-1,3-ペンタンジオール、3-メチルペンテン-1,5-ジオール、1,4-シクロヘキサンジメタノール、ビスフェノールAまたは水素化ビスフェノールAのエチレンオキシドもしくはプロピレノキシド、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリブチレングリコール、2,2-ジエチル-1,3-プロパンジオール、2-n-ブチル-エチル-1,3-プロパンジオール、トリシクロデカンジメタノール、シクロヘキサンジカルボン酸、シクロヘキサンジメタノール、シクロヘキサンジオールなどの2価アルコール成分;合成グリセリン(植物油由来ではない)、トリメチロールプロパン、トリメチロールエタンなどの3価アルコール成分;ペンタエリスリトールなどの4価アルコール;等が挙げられる。なお、アルコール成分は、1種のみであってもよいし、2種以上であってもよい。 Examples of the alcohol component that can be used for obtaining the polyester polyol include ethylene glycol, neopentyl glycol, diethylene glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and 2,3,4-trimethyl-1 , 3-pentanediol, 3-methylpentene-1,5-diol, 1,4-cyclohexanedimethanol, ethylene oxide or propylenoxide of bisphenol A or hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene Glycol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-ethyl-1,3-propanediol, trisic Divalent alcohol components such as decanedimethanol, cyclohexanedicarboxylic acid, cyclohexanedimethanol, cyclohexanediol; trivalent alcohol components such as synthetic glycerin (not derived from vegetable oil), trimethylolpropane, trimethylolethane; tetravalent such as pentaerythritol Alcohol; etc. are mentioned. In addition, only 1 type may be sufficient as an alcohol component, and 2 or more types may be sufficient as it.

 ポリエステルポリオールを得るにあたり、植物油由来原料の使用量は、得られるポリエステルポリオール中に占める植物油由来原料の含有割合は随意でよいが、30~100質量%となるように設定することが好ましい。ポリエステルポリオール中に占める植物油由来原料の含有割合が30質量%未満であると、カーボンニュートラルな材料を利用することにより得られる地球温暖化防止効果がやや小さくなる傾向がある。なお、ポリエステルポリオールを得る際のエステル化反応は、従来公知のエステル化方法や条件等を適宜採用して行えばよい。 In obtaining the polyester polyol, the amount of the vegetable oil-derived raw material used is preferably set so as to be 30 to 100% by mass, although the content of the vegetable oil-derived raw material in the obtained polyester polyol may be optional. When the content ratio of the vegetable oil-derived raw material in the polyester polyol is less than 30% by mass, the effect of preventing global warming obtained by using a carbon neutral material tends to be slightly reduced. In addition, what is necessary is just to employ | adopt suitably a conventionally well-known esterification method, conditions, etc. for the esterification reaction at the time of obtaining polyester polyol.

 [2-5.ポリイソシアネート]
 架橋構造を有するポリウレタン樹脂の原料となるポリイソシアネートについて説明する。
[2-5. Polyisocyanate]
The polyisocyanate used as the raw material for the polyurethane resin having a crosslinked structure will be described.

 ポリイソシアネートは、少なくとも1つのイソシアネート基を有し、2つ以上のイソシアネート基を有することが好ましい。 The polyisocyanate has at least one isocyanate group and preferably has two or more isocyanate groups.

 ポリイソシアネートとしては、例えば、芳香族系ポリイソシアネート、脂肪族系ポリイソシアネート、環式脂肪族系ポリイソシアネート、脂環式ポリイソシアネート、またはこれらポリイソシアネートとポリオールとの反応生成物等が挙げられる。これらの中でも、トリレンジイソシアネート(TDI)、ジフェニルメタンジイソシアネート(MDI)、ポリフェニルメタンポリイソシアネート(クルードMDI)、変性ジフェニルメタンジイソシアネート(変性MDI)、キシリレンジイソシアネート(XDI)、ヘキサメチレンジイソシアネート(HMDI)などの芳香族系ポリイソシアネートあるいはこれらポリイソシアネートの三量体化合物や、これらポリイソシアネートとポリオールとの反応生成物等が好ましい。本技術に係る第1の実施形態の樹脂組成物において、ポリイソシアネートとして、1種のみのポリイソシアネートを用いてもよいし、2種以上のポリイソシアネートを用いてもよい。 Examples of the polyisocyanate include aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, alicyclic polyisocyanates, or reaction products of these polyisocyanates and polyols. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), etc. Aromatic polyisocyanates or trimer compounds of these polyisocyanates, reaction products of these polyisocyanates and polyols, and the like are preferable. In the resin composition of the first embodiment according to the present technology, as the polyisocyanate, only one type of polyisocyanate may be used, or two or more types of polyisocyanate may be used.

 [2-6.有機スルホン酸及び有機スルホン酸金属塩化合物]
 本技術に係る第1の実施形態の樹脂組成物は、有機スルホン酸及び/又は有機スルホン酸金属塩化合物を、芳香族ポリカーボネート樹脂100質量部に対して0.01~3.0質量部で更に含んでもよい。以下に、有機スルホン酸及び有機スルホン酸金属塩化合物について、詳細に説明する。
[2-6. Organic sulfonic acid and organic sulfonic acid metal salt compound]
In the resin composition of the first embodiment according to the present technology, the organic sulfonic acid and / or the organic sulfonic acid metal salt compound is further added in an amount of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. May be included. Hereinafter, the organic sulfonic acid and the organic sulfonic acid metal salt compound will be described in detail.

 有機スルホン酸は、特に限定されないが、芳香族有機スルホン酸であることが好ましい。有機スルホン酸金属塩化合物は、特に限定されないが、芳香族スルホン酸金属塩化合物であることが好ましい。芳香族スルホン酸金属塩化合物は、スルホン酸金属塩基を含有し、スルホン酸金属塩基の含有量は、適宜調整されて任意の量でよいが、0.1~10モル%であることが好ましい。有機スルホン酸及び有機スルホン酸金属塩化合物において、低分子量の化合物としては、例えばパーフルオロアルカンスルホン酸、アルキルベンゼンスルホン酸、ハロゲン化アルキルベンゼンスルホン酸、アルキルスルホン酸、ナフタレンスルホン酸等、又はそれらのアルカリ金属塩若しくはアルカリ土類金属塩、また、高分子量の化合物としては、例えば、特許4196862及び特許4196861に記載されている、芳香族環を有するポリマーにスルホン酸および/又はその金属塩が所定量含まれているものが挙げられる。芳香族環を有するポリマーとしては、例えば、ポリスチレン(PS)スルホン酸若しくはポリスチレン(PS)スルホン酸金属塩、ハイインパクトポリスチレン(HIPS)スルホン酸若しくはハイインパクトポリスチレン(HIPS)スルホン酸金属塩、又はスルホン酸基及び/若しくはスルホン酸塩基含有のスチレン・アクリロニトリル共重合樹脂(AS)が挙げられる。 The organic sulfonic acid is not particularly limited, but is preferably an aromatic organic sulfonic acid. The organic sulfonic acid metal salt compound is not particularly limited, but is preferably an aromatic sulfonic acid metal salt compound. The aromatic sulfonic acid metal salt compound contains a sulfonic acid metal base, and the content of the sulfonic acid metal base may be arbitrarily adjusted and may be any amount, but is preferably 0.1 to 10 mol%. In the organic sulfonic acid and the organic sulfonic acid metal salt compound, examples of the low molecular weight compound include perfluoroalkanesulfonic acid, alkylbenzene sulfonic acid, halogenated alkylbenzene sulfonic acid, alkyl sulfonic acid, naphthalene sulfonic acid and the like, or alkali metals thereof. Examples of the salt or the alkaline earth metal salt and the high molecular weight compound include, for example, a polymer having an aromatic ring and a predetermined amount of sulfonic acid and / or a metal salt thereof described in Patent 4196862 and Patent 4196661. Are listed. Examples of the polymer having an aromatic ring include polystyrene (PS) sulfonic acid or polystyrene (PS) sulfonic acid metal salt, high impact polystyrene (HIPS) sulfonic acid or high impact polystyrene (HIPS) sulfonic acid metal salt, or sulfonic acid. Styrene / acrylonitrile copolymer resin (AS) containing a group and / or a sulfonate group.

 有機スルホン酸又は有機スルホン酸金属塩化合物として、以上に記載した通り低分子量のものから高分子量のものまで各種あるものの、一般的には高分子量の方が芳香族ポリカーボネート樹脂に混練した場合の分散性が良好であることや、高温高湿条件下での保存安定性が優れることから好ましい。 As described above, there are various types of organic sulfonic acid or organic sulfonic acid metal salt compounds ranging from low molecular weight to high molecular weight, but in general, dispersion when high molecular weight is kneaded into aromatic polycarbonate resin It is preferable because of its good properties and excellent storage stability under high temperature and high humidity conditions.

 更に好ましくは、粒子表層部にスルホン酸基が結合しているコア・シェル型のスチレン系ポリマーおよびそのアルカリ金属塩やアルカリ土類金属塩などであり、具体的には例えばポリスチレンスルホン酸やそのカリウム塩がある。これらの中から選ばれる一つまたは複数を適切な比率で混合して用いてもよいが、ポリスチレンスルホン酸やそのカリウム塩を用いると、極少量の添加量で高い難燃効果を得られるため、好ましい。また、それらの重量平均分子量(ポリスチレン換算)が30000以上であることが好ましく、40000以上300000以下であると耐溶剤性と相溶性のバランスが更に保たれるため、より好ましい。 More preferably, a core-shell type styrene polymer having a sulfonic acid group bonded to the particle surface layer portion, and an alkali metal salt or alkaline earth metal salt thereof, specifically, for example, polystyrene sulfonic acid or potassium thereof. There is salt. One or more selected from these may be mixed and used at an appropriate ratio, but when using polystyrene sulfonic acid or its potassium salt, a high flame retardant effect can be obtained with a very small amount of addition, preferable. Moreover, it is preferable that those weight average molecular weights (polystyrene conversion) are 30000 or more, and when it is 40000 or more and 300000 or less, since the balance of solvent resistance and compatibility is further maintained, it is more preferable.

 有機スルホン酸又は有機スルホン酸金属塩化合物の含有量としては、上述のとおり、芳香族ポリカーボネート樹脂100質量部に対して0.01~3.0質量部であるが、0.05~1.5質量部である場合に難燃効果が更に強まり、0.05~1質量部であるとより更に強い難燃効果を得られるため、より好ましい。0.05質量部未満の場合、難燃効果が得られにくい場合があり、また、1.5質量部超の場合、芳香族ポリカーボネート樹脂との相溶性が低下する場合があり、負の難燃効果、すなわち不含有の場合よりも難燃レベルが低下する場合がある。 As described above, the content of the organic sulfonic acid or the organic sulfonic acid metal salt compound is 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. In the case of mass parts, the flame retardant effect is further enhanced, and in the case of 0.05 to 1 mass part, a stronger flame retardant effect can be obtained. If it is less than 0.05 parts by mass, it may be difficult to obtain a flame retardant effect. If it exceeds 1.5 parts by mass, the compatibility with the aromatic polycarbonate resin may be reduced, and negative flame retardant. The flame retardant level may be lower than the effect, that is, the case of not containing.

 [2-7.ドリップ防止剤]
 本技術に係る第1の実施形態の樹脂組成物はドリップ防止剤を更に含んでもよい。ドリップ防止剤の含有量は、芳香族ポリカーボネート樹脂100質量部に対して、0.8質量部以下でよい。本技術に係る第1の実施形態の樹脂組成物が難燃性樹脂組成物として用いられる場合、有機スルホン酸及び有機スルホン酸金属塩化合物(難燃剤)の他に、ドリップ防止剤を含ませて、燃焼時のドリップ現象を抑制することできる。ドリップ防止剤は、例えば、フルオロオレフィン樹脂等が挙げられる。
[2-7. Anti-drip agent]
The resin composition of the first embodiment according to the present technology may further include an anti-drip agent. The content of the anti-drip agent may be 0.8 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin. When the resin composition of the first embodiment according to the present technology is used as a flame retardant resin composition, in addition to the organic sulfonic acid and the organic sulfonic acid metal salt compound (flame retardant), an anti-drip agent is included. The drip phenomenon during combustion can be suppressed. Examples of the anti-drip agent include a fluoroolefin resin.

 ドリップ現象を抑制することできるフルオロオレフィン樹脂としては、例えばジフルオロエチレン重合体、テトラフルオロエチレン重合体、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン-エチレン系モノマーとの共重合体等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Examples of the fluoroolefin resin capable of suppressing the drip phenomenon include a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a copolymer with a tetrafluoroethylene-ethylene monomer. Any one of them or a mixture of two or more of them can be used.

 これらのフルオロオレフィン樹脂の中でも、特にテトラフルオロエチレン重合体等を用いることが好ましく、その平均分子量は50000以上であり、好ましくは100000~20000000の範囲である。なお、フルオロオレフィン樹脂としては、フィブリル形成能を有するものがより好ましい。 Among these fluoroolefin resins, it is particularly preferable to use a tetrafluoroethylene polymer or the like, and the average molecular weight is 50,000 or more, and preferably in the range of 100,000 to 20,000,000. In addition, as fluoroolefin resin, what has fibril formation ability is more preferable.

 フルオロオレフィン樹脂等のドリップ防止剤の含有量は、芳香族ポリカーボネート樹脂100質量部に対して、上述したとおり、0.8質量部以下でよく、0.001~0.8質量部の範囲が好ましく、0.01~0.5質量部の範囲がより好ましく、0.05~0.3質量部の範囲が更に好ましい。 As described above, the content of the anti-drip agent such as fluoroolefin resin may be 0.8 parts by mass or less, preferably in the range of 0.001 to 0.8 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. The range of 0.01 to 0.5 parts by mass is more preferable, and the range of 0.05 to 0.3 parts by mass is even more preferable.

 フルオロオレフィン樹脂等のドリップ防止剤の含有量が、芳香族ポリカーボネート樹脂100質量部に対して0.001質量部より少なくなると、ドリップ現象を抑制させることが困難になる場合がある。一方、フルオロオレフィン樹脂等のドリップ防止剤の含有量が0.8質量部より多くなると、成形物はやや白化し、透明性がやや損なわれる場合がある。 If the content of the anti-drip agent such as fluoroolefin resin is less than 0.001 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin, it may be difficult to suppress the drip phenomenon. On the other hand, if the content of the anti-drip agent such as fluoroolefin resin is more than 0.8 parts by mass, the molded product may be slightly whitened and transparency may be slightly impaired.

 [2-8.その他成分]
 本技術に係る第1の実施形態の樹脂組成物は、上述した他に、その他成分(他の添加剤)として、例えば、酸化防止剤(ヒンダードフェノール系、リン系、硫黄系)、帯電防止剤、紫外線吸収剤(ベンゾフェノン系、ベンゾトリアゾール系、ヒドロキシフェニルトリアジン系、環状イミノエステル系、シアノアクリレート系)、光安定化剤、可塑剤、相溶化剤、着色剤(顔料、染料)、光安定剤、結晶核剤、抗菌剤、流動改質剤、赤外線吸収剤、蛍光体、加水分解防止剤、離型剤、シリコーン系の難燃剤あるいは表面処理剤などを含有していてもよい。これにより、射出成形性、耐衝撃性、外観、耐熱性、耐候性、色あるいは剛性などが改善される。特にシリコーン系の難燃剤として下記のシリコーン化合物を挙げることができる。
[2-8. Other ingredients]
In addition to the above, the resin composition of the first embodiment according to the present technology includes, as other components (other additives), for example, an antioxidant (hindered phenol-based, phosphorus-based, sulfur-based), antistatic Agent, UV absorber (benzophenone, benzotriazole, hydroxyphenyltriazine, cyclic imino ester, cyanoacrylate), light stabilizer, plasticizer, compatibilizer, colorant (pigment, dye), light stability Agents, crystal nucleating agents, antibacterial agents, flow modifiers, infrared absorbers, phosphors, hydrolysis inhibitors, mold release agents, silicone flame retardants or surface treatment agents may be contained. Thereby, injection moldability, impact resistance, appearance, heat resistance, weather resistance, color or rigidity are improved. In particular, the following silicone compounds can be listed as silicone-based flame retardants.

 シリコーン化合物は、本技術に係る第1の実施形態の樹脂組成物に難燃性を付与するために用いられる。樹脂組成物中におけるシリコーン系の難燃剤の添加量は、樹脂組成物に対する質量比で0.001~0.02(0.1~2質量%)であることが好ましい。シリコーン系の難燃剤の添加量が、樹脂組成物に対する質量比で0.001(0.1質量%)より少なくなると、樹脂組成物に難燃性を付与する効果が十分ではない場合がある。一方、添加量が0.02(2質量%)より多くなると、効率の低下によって経済性が悪くなる場合があり、難燃性を付与する効果も飽和して効率が低下する場合がある。 The silicone compound is used to impart flame retardancy to the resin composition of the first embodiment according to the present technology. The addition amount of the silicone-based flame retardant in the resin composition is preferably 0.001 to 0.02 (0.1 to 2% by mass) as a mass ratio with respect to the resin composition. When the addition amount of the silicone-based flame retardant is less than 0.001 (0.1% by mass) in terms of mass ratio with respect to the resin composition, the effect of imparting flame retardancy to the resin composition may not be sufficient. On the other hand, when the addition amount is more than 0.02 (2% by mass), the economy may be deteriorated due to the decrease in efficiency, and the effect of imparting flame retardancy may be saturated and the efficiency may be decreased.

 <3.第2の実施形態(樹脂組成物の製造方法の例)>
 [3-1.樹脂組成物の製造方法]
 以下、本技術に係る第2の実施形態(樹脂組成物の例)の樹脂組成物の製造方法について詳細に説明をする。
<3. Second Embodiment (Example of Manufacturing Method of Resin Composition)>
[3-1. Method for producing resin composition]
Hereinafter, the manufacturing method of the resin composition of 2nd Embodiment (example of a resin composition) which concerns on this technique is demonstrated in detail.

 本技術に係る第2の実施形態(樹脂組成物の例)の樹脂組成物の製造方法は、芳香族ポリカーボネート樹脂100質量部に、架橋構造を有するポリウレタン樹脂0.01~5.0重量部を添加することと、芳香族ポリカーボネート樹脂と架橋構造を有するポリウレタン樹脂とを混錬することとを含む、樹脂組成物の製造方法である。架橋構造を有するポリウレタン樹脂は、硬化樹脂であることが好ましく、光硬化樹脂でもよいし、熱硬化樹脂でもよい。なお、本技術に係る第2の実施形態の樹脂組成物の製造方法で用いられる芳香族ポリカーボネート樹脂及び架橋構造を有するポリウレタン樹脂については、下記に述べること以外は、本技術に係る第1の実施形態の樹脂組成物に含まれる芳香族ポリカーボネート樹脂及び架橋構造を有するポリウレタン樹脂の内容が、本技術に係る第2の実施形態の樹脂組成物の製造方法で用いられる芳香族ポリカーボネート樹脂及び架橋構造を有するポリウレタン樹脂にそのまま適用され得る。 In the method for producing a resin composition of the second embodiment (example of resin composition) according to the present technology, 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure is added to 100 parts by weight of an aromatic polycarbonate resin. It is a manufacturing method of the resin composition including adding and knead | mixing the aromatic polycarbonate resin and the polyurethane resin which has a crosslinked structure. The polyurethane resin having a crosslinked structure is preferably a curable resin, and may be a photocurable resin or a thermosetting resin. The aromatic polycarbonate resin and the polyurethane resin having a cross-linked structure used in the method for producing the resin composition of the second embodiment according to the present technology are the first operations according to the present technology, except as described below. The content of the aromatic polycarbonate resin and the polyurethane resin having a crosslinked structure contained in the resin composition in the form is the same as the aromatic polycarbonate resin and the crosslinked structure used in the method for producing the resin composition of the second embodiment according to the present technology. It can be applied as it is to the polyurethane resin it has.

 本技術に係る第2の実施形態の樹脂組成物の製造方法によって製造される樹脂組成物によれば、耐衝撃性等の機械的物性の性能を維持させながら、流動性や、耐溶剤性、耐薬品性、耐擦傷性等の表面物性を向上させることができる。なお、流動性の向上は、樹脂組成物の加工適性を良化させる。 According to the resin composition produced by the method for producing a resin composition of the second embodiment according to the present technology, while maintaining the performance of mechanical properties such as impact resistance, fluidity, solvent resistance, Surface properties such as chemical resistance and scratch resistance can be improved. The improvement in fluidity improves the processability of the resin composition.

 芳香族ポリカーボネート樹脂100質量部に、架橋構造を有するポリウレタン樹脂を添加する量は、芳香族ポリカーボネート樹脂100質量部に対して0.01~5.0質量部であるが、機械的物性の更なる向上の観点から、0.05~3.0質量部であることが好ましい。 The amount of the polyurethane resin having a crosslinked structure added to 100 parts by mass of the aromatic polycarbonate resin is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. From the viewpoint of improvement, the amount is preferably 0.05 to 3.0 parts by mass.

 本技術に係る第2の実施形態の樹脂組成物の製造方法は、例えば、以下のとおりである。
 100質量部の芳香族ポリカーボネート樹脂の成分に、0.01~5.0質量部の架橋構造を有するポリウレタン樹脂の成分、並びに樹脂組成物の用途等の必要性に応じて、<2.第1の実施形態(樹脂組成物の例)>で述べた、有機スルホン酸及び/又は有機スルホン酸金属塩化合物、ドリップ防止剤、その他成分及び/又はシリコーン化合物の各成分を所定量で添加して、混合する。混合後、例えば、ヘンシェルミキサーやタンブラーにて略均一に分散させる。その後、単軸あるいは二軸押し出し機によって溶融混練して、得られるストランドをペレタイザーでカットしてペレットを作製して樹脂組成物が得られる。なお、本技術に係る第2の実施形態の樹脂組成物の製造方法によって製造される樹脂組成物は、ペレット状に加工したものに限られず、各成分を混合した状態(粉末状態や流体状態)やペレットとは異なる形態(シート状等)に加工したものも含む。
The manufacturing method of the resin composition of 2nd Embodiment which concerns on this technique is as follows, for example.
Depending on the necessity of the component of the polyurethane resin having a cross-linked structure of 0.01 to 5.0 parts by mass and the use of the resin composition in addition to 100 parts by mass of the aromatic polycarbonate resin, <2. First embodiment (example of resin composition)> The organic sulfonic acid and / or organic sulfonic acid metal salt compound, the anti-drip agent, other components and / or the silicone compound are added in predetermined amounts. And mix. After mixing, for example, it is dispersed substantially uniformly with a Henschel mixer or a tumbler. Thereafter, the resin composition is obtained by melt-kneading with a single screw or twin screw extruder and cutting the resulting strand with a pelletizer to produce pellets. In addition, the resin composition manufactured by the manufacturing method of the resin composition of 2nd Embodiment which concerns on this technique is not restricted to what was processed into the pellet form, The state (powder state or fluid state) which mixed each component And those processed into a form different from the pellet (such as a sheet).

 100質量部の芳香族ポリカーボネート樹脂の成分に、0.01~5.0質量部の架橋構造を有するポリウレタン樹脂の成分等を添加する方法は、例えば、100質量部の芳香族ポリカーボネートの樹脂のペレット表面に、塗膜が形成されるように、0.01~5.0質量部のポリウレタン樹脂の成分等を添加する方法、100質量部の芳香族ポリカーボネート樹脂からなるカラープレート上に、0.01~5.0質量部のポリウレタン樹脂の成分等をコートするように添加する方法が挙げられる。芳香族ポリカーボネート樹脂からなるカラープレート上に、ポリウレタン樹脂の成分等をコートするように添加する方法の場合は、コート後に、得られた樹脂組成物を粉砕し、リペレットすることが必要な場合がある。 A method of adding a component of a polyurethane resin having a cross-linked structure of 0.01 to 5.0 parts by mass to a component of 100 parts by mass of an aromatic polycarbonate resin includes, for example, pellets of 100 parts by mass of an aromatic polycarbonate resin A method of adding 0.01 to 5.0 parts by mass of a polyurethane resin component or the like so that a coating film is formed on the surface, 0.01% on a color plate made of 100 parts by mass of an aromatic polycarbonate resin An example is a method of adding a component of polyurethane resin of up to 5.0 parts by mass so as to coat it. In the case of a method of adding a polyurethane resin component or the like on a color plate made of an aromatic polycarbonate resin, it may be necessary to pulverize and repellet the resulting resin composition after coating. .

 本技術に係る第2の実施形態の樹脂組成物の製造方法は、ポリエステルポリオールとポリイソシアネートとを反応させて架橋構造を有するポリウレタン樹脂を製造することを含むことが好ましい。ポリエステルポリオールとポリイソシアネートとを反応させて架橋構造を有するポリウレタン樹脂を製造する方法は、例えば、ポリエステルポリオールとポリイソシアネートとの2液を混合することと、その後、熱硬化反応すること又は光硬化することを含む、製造方法である。 It is preferable that the method for producing the resin composition of the second embodiment according to the present technology includes producing a polyurethane resin having a crosslinked structure by reacting a polyester polyol and a polyisocyanate. A method for producing a polyurethane resin having a crosslinked structure by reacting a polyester polyol and a polyisocyanate is, for example, mixing two liquids of a polyester polyol and a polyisocyanate, and then performing a thermosetting reaction or photocuring. This is a manufacturing method.

 <4.第3の実施形態(樹脂成形体の例)>
 [4-1.樹脂成形体]
 本技術に係る第3の実施形態の樹脂成形体は、本技術に係る第1の実施形態の樹脂組成物を成形加工して得られる樹脂成形体である。また、本技術に係る第3の実施形態の樹脂成形体は、本技術に係る第1の実施形態の樹脂組成物を含んでなる樹脂成形体でもよい。本技術に係る第1の実施形態の樹脂組成物は、機械的物性を低下させることなく、流動性の向上により加工適性が良化し、さらに、耐薬品性等の表面物性が向上するので、OA機器・複写機向けや、車載、医療系用途の好適な樹脂成形体を得ることができる。
<4. Third Embodiment (Example of Resin Molded Body)>
[4-1. Resin molded body]
The resin molded body of the third embodiment according to the present technology is a resin molded body obtained by molding the resin composition of the first embodiment according to the present technology. In addition, the resin molded body of the third embodiment according to the present technology may be a resin molded body including the resin composition of the first embodiment according to the present technology. The resin composition of the first embodiment according to the present technology improves processability by improving fluidity without lowering mechanical properties, and further improves surface properties such as chemical resistance. It is possible to obtain a resin molded article suitable for equipment / copiers, in-vehicle use, and medical use.

 [4-2.樹脂成形体の製造方法]
 本技術に係る第3の実施形態の樹脂成形体は、例えば、以下のようにして製造することができる。本技術に係る第1の実施形態の樹脂組成物からなるペレット等、又は本技術に係る第2の実施形態の樹脂組成物の製造方法から製造された樹脂組成物からなるペレット等を、射出成形、射出圧縮成形、押出成形、ブロー成形、真空成形、プレス成形、発泡成形、あるいは超臨界成形などといった成形法により所定の形状(例えば、家電、自動車、情報機器、事務機器、電話機、文房具、家具、あるいは繊維などの各種製品の筐体や部品材)に成形して、樹脂成形体を得ることができる。
[4-2. Manufacturing method of resin molding]
The resin molded body of the third embodiment according to the present technology can be manufactured as follows, for example. Injection molding of pellets made of the resin composition of the first embodiment according to the present technology, or pellets made of the resin composition manufactured from the method for producing the resin composition of the second embodiment according to the present technology , Injection compression molding, extrusion molding, blow molding, vacuum molding, press molding, foam molding, or supercritical molding, etc. to a predetermined shape (for example, home appliances, automobiles, information equipment, office equipment, telephones, stationery, furniture) Or molded into housings or parts of various products such as fibers) to obtain a resin molded body.

 本技術は、上記各実施形態にのみ限定されるものではなく、本技術の要旨を逸脱しない範囲内において変更することが可能である。 The present technology is not limited to the above embodiments, and can be changed without departing from the gist of the present technology.

 なお、本明細書に記載された効果はあくまでも例示であって限定されるものではなく、また他の効果があってもよい。 It should be noted that the effects described in this specification are merely examples and are not limited, and other effects may be obtained.

 また、本技術は、以下のような構成も取ることができる。
[1]
 芳香族ポリカーボネート樹脂100質量部と、架橋構造を有するポリウレタン樹脂0.01~5.0質量部とを含み、
 該ポリウレタン樹脂が硬化樹脂である、樹脂組成物。
[2]
 前記架橋構造を有するポリウレタン樹脂の粉体の平均粒径が0.5mm~1.5mmである、[1]に記載の樹脂組成物。
[3]
 前記架橋構造を有するポリウレタン樹脂の全粉体に対して、前記架橋構造を有するポリウレタン樹脂の粉体の粒径が0.5mm~1.5mmである割合が70%以上である、[1]又は[2]に記載の樹脂組成物。
[4]
 前記架橋構造を有するポリウレタン樹脂が、ポリエステルポリオールとポリイソシアネートとの反応から得られる、[1]から[3]のいずれか1つに記載の樹脂組成物。
[5]
 前記ポリエステルポリオールと前記ポリイソシアネートとの質量比が、100:50~100:200である、[4]に記載の樹脂組成物。
[6]
 前記ポリエステルポリオールの水酸基価が30~300である、[4]又は[5]に記載の樹脂組成物。
[7]
 前記ポリエステルポリオールのポリスチレン換算の重量平均分子量が、10,000以上500,000以下である、[4]から[6]のいずれか1つに記載の樹脂組成物。
[8]
 前記ポリイソシアネートが2つ以上のイソシアネート基を有する、[4]から[7]のいずれか1つに記載の樹脂組成物。
[9]
 前記芳香族ポリカーボネート樹脂100質量部に対して、有機スルホン酸及び/又は有機スルホン酸金属塩化合物0.01~3.0質量部を更に含む、[1]から[8]のいずれか1つに記載の樹脂組成物。
[10]
 前記有機スルホン酸金属塩化合物のポリスチレン換算の重量平均分子量が、30,000以上である、[9]に記載の樹脂組成物。
[11]
 前記有機スルホン酸金属塩化合物がスルホン酸金属塩基を含有し、該スルホン酸金属塩基の含有量が0.1~10モル%である、[9]又は[10]に記載の樹脂組成物。
[12]
 前記芳香族ポリカーボネート樹脂が、再生ポリカーボネート樹脂を含み、該再生ポリカーボネート樹脂の含有量が、前記芳香族ポリカーボネート樹脂の全質量に対して1~100質量%未満である、[1]から[11]のいずれか1つに記載の樹脂組成物。
[13]
 前記芳香族ポリカーボネート樹脂100質量部に、前記架橋構造を有するポリウレタン樹脂0.01~5.0重量部を添加して、前記芳香族ポリカーボネート樹脂と前記架橋構造を有するポリウレタン樹脂とを混錬して得られる、[1]から[12]のいずれか1つに記載の樹脂組成物。
[14]
 芳香族ポリカーボネート樹脂100質量部に、架橋構造を有するポリウレタン樹脂0.01~5.0重量部を添加することと、
 該芳香族ポリカーボネート樹脂と該架橋構造を有するポリウレタン樹脂とを混錬することとを含む、樹脂組成物の製造方法。
[15]
 ポリエステルポリオールとポリイソシアネートとを反応させて前記架橋構造を有するポリウレタン樹脂を製造することを含む、[14]に記載の樹脂組成物の製造方法。
In addition, the present technology may have the following configurations.
[1]
Including 100 parts by weight of an aromatic polycarbonate resin and 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure,
A resin composition, wherein the polyurethane resin is a cured resin.
[2]
The resin composition according to [1], wherein the polyurethane resin powder having a crosslinked structure has an average particle size of 0.5 mm to 1.5 mm.
[3]
The ratio of the particle size of the polyurethane resin powder having the crosslinked structure to 0.5 mm to 1.5 mm is 70% or more with respect to the total powder of the polyurethane resin having the crosslinked structure, [1] or The resin composition as described in [2].
[4]
The resin composition according to any one of [1] to [3], wherein the polyurethane resin having the crosslinked structure is obtained from a reaction between a polyester polyol and a polyisocyanate.
[5]
The resin composition according to [4], wherein a mass ratio of the polyester polyol to the polyisocyanate is 100: 50 to 100: 200.
[6]
[4] or [5], wherein the polyester polyol has a hydroxyl value of 30 to 300.
[7]
The resin composition according to any one of [4] to [6], wherein the polyester polyol has a polystyrene-equivalent weight average molecular weight of 10,000 or more and 500,000 or less.
[8]
The resin composition according to any one of [4] to [7], wherein the polyisocyanate has two or more isocyanate groups.
[9]
[1] to [8], further comprising 0.01 to 3.0 parts by mass of an organic sulfonic acid and / or organic sulfonic acid metal salt compound with respect to 100 parts by mass of the aromatic polycarbonate resin. The resin composition as described.
[10]
The resin composition according to [9], wherein the organic sulfonic acid metal salt compound has a polystyrene-equivalent weight average molecular weight of 30,000 or more.
[11]
The resin composition according to [9] or [10], wherein the organic sulfonic acid metal salt compound contains a sulfonic acid metal base, and the content of the sulfonic acid metal base is 0.1 to 10 mol%.
[12]
[1] to [11], wherein the aromatic polycarbonate resin includes a regenerated polycarbonate resin, and the content of the regenerated polycarbonate resin is 1 to less than 100% by mass with respect to the total mass of the aromatic polycarbonate resin. The resin composition as described in any one.
[13]
0.01 to 5.0 parts by weight of the polyurethane resin having the crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the polyurethane resin having the crosslinked structure are kneaded. The obtained resin composition according to any one of [1] to [12].
[14]
Adding 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure to 100 parts by weight of an aromatic polycarbonate resin;
A method for producing a resin composition, comprising kneading the aromatic polycarbonate resin and a polyurethane resin having a crosslinked structure.
[15]
The method for producing a resin composition according to [14], comprising producing a polyurethane resin having the crosslinked structure by reacting a polyester polyol and a polyisocyanate.

 以下に、実施例を挙げて、本技術の効果について具体的に説明をする。なお、本技術の範囲は実施例に限定されるものではない。 Hereinafter, the effects of the present technology will be described in detail with examples. Note that the scope of the present technology is not limited to the examples.

 実施例1-1~1-10及び実施例2-1~2-10に係る樹脂組成物、並びに比較例1-1~1-5及び比較例2-1~2-4に係る樹脂組成物を準備し、各々の樹脂組成物について評価を実施した。なお、比較例1-5はコート品であり、以下のように製造をした。
 比較例1-5(コート品)は、コーティング材をロールコーター法、スプレー法、又はディッピング法の方法で、基材表面に塗装した。塗装後は、必要に応じて、60~120℃の範囲で数秒~10分程度加熱乾燥することによって、基材表面に所望の塗膜を形成した。コーティング材は、ポリエステルポリオール(プラクセルPCL305(ダイセル化学工業(株)製))成分とポリイソシアネート系硬化剤(デュラネートTPA-100(旭化成工業(株)製))のイソシアネート当量数=100:100となるように組み合わせて、二液硬化型塗料組成物とした。
Resin compositions according to Examples 1-1 to 1-10 and Examples 2-1 to 2-10, and resin compositions according to Comparative Examples 1-1 to 1-5 and Comparative Examples 2-1 to 2-4 Was prepared, and each resin composition was evaluated. Comparative Example 1-5 was a coated product, and was manufactured as follows.
In Comparative Example 1-5 (coated product), the coating material was applied to the surface of the substrate by a roll coater method, a spray method, or a dipping method. After coating, a desired coating film was formed on the substrate surface by heating and drying at 60 to 120 ° C. for several seconds to 10 minutes as necessary. The number of isocyanate equivalents of the polyester polyol (Placcel PCL305 (manufactured by Daicel Chemical Industries)) and the polyisocyanate curing agent (Duranate TPA-100 (manufactured by Asahi Kasei Kogyo)) is 100: 100. Thus, a two-component curable coating composition was obtained.

 実施例1-1~1-10の樹脂組成物の各成分の組成(質量部)と、流動性(g/10min)、引張強度(%)、耐薬品性及び折り曲げ強度の評価結果とを下記の表1に示す。また、比較例1-1~1-5の樹脂組成物の各成分の組成(質量部)と、流動性(g/10min)、引張強度(%)、耐薬品性及び折り曲げ強度の評価結果とを下記の表2に示す。 The composition (parts by mass) of each component of the resin compositions of Examples 1-1 to 1-10 and the evaluation results of fluidity (g / 10 min), tensile strength (%), chemical resistance and bending strength are shown below. Table 1 shows. Further, the composition (parts by mass) of each component of the resin compositions of Comparative Examples 1-1 to 1-5, and evaluation results of fluidity (g / 10 min), tensile strength (%), chemical resistance, and bending strength Is shown in Table 2 below.

 実施例2-1~2-10の樹脂組成物の各成分の組成(質量部)と、流動性(g/10min)、引張強度(%)、耐薬品性、難燃性(UL94、1.6mm)及び折り曲げ強度の評価結果とを下記の表3に示す。また、比較例2-1~2-4の樹脂組成物の各成分の組成(質量部)と、流動性(g/10min)、引張強度(%)、耐薬品性、難燃性(UL94、1.6mm)及び折り曲げ強度の評価結果とを下記の表4に示す。 Composition (parts by mass) of each component of the resin compositions of Examples 2-1 to 2-10, fluidity (g / 10 min), tensile strength (%), chemical resistance, flame resistance (UL94, 1. 6 mm) and the evaluation results of the bending strength are shown in Table 3 below. Further, the composition (parts by mass) of each component of the resin compositions of Comparative Examples 2-1 to 2-4, fluidity (g / 10 min), tensile strength (%), chemical resistance, flame resistance (UL94, 1.6 mm) and the evaluation results of the bending strength are shown in Table 4 below.

[実施例1-1~1-10及び実施例2-1~2-10に係る樹脂組成物、並びに比較例1-1~1-5及び2-1~2-4に係る樹脂組成物の構成]
 実施例1-1~1-10及び実施例2-1~2-10に係る樹脂組成物、並びに比較例1-1~1-5及び2-1~2-4に係る樹脂組成物に含有される各成分について説明する。なお、各成分(A成分、B成分、C成分、D成分、E成分及びF成分)は、上記の本技術に係る第1の実施形態の樹脂組成物において説明した、芳香族ポリカーボネート樹脂、架橋構造を有するポリウレタン樹脂、ポリエステルポリオール、ポリイソシアネート、有機スルホン酸及び/又は有機スルホン酸金属塩化合物、並びにドリップ防止剤のそれぞれと対応する。
[The resin compositions according to Examples 1-1 to 1-10 and Examples 2-1 to 2-10 and the resin compositions according to Comparative Examples 1-1 to 1-5 and 2-1 to 2-4] Constitution]
Included in the resin compositions according to Examples 1-1 to 1-10 and Examples 2-1 to 2-10, and the resin compositions according to Comparative Examples 1-1 to 1-5 and 2-1 to 2-4 Each component to be described will be described. In addition, each component (A component, B component, C component, D component, E component, and F component) is the aromatic polycarbonate resin described in the resin composition of 1st Embodiment which concerns on said this technique, bridge | crosslinking. It corresponds to each of polyurethane resin having a structure, polyester polyol, polyisocyanate, organic sulfonic acid and / or organic sulfonic acid metal salt compound, and anti-drip agent.

 (A成分:芳香族ポリカーボネート樹脂)
 A成分である芳香族ポリカーボネート樹脂として、以下のA-1~A-4の成分を用いた。
(Component A: aromatic polycarbonate resin)
The following components A-1 to A-4 were used as the aromatic polycarbonate resin as the component A.

  ・A-1:市販の中分子量PC樹脂(L-1225L:帝人化成品、PS換算のMw45000)。
  ・A-2:市販の低分子量PC樹脂(L-1225LLL:帝人化成品、PS換算のMw33000)。
  ・A-3:使用済み建材用シートを粗粉砕し、二軸押し出し機にて溶融・混練の後ペレット化したPC樹脂(PS換算のMw:46000)。
  ・A-4:使用済みCDを粉砕処理(2~20mm)したものをアルカリ性の熱水溶液で処理することにより塗装膜(記録材料層、レーベル、接着剤層、硬化層、金属反射層等)を除去した後、二軸押し出し機にて溶融・混練の後ペレット化したPC樹脂(PS換算のMw:32000)。
A-1: Commercially available medium molecular weight PC resin (L-1225L: Teijin Chemicals, PS converted Mw 45000).
A-2: Commercially available low molecular weight PC resin (L-1225LLL: Teijin Chemicals, Mw 33000 in terms of PS).
A-3: PC resin (Mw in PS conversion: 46000) obtained by roughly pulverizing used building material sheets, melting and kneading with a twin screw extruder, and then pelletizing.
A-4: Used CD is pulverized (2 to 20 mm) and treated with an alkaline hot water solution to form a coating film (recording material layer, label, adhesive layer, cured layer, metal reflective layer, etc.) After removing, PC resin (Mw in PS conversion: 32000) pelletized after melting and kneading with a twin screw extruder.

 (B成分:架橋構造を有するポリウレタン樹脂)
 B成分である架橋構造を有するポリウレタン樹脂として、以下の熱硬化樹脂であるB-1~B-3の成分を用いた。なお、B-3の成分で用いられたC-1成分及びD-1成分は下記に示す。
(B component: polyurethane resin having a crosslinked structure)
The following components B-1 to B-3, which are thermosetting resins, were used as the polyurethane resin having a crosslinked structure as the B component. The C-1 component and D-1 component used in the B-3 component are shown below.

  ・B-1:ネオラバサンN781(武蔵塗料(株)製)。
  ・B-2:ネオラバサンソフトNS781(武蔵塗料(株)製)。
  ・B-3:C-1及びD-1を、100質量部:100質量部(C-1:D-1)で混合後、80℃で10分間加熱して反応させてなる架橋構造を有するポリウレタン樹脂。
B-1: Neolabasan N781 (Musashi Paint Co., Ltd.)
B-2: Neo Rabasan Soft NS781 (Musashi Paint Co., Ltd.)
B-3: having a cross-linked structure obtained by mixing C-1 and D-1 with 100 parts by mass: 100 parts by mass (C-1: D-1) and then reacting by heating at 80 ° C. for 10 minutes. Polyurethane resin.

 (C成分:ポリエステルポリオール)
 C成分であるポリエステルポリオールとして、以下のC-1の成分を用いた。
(C component: polyester polyol)
The following component C-1 was used as the polyester polyol as component C.

  ・C-1:プラクセルPCL305(ダイセル化学工業(株)製)。 C-1: Plaxel PCL305 (manufactured by Daicel Chemical Industries).

 (D成分:ポリイソシアネート)
 D成分であるポリイソシアネートとして、以下のD-1の成分を用いた。
(D component: polyisocyanate)
The following component D-1 was used as the polyisocyanate as component D.

  ・D-1:デュラネートTPA-100(旭化成工業(株)製)。 D-1: Duranate TPA-100 (manufactured by Asahi Kasei Corporation).

 (E成分:有機スルホン酸及び有機スルホン酸金属塩化合物)
 E成分である有機スルホン酸及び有機スルホン酸金属塩化合物として、以下のE-1~E-2の成分を用いた。
(E component: organic sulfonic acid and organic sulfonic acid metal salt compound)
The following components E-1 to E-2 were used as the organic sulfonic acid and organic sulfonic acid metal salt compound as the E component.

  ・E-1:有機スルホン酸金属塩化合物、ポリスチレンの表層部にスルホン酸カリウム塩を導入したもの(ソニー(株)製:PSS-K)。
  ・E-2:有機スルホン酸、ポリスチレンの表層部にスルホン酸を導入したもの(ソニー(株)製:PSS-H)。
E-1: organic sulfonic acid metal salt compound, in which potassium sulfonate is introduced into the surface layer of polystyrene (manufactured by Sony Corporation: PSS-K).
E-2: Organic sulfonic acid, one obtained by introducing sulfonic acid into the surface layer of polystyrene (manufactured by Sony Corporation: PSS-H).

 (F成分:ドリップ防止剤)
 F成分であるドリップ防止剤として、以下のF-1の成分を用いた。
  ・F-1:フィブリル形成能を有するポリテトラフルオロエチレンとして市販のPTFE(ダイキン工業株式会社製:ポリフロンFA500H)。
(F component: anti-drip agent)
The following components of F-1 were used as the anti-drip agent which is the F component.
F-1: PTFE commercially available as polytetrafluoroethylene having fibril-forming ability (manufactured by Daikin Industries, Ltd .: Polyflon FA500H).

 [実施例1-1~1-10及び実施例2-1~2-10に係る樹脂組成物、並びに比較例1-1~1-5及び2-1~2-4に係る樹脂組成物の成形]
 以上に示した各種成分(A-1~A-4の成分、B-1~B-3の成分、E-1~E-2の成分、及びF-1の成分)を、表1(実施例1-1~実施例1-10)、表2(比較例1-1~比較例1-5)、表3(実施例2-1~実施例2-10)及び表4(比較例2-1~比較例2-4)に示される各々の配合比にて配合を行い、タンブラーにてブレンドした後、二軸同方向回転混連押出機(東洋精機製作所製:ラボプラストミル、二軸押し出しユニット使用)を用いて溶融混練しペレットを得た。押出条件は吐出量4kg/h、スクリュー回転数48rpmであり、また押出温度は第1供給口からダイス部分まで270℃とした。得られたペレットを120℃で8時間、熱風循環式乾燥機にて乾燥した後、射出成形機を用いて、シリンダー温度290℃および金型温度70℃で、下記に示される試験方法で用いられる試験片を成形した。
[The resin compositions according to Examples 1-1 to 1-10 and Examples 2-1 to 2-10 and the resin compositions according to Comparative Examples 1-1 to 1-5 and 2-1 to 2-4] Molding]
The various components shown above (components A-1 to A-4, components B-1 to B-3, components E-1 to E-2, and components F-1) are shown in Table 1 (implementation). Example 1-1 to Example 1-10), Table 2 (Comparative Example 1-1 to Comparative Example 1-5), Table 3 (Example 2-1 to Example 2-10) and Table 4 (Comparative Example 2) -1 to Comparative Example 2-4) After blending at each blending ratio and blending with a tumbler, a twin-screw co-rotating extruder (Toyo Seiki Seisakusho: Labo Plast Mill, twin-screw) Using an extrusion unit, the mixture was melt-kneaded to obtain pellets. Extrusion conditions were a discharge rate of 4 kg / h, a screw rotation speed of 48 rpm, and an extrusion temperature of 270 ° C. from the first supply port to the die part. The obtained pellets were dried in a hot air circulating dryer at 120 ° C. for 8 hours, and then used in the test method shown below at a cylinder temperature of 290 ° C. and a mold temperature of 70 ° C. using an injection molding machine. A test piece was molded.

 次に、以下の試験方法にしたがって、上記で作製した試験片を用いて、流動性(g/10min)、引張強度(%)、耐薬品性及び難燃性の評価を行った。 Next, according to the following test method, fluidity (g / 10 min), tensile strength (%), chemical resistance and flame retardance were evaluated using the test pieces prepared above.

 [流動性(g/10min)(MFR:メルトフローレート)の試験方法]
 JIS K7210に従い、樹脂温度280℃、荷重2.16Kgの条件で、溶融時の樹脂組成物の流れ性の測定を行った。流動性(g/10min)の評価結果を下記の表1~表4に示す。
[Test method for fluidity (g / 10 min) (MFR: melt flow rate)]
According to JIS K7210, the flowability of the resin composition at the time of melting was measured under the conditions of a resin temperature of 280 ° C. and a load of 2.16 Kg. The evaluation results of fluidity (g / 10 min) are shown in Tables 1 to 4 below.

 [引張強度(%)の試験方法]
 試験片について、JIS K7162法に従って引張試験を行い、引張強度を測定した。引張強度(%)の評価結果を下記の表1~表4に示す。
[Test method for tensile strength (%)]
The test piece was subjected to a tensile test according to JIS K7162 method, and the tensile strength was measured. The evaluation results of tensile strength (%) are shown in Tables 1 to 4 below.

 [耐薬品性の試験方法]
 試験片を用いて、3点曲げ試験法にて、1%歪みをかけた後、日焼け止めクリーム:サンプレイスーパーブロックd(ロート製薬(株)製)を含浸させた布をかけ、23℃で72時間放置した後に、外観変化の有無を確認した。耐薬品性の評価結果を下記の表1~表4に示す。なお、評価は下記の基準で実施した。
[Chemical resistance test method]
Using a test piece, after applying a strain of 1% by a three-point bending test method, a cloth impregnated with sunscreen cream: Sunplay Super Block d (manufactured by Rohto Pharmaceutical Co., Ltd.) is applied at 23 ° C. After leaving for 72 hours, the presence or absence of appearance change was confirmed. The evaluation results of chemical resistance are shown in Tables 1 to 4 below. The evaluation was performed according to the following criteria.

 (耐薬品性の評価基準)
  ○:外観変化が見られないもの。
  △:微細なクラックの発生が見られるもの。
  ×:破断にいたるような大きなクラックが見られるもの。
(Evaluation criteria for chemical resistance)
○: No change in appearance.
Δ: The occurrence of fine cracks.
X: The thing by which the big crack which leads to a fracture | rupture is seen.

 [難燃性の試験方法]
 UL規格94の垂直燃焼試験を、厚み1.6mmで行いその等級を評価し、V-1以上を良好として判定した。UL94V規格と判定基準を下記の表5に示す。難燃性の評価結果を下記の表3~表4に示す。なお、UL94V規格と判定基準を下記の表5に示す。
[Flame retardancy test method]
A vertical combustion test of UL standard 94 was conducted at a thickness of 1.6 mm, the grade was evaluated, and V-1 or higher was judged as good. The UL94V standard and criteria are shown in Table 5 below. The evaluation results of flame retardancy are shown in Tables 3 to 4 below. The UL94V standard and determination criteria are shown in Table 5 below.

 [折り曲げ強度の試験方法]
 折り曲げ試験は、作製した試験片(長さ110mm、横幅13mm、厚さ1.0mm)を折り曲げていき、破壊した角度を測定することで、耐衝撃性を定性評価する試験の一種である。本評価では、破壊した角度が90℃以上である場合、○とし、90℃以内である場合、×とした。
[Bending strength test method]
The bending test is a kind of test for qualitatively evaluating impact resistance by bending a prepared test piece (length: 110 mm, width: 13 mm, thickness: 1.0 mm) and measuring a broken angle. In this evaluation, when the destroyed angle was 90 ° C. or more, it was evaluated as “◯”, and when it was within 90 ° C., it was evaluated as “X”.

 下記の表1に実施例1-1~1-10の結果、及び表2に比較例1-1~1-5の結果を示す。 Table 1 below shows the results of Examples 1-1 to 1-10, and Table 2 shows the results of Comparative Examples 1-1 to 1-5.

 表1及び表2から明らかなように、実施例1-1~1-10に係る樹脂組成物は、薄肉成形品に対応可能であった。また、実施例1-1~1-10に係る樹脂組成物は、比較例1-1~1-5に係る樹脂組成物と比べて、成形性(流動性)、機械的物性(引張強度及び折り曲げ強度)及び表面物性(耐薬品性)に優れる樹脂組成物であった。 As is clear from Tables 1 and 2, the resin compositions according to Examples 1-1 to 1-10 were compatible with thin molded products. In addition, the resin compositions according to Examples 1-1 to 1-10 have moldability (fluidity), mechanical properties (tensile strength and tensile strength) as compared with the resin compositions according to Comparative Examples 1-1 to 1-5. The resin composition had excellent bending strength and surface properties (chemical resistance).

 実施例と比較例とを芳香族ポリカーボネート樹脂の同分子量で比較すると、すなわち、実施例1-1~1-3及び実施例1-7~1-8並びに比較例1-1の比較、実施例1-4及び比較例1-2の比較、実施例1-5及び比較例1-3の比較、並びに実施例1-6及び比較例1-4の比較をすると、実施例は比較例に対して、機械的物性(引張強度及び折り曲げ強度)は略同等であったが、流動性、表面物性(耐薬品性)は優れていた。 When Examples and Comparative Examples are compared with the same molecular weight of the aromatic polycarbonate resin, that is, Examples 1-1 to 1-3, Examples 1-7 to 1-8, and Comparative Example 1-1 are compared. When comparing 1-4 and comparative example 1-2, comparing example 1-5 and comparative example 1-3, and comparing example 1-6 and comparative example 1-4, the example was compared to the comparative example. The mechanical properties (tensile strength and bending strength) were substantially the same, but the fluidity and surface properties (chemical resistance) were excellent.

 実施例1-1~1-10と比較例1-5とを比較した。比較例1-5は、耐薬品性の向上を目的とした、ポリウレタン樹脂をカーボネート樹脂にコートしたコート品である。実施例1-1~1-10に係る樹脂組成物は、比較例1-5に係る樹脂組成物に対して、機械的物性(引張強度及び折り曲げ強度)を低下させることなく、表面物性(耐薬品性)を付与することができるため、優れていた。また、実施例1-1~1-10に係る樹脂組成物は、比較例1-5に係る樹脂組成物に対して、成形(流動性)の自由度が向上する点も非常に優れていた。 Examples 1-1 to 1-10 were compared with Comparative Example 1-5. Comparative Example 1-5 is a coated product in which a carbonate resin is coated with a polyurethane resin for the purpose of improving chemical resistance. The resin compositions according to Examples 1-1 to 1-10, compared with the resin composition according to Comparative Example 1-5, have a surface physical property (anti-resistance) without reducing mechanical properties (tensile strength and bending strength). Since chemical properties can be imparted, it was excellent. In addition, the resin compositions according to Examples 1-1 to 1-10 were very excellent in that the degree of freedom of molding (fluidity) was improved as compared with the resin composition according to Comparative Example 1-5. .

 下記の表3に実施例2-1~2-10の結果、及び表4に比較例2-1~2-4の結果を示す。 Table 3 below shows the results of Examples 2-1 to 2-10, and Table 4 shows the results of Comparative Examples 2-1 to 2-4.

 表3及び表4から明らかなように、実施例2-1~2-10に係る樹脂組成物は、薄肉成形品に対応可能であった。また、有機スルホン酸又は有機スルホン酸金属塩化合物(難燃剤)を添加した実施例2-1~2-10に係る樹脂組成物は、比較例2-1~2-4に係る樹脂組成物と比べて、成形性(流動性)、機械的物性(引張強度及び折り曲げ強度)及び表面物性(耐薬品性)並びに難燃性に優れる樹脂組成物であった。 As is clear from Tables 3 and 4, the resin compositions according to Examples 2-1 to 2-10 were compatible with thin molded products. In addition, the resin compositions according to Examples 2-1 to 2-10 to which organic sulfonic acid or organic sulfonic acid metal salt compound (flame retardant) was added are the same as the resin compositions according to Comparative Examples 2-1 to 2-4. In comparison, the resin composition was excellent in moldability (fluidity), mechanical properties (tensile strength and bending strength), surface properties (chemical resistance) and flame retardancy.

Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009

Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010

Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011

Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012

Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013

Claims (15)

 芳香族ポリカーボネート樹脂100質量部と、架橋構造を有するポリウレタン樹脂0.01~5.0質量部とを含み、
 該ポリウレタン樹脂が硬化樹脂である、樹脂組成物。
Including 100 parts by weight of an aromatic polycarbonate resin and 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure,
A resin composition, wherein the polyurethane resin is a cured resin.
 前記架橋構造を有するポリウレタン樹脂の粉体の平均粒径が0.5mm~1.5mmである、請求項1に記載の樹脂組成物。 2. The resin composition according to claim 1, wherein the polyurethane resin powder having a crosslinked structure has an average particle size of 0.5 mm to 1.5 mm.  前記架橋構造を有するポリウレタン樹脂の全粉体に対して、前記架橋構造を有するポリウレタン樹脂の粉体の粒径が0.5mm~1.5mmである割合が70%以上である、請求項1に記載の樹脂組成物。 2. The ratio of the particle size of the polyurethane resin powder having the crosslinked structure to 0.5 mm to 1.5 mm is 70% or more with respect to the total powder of the polyurethane resin having the crosslinked structure. The resin composition as described.  前記架橋構造を有するポリウレタン樹脂が、ポリエステルポリオールとポリイソシアネートとの反応から得られる、請求項1に記載の樹脂組成物。 The resin composition according to claim 1, wherein the polyurethane resin having a crosslinked structure is obtained from a reaction between a polyester polyol and a polyisocyanate.  前記ポリエステルポリオールと前記ポリイソシアネートとの質量比が、100:50~100:200である、請求項4に記載の樹脂組成物。 The resin composition according to claim 4, wherein a mass ratio of the polyester polyol to the polyisocyanate is 100: 50 to 100: 200.  前記ポリエステルポリオールの水酸基価が30~300である、請求項4に記載の樹脂組成物。 The resin composition according to claim 4, wherein the polyester polyol has a hydroxyl value of 30 to 300.  前記ポリエステルポリオールのポリスチレン換算の重量平均分子量が、10,000以上500,000以下である、請求項4に記載の樹脂組成物。 The resin composition according to claim 4, wherein the polyester polyol has a polystyrene-equivalent weight average molecular weight of 10,000 or more and 500,000 or less.  前記ポリイソシアネートが2つ以上のイソシアネート基を有する、請求項4に記載の樹脂組成物。 The resin composition according to claim 4, wherein the polyisocyanate has two or more isocyanate groups.  前記芳香族ポリカーボネート樹脂100質量部に対して、有機スルホン酸及び/又は有機スルホン酸金属塩化合物0.01~3.0質量部を更に含む、請求項1に記載の樹脂組成物。 The resin composition according to claim 1, further comprising 0.01 to 3.0 parts by mass of an organic sulfonic acid and / or an organic sulfonic acid metal salt compound with respect to 100 parts by mass of the aromatic polycarbonate resin.  前記有機スルホン酸金属塩化合物のポリスチレン換算の重量平均分子量が、30,000以上である、請求項9に記載の樹脂組成物。 The resin composition according to claim 9, wherein the weight average molecular weight in terms of polystyrene of the organic sulfonic acid metal salt compound is 30,000 or more.  前記有機スルホン酸金属塩化合物がスルホン酸金属塩基を含有し、該スルホン酸金属塩基の含有量が0.1~10モル%である、請求項9に記載の樹脂組成物。 The resin composition according to claim 9, wherein the organic sulfonic acid metal salt compound contains a sulfonic acid metal base, and the content of the sulfonic acid metal base is 0.1 to 10 mol%.  前記芳香族ポリカーボネート樹脂が、再生ポリカーボネート樹脂を含み、該再生ポリカーボネート樹脂の含有量が、前記芳香族ポリカーボネート樹脂の全質量に対して1~100質量%未満である、請求項1に記載の樹脂組成物。 The resin composition according to claim 1, wherein the aromatic polycarbonate resin includes a regenerated polycarbonate resin, and a content of the regenerated polycarbonate resin is 1 to less than 100% by mass with respect to a total mass of the aromatic polycarbonate resin. object.  前記芳香族ポリカーボネート樹脂100質量部に、前記架橋構造を有するポリウレタン樹脂0.01~5.0重量部を添加して、前記芳香族ポリカーボネート樹脂と前記架橋構造を有するポリウレタン樹脂とを混錬して得られる、請求項1に記載の樹脂組成物。 0.01 to 5.0 parts by weight of the polyurethane resin having the crosslinked structure is added to 100 parts by mass of the aromatic polycarbonate resin, and the aromatic polycarbonate resin and the polyurethane resin having the crosslinked structure are kneaded. The resin composition of Claim 1 obtained.  芳香族ポリカーボネート樹脂100質量部に、架橋構造を有するポリウレタン樹脂0.01~5.0重量部を添加することと、
 該芳香族ポリカーボネート樹脂と該架橋構造を有するポリウレタン樹脂とを混錬することとを含む、樹脂組成物の製造方法。
Adding 0.01 to 5.0 parts by weight of a polyurethane resin having a crosslinked structure to 100 parts by weight of an aromatic polycarbonate resin;
A method for producing a resin composition, comprising kneading the aromatic polycarbonate resin and a polyurethane resin having a crosslinked structure.
 ポリエステルポリオールとポリイソシアネートとを反応させて前記架橋構造を有するポリウレタン樹脂を製造することを含む、請求項14に記載の樹脂組成物の製造方法。 The manufacturing method of the resin composition of Claim 14 including reacting polyester polyol and polyisocyanate and manufacturing the polyurethane resin which has the said crosslinked structure.
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