[go: up one dir, main page]

WO2010103719A1 - Ensemble de matériaux de formation d'un film de revêtement de résine de polyuréthane formé sur un substrat - Google Patents

Ensemble de matériaux de formation d'un film de revêtement de résine de polyuréthane formé sur un substrat Download PDF

Info

Publication number
WO2010103719A1
WO2010103719A1 PCT/JP2010/000591 JP2010000591W WO2010103719A1 WO 2010103719 A1 WO2010103719 A1 WO 2010103719A1 JP 2010000591 W JP2010000591 W JP 2010000591W WO 2010103719 A1 WO2010103719 A1 WO 2010103719A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyol
polyurethane resin
material set
resin film
film material
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/JP2010/000591
Other languages
English (en)
Japanese (ja)
Inventor
川口忠之
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.)
Nippon Polyurethane Industry Co Ltd
Original Assignee
Nippon Polyurethane Industry Co Ltd
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 Nippon Polyurethane Industry Co Ltd filed Critical Nippon Polyurethane Industry Co Ltd
Priority to CN2010800080646A priority Critical patent/CN102317390B/zh
Priority to KR1020117017059A priority patent/KR101224777B1/ko
Publication of WO2010103719A1 publication Critical patent/WO2010103719A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to a solvent-free polyurethane resin film material formed on a substrate to be coated, for example.
  • Polyurethane resin is used in various fields such as electronic / electrical materials, automobile / railway vehicle materials, civil engineering / building materials.
  • polyurethane resin paints are often used in the fields of architecture, civil engineering structures and vehicles, and have excellent coating appearance, good coating film performance, and excellent durability.
  • Polyurethane resin paints are often used together with organic solvents. In this case, improvement of environmental problems and work safety problems is a major issue.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a polyurethane resin film material set formed on a substrate that is excellent in film strength under solvent-free conditions.
  • the polyurethane resin film material set formed on the base material according to the present invention comprises a polyol obtained by the reaction of polycarbonate polyol and polycaprolactone polyol, and an isocyanate group-terminated prepolymer obtained by the reaction of polytetramethylene glycol and polyisocyanate.
  • the ratio of the polycarbonate polyol to the polycaprolactone polyol is 65/35 or more by mass ratio.
  • the polyurethane resin film material set formed on the substrate according to the present invention is preferably characterized in that both the polyol and the isocyanate group-terminated prepolymer are liquid at room temperature.
  • the polyol further contains a fine powdery organometallic catalyst for curing reaction and a curing reaction inhibitor at room temperature. It is characterized by that.
  • the polyurethane resin film material set formed on the substrate according to the present invention is preferably characterized in that the polyol is obtained by reaction of polycarbonate polyol, polycaprolactone polyol and aliphatic glycol. .
  • the polyurethane resin film material set formed on the substrate according to the present invention is preferably characterized in that the polycarbonate polyol is obtained by a reaction of 1,6-hexanediol and dialkyl carbonate. .
  • the polyurethane resin film material set formed on the substrate according to the present invention is preferably characterized in that the polyisocyanate is an aliphatic diisocyanate.
  • the polyurethane resin film material set formed on the substrate according to the present invention is preferably characterized in that the aliphatic diisocyanate is hexamethylene diisocyanate.
  • the polyurethane resin film material set formed on the base material according to the present invention comprises a polyol obtained by the reaction of polycarbonate polyol and polycaprolactone polyol, and an isocyanate group-terminated prepolymer obtained by the reaction of polytetramethylene glycol and polyisocyanate.
  • a polyol obtained by the reaction of polycarbonate polyol and polycaprolactone polyol obtained by the reaction of polytetramethylene glycol and polyisocyanate.
  • the ratio of the polycarbonate polyol to the polycaprolactone polyol is 65/35 or more by mass ratio, the strength of the polyurethane resin film formed on the substrate is excellent.
  • the polyurethane resin film material set (hereinafter simply referred to as the polyurethane resin film material set) formed on the base material according to the present embodiment forms a paint film on the substrate to be coated, for example, as a paint. Used to do.
  • the present invention is not limited to this, and it goes without saying that it can be used to form a polyurethane resin film on another substrate as long as the effects of the present invention are exhibited.
  • a polyol and an isocyanate group-terminated prepolymer are separately managed and used together with a curing catalyst during film formation.
  • the polyurethane resin film material set according to the second example of the present embodiment is used by further blending and containing a polyol and an organometallic catalyst for curing reaction and a curing reaction inhibitor at room temperature. Thereby, it is excellent in the handleability at the time of use of a polyurethane resin membrane material set.
  • the polyurethane resin film material set according to the first example and the second example of the present embodiment is a solvent-free film material that does not contain an organic solvent that may cause environmental problems.
  • the polyurethane resin film material set formed on the base material according to the first example includes a polyol obtained by reaction of polycarbonate polyol and polycaprolactone polyol, and an isocyanate group-terminated prepolymer obtained by reaction of polytetramethylene glycol and polyisocyanate. It consists of a polymer, and the ratio of polycarbonate polyol to polycaprolactone polyol (polycarbonate polyol / polycaprolactone polyol) is 65/35 or more in mass ratio.
  • Either one or both of the polyol and the isocyanate group-terminated prepolymer may be solid at room temperature. However, from the viewpoint of handling during storage and transportation, and the necessity of heating and melting when mixing and curing the two during film formation, both the polyol and the isocyanate group-terminated prepolymer are at room temperature. It is preferably liquid.
  • the polycarbonate polyol which is one of the raw materials of the polyol is not particularly limited in type, for example, a dehydrochlorination reaction of a short chain polyol and phosgene, or a low molecular weight such as a short chain polyol and a dialkyl carbonate, an alkylene carbonate or a diaryl carbonate. It can be suitably obtained by a transesterification condensation reaction with carbonate.
  • Examples of the short-chain polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane.
  • dialkyl carbonate examples include dimethyl carbonate and diethyl carbonate.
  • alkylene carbonate examples include ethylene carbonate and propylene carbonate.
  • diaryl carbonate examples include diphenyl carbonate. Any of these may be used alone or in admixture of two or more.
  • a polycarbonate polyol using a linear aliphatic glycol that contributes to the mechanical strength due to the expression of crystallinity is preferred, and in particular, 1,6-hexanediol and dialkyl It is preferably obtained by a carbonate reaction.
  • Polycaprolactone polyol which is one of the raw materials of polyol, is, for example, ring-opening addition of either or both of ⁇ -caprolactone and alkyl-substituted ⁇ -caprolactone using the short-chain polyol used in the aforementioned polycarbonate as an initiator. What is obtained can be used.
  • the polyol is obtained by transesterification by further blending an aliphatic glycol together with the polycarbonate polyol and the polycaprolactone polyol. It is preferable.
  • Aliphatic glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, dimethylolheptane, diethylene glycol, Examples thereof include dipropylene glycol and neopentyl glycol. From the viewpoint of further increasing the mechanical strength of the resulting polyurethane resin film, the aliphatic glycol preferably has a molecular weight of 200 or less, and most preferably 1,6-hexanediol.
  • the blending ratio of the polyol raw material is such that the ratio of polycarbonate polyol to polycaprolactone polyol (polycarbonate polyol / polycaprolactone polyol) is 65/35 or more by mass ratio.
  • the upper limit of the ratio is not particularly limited, and the polycarbonate polyol may be close to 100%, but from the viewpoint of handling it as a liquid at room temperature, it is preferably 75% or less (75/25 as a ratio).
  • the blending ratio is counted by using aliphatic glycol as the number of polycarbonate polyols [(polycarbonate polyol + aliphatic glycol) / polycaprolactone polyol].
  • Polytetramethylene glycol which is one of the raw materials for the isocyanate group-terminated prepolymer, is not particularly limited in molecular weight, but from the viewpoint of the appearance of the resulting polyurethane resin film, the number average molecular weight may be 500 or more. preferable.
  • 2,4-tolylene diisocyanate (hereinafter abbreviated as 2,4-TDI), 2 , 6-TDI, 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as 4,4′-MDI), 2,4′-MDI, 2,2′-MDI, 1,5-naphthylene diisocyanate, 1, 4-naphthylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2- Nitrodiphenyl-4,4'- Isocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphene
  • aliphatic aliphatic diisocyanate and alicyclic diisocyanate are preferable from the viewpoint of ease of blending with a polyol during the production of a polyurethane film, the appearance of the resulting polyurethane resin film, and mechanical strength.
  • Most preferred is hexamethylene diisocyanate (HDI).
  • the isocyanate group-terminated prepolymer has an isocyanate content of 4 to 12% by mass and an unreacted polyisocyanate content of 1% by mass or less.
  • the blending ratio of the polyol and the isocyanate group-terminated prepolymer when forming the film is not particularly limited, but the isocyanate group in the isocyanate group-terminated prepolymer is 0.90 per mole of hydroxyl group in the polyol. It is a preferable example to mix
  • the polyol of the polyurethane resin film material set formed on the base material according to the present embodiment is cured in a fine powder form at room temperature. It further contains a reaction organometallic catalyst and a curing reaction inhibitor.
  • a reaction organometallic catalyst and a curing reaction inhibitor As a result, the state in which the organometallic catalyst for curing reaction is dispersed in the polyol is maintained, so that compared with the case of adding the usual organometallic catalyst for curing reaction when forming a polyurethane resin film on the substrate. In other words, the so-called pot life can be extended and the curing time can be prevented from being delayed. This will be specifically described below.
  • the organometallic catalyst is not particularly limited as long as it is an organometallic compound that catalyzes a curing reaction under a predetermined curing temperature condition.
  • organometallic compound that catalyzes a curing reaction under a predetermined curing temperature condition.
  • Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Fe , Ti, Cu, Co, Ni, In, Ca, Y, Ce, Sr, Mo, La, etc. containing malate compounds, oxide compounds, ester compounds, mercaptide compounds and chelate compounds at room temperature solid or Mixtures of them can be employed.
  • organotin compounds include dibutyltin distelate, dibutyltin maleate polymer, dibutyltin bis (maleic acid alkyl ester) salt, bis (dibutyltin maleic acid alkyl ester) maleate, dibutyltin s, o-mercaptocarboxylic acid Salt polymer, dioctyltin distearate, dioctyltin maleate polymer, dioctyltin bis (maleic acid alkyl ester) salt, bis (dioctyltin maleic acid alkyl ester) maleate, dioctyltin s, o-mercaptocarboxylate polymer, Dioctyltin dioctate, dioctyltin oxide, etc.
  • the particle size of the organometallic catalyst is preferably 70 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the addition amount of the organometallic catalyst to the polyol is preferably in the range of 50 to 2000 ppm, more preferably, relative to the total amount of polyol and isocyanate group-terminated prepolymer used as the polyurethane resin film material set. The range is 80 to 1500 ppm.
  • adding a tertiary amine catalyst is not prevented.
  • the curing reaction inhibitor can contain at least one of phosphoric acid, phosphorous acid, acidic phosphoric acid ester, acidic phosphorous acid ester or a mixture thereof, and has a viewpoint of achieving both a long pot life and a short curing time.
  • Examples of the acidic phosphate ester include ethyl phosphate, diethyl phosphate, isopropyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) acid phosphate, isodecyl acid phosphate, lauryl acid
  • Examples thereof include phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, stearyl acid phosphate and the like.
  • the addition amount of the curing reaction inhibitor to the polyol is preferably in the range of 25 to 1000 ppm by mass with respect to the total amount of polyol and isocyanate group-terminated prepolymer used as the polyurethane resin film material set. Preferably, it is in the range of 40 to 750 ppm, more preferably in the range of 50 to 600 ppm.
  • a method for forming a polyurethane resin film formed on a substrate using the polyurethane resin film material set formed on the substrate according to the first example or the second example of the present embodiment A method for forming a coating film on a substrate using a polyurethane resin as a paint will be schematically described as an example.
  • the polyurethane resin film material set according to the present embodiment is mixed with release paper or the like at room temperature to prepare a film material (raw material) solution.
  • the amount of each of the polyol and the isocyanate group-terminated prepolymer is adjusted so that the isocyanate group in the isocyanate group-terminated prepolymer is 0.90 to 1.10 with respect to 1 mol of the hydroxyl group in the polyol.
  • the curing catalyst is added at a ratio of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the mixture of polyol and isocyanate group-terminated prepolymer. Further, when the coating material (raw material) is solid at normal temperature, it is heated to an appropriate temperature until it is liquefied.
  • the curing catalyst to be added uses the above-described organometallic catalyst together with the curing reaction inhibitor.
  • the curing catalyst is not particularly limited.
  • triethylamine triethylenediamine, N-methylimidazole, N-ethylmorpholine
  • Amines such as 1,8-diazabicyclo-5,4,0-undecene-7 (DBU), Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Fe, Ti, Cu, Co, Ni, In , Ca, Y, Ce, Sr, Mo, La, and other metal-containing malate compounds, oxide compounds, ester compounds, mercaptide compounds And chelate compounds, specifically can be used potassium acetate, stannous octoate, dibutyl tin dilaurate, organometallics, such as dioctyl dilaurate (DOTDL) or the like suitably.
  • the polyurethane resin film material set or the like formed on the base material according to the present embodiment described above is excellent in the strength of the polyurethane resin film formed on the base material.
  • the strength of the polyurethane resin film can be evaluated as, for example, TB (tensile strength), EB (elongation), and TR (tear strength), as will be described later.
  • the polyurethane resin film material set or the like formed on the base material according to the present embodiment can be suitably used as a resin film formed on a paint or other base material. In addition, it can be applied to adhesives, synthetic leather, plastic films, and the like.
  • Polyol which is one material of the polyurethane resin film material set, is mixed with raw materials under the conditions shown in Table 1 and stirred (190 rpm) at 190 ° C for 24 hours while bubbling nitrogen gas in a 2 liter separable flask. Obtained by transesterification.
  • each polyol raw material indicated by a symbol is as follows.
  • ⁇ 1,6-HD 1,6-hexanediol
  • PCD-HG-1000 Polycarbonate diol having a number average molecular weight of 1000 obtained from deethanol reaction of 1,6-hexanediol and diethyl carbonate
  • PCD-HG-2000 Polycarbonate diol having a number average molecular weight of 2000 obtained from deethanol reaction of 1,6-hexanediol and diethyl carbonate
  • PCD-HG-5000 Number average molecular weight of 5000 obtained from deethanol reaction of 1,6-hexanediol and diethyl carbonate
  • Polycarbonate diol of PCL-210 Bifunctional polycaprolactone diol having a number average molecular weight of 1000 obtained by
  • Polyisocyanate which is one material of the polyurethane resin film material set, was blended with raw materials under the conditions shown in Table 2, and subjected to urethanization reaction at 80 ° C. for 4 hours while bubbling nitrogen gas in a separable flask. Thereafter, thin film distillation was performed at 140 ° C. and 0.3 Torr to remove unreacted HDI.
  • each polyisocyanate raw material indicated by a symbol is as follows.
  • ⁇ HDI Hexamethylene diisocyanate
  • PTG-250 Polytetramethylene glycol (polypropylene glycol) with a number average molecular weight of 250
  • PTG-650 Polytetramethylene glycol with a number average molecular weight of 650
  • PTG-1000 Polytetramethylene glycol with a number average molecular weight of 1000
  • PTG-2000 Polytetramethylene glycol with a number average molecular weight of 2000
  • PPG-600 Number average molecular weight
  • PPG-1000 Polypropylene glycol having a number average molecular weight of 1000
  • the isocyanate species C-HX is as follows.
  • Examples 1 to 12 and Comparative Examples 1 to 6 A polyol and a polyisocyanate were blended under the conditions shown in Tables 3 to 5, and dioctyltin dilaurate (DOTDL) was added as a curing catalyst in an amount of 0.01% by mass with respect to 100 parts by mass of the polyol / isocyanate group-terminated prepolymer.
  • a polyurethane film (film) was prepared and evaluated by adding parts.
  • a curing catalyst was added after heat-melting treatment to prepare a polyurethane film (film) and evaluated.
  • Example 13 In a 2 liter separable flask, 1000 g of OH-5, 2 g of organometallic catalyst (NW-96), and 1 g of a curing reaction inhibitor (JP-508) were charged and stirred at 25 ° C. for 30 minutes. As a result, a polyol premix (hereinafter referred to as OH-10) in which JP-508 was uniformly mixed with the polyol and NW-96 was dispersed in the polyol was obtained.
  • OH-10 polyol premix in which JP-508 was uniformly mixed with the polyol and NW-96 was dispersed in the polyol was obtained.
  • NW-96 is composed of KS-1010A-1 (di-n-octyltin malate polymer: manufactured by Kyodo Yakuhin Co., Ltd.), which is an organotin compound catalyst, and PN-250, which is an adipate ester plasticizer. (Adeka Co., Ltd.) is blended at an equal mass ratio and kneaded with three rolls until the particle size of KS-1010-A reaches a maximum of 30 ⁇ m.
  • JP-508 is Johoku Chemical Industry Co., Ltd. Acid phosphoric acid ester manufactured by Co., Ltd .: a mixture of mono (2-ethylhexyl acid phosphate) and bis (2-ethylhexyl acid phosphate).
  • NCO-1 and OH-10 were mixed in an atmosphere of 25 ° C. for 30 seconds.
  • the state immediately after mixing was a state in which the organometallic component was dispersed.
  • 400 g of this mixed solution was put into a glass sample bottle having a capacity of 500 cc and left to stand in an atmosphere at 25 ° C., the fluidity was maintained even after 5 hours had passed since mixing.
  • the liquid 5 hours after mixing is poured onto the release paper, cast with a bar coater to a film with a thickness of 100 ⁇ m and a plane dimension of 300 mm ⁇ 300 mm, and cured at 150 ° C. for 3 minutes to form a polyurethane film Got.
  • the obtained polyurethane film had a TB of 50 MPa, an EB of 600%, and a TR of 80 kN / m.
  • the liquid immediately after mixing is poured onto a release paper, cast with a bar coater so as to be a film having a thickness of 100 ⁇ m and a plane dimension of 300 mm ⁇ 300 mm, and cured at 150 ° C. for 3 minutes to form a polyurethane film. Obtained.
  • the obtained polyurethane film had a TB of 50 MPa, an EB of 600%, and a TR of 80 kN / m.
  • Example 14 A 2-liter separable flask was charged with 1000 g of OH-5, 0.2 g of DOTDL (dioctyltin dilaurate, normal temperature solid) and 0.1 g of JP-508, respectively, and stirred at 25 ° C. for 30 minutes.
  • a polyol premix in which 508 is uniform with the polyol is hereinafter referred to as OH-11.
  • NCO-1 and OH-11 were mixed in an atmosphere of 25 ° C. for 30 seconds. The state immediately after mixing was uniform.
  • the liquid immediately after mixing is poured onto a release paper, cast with a bar coater so as to be a film having a thickness of 100 ⁇ m and a plane dimension of 300 mm ⁇ 300 mm, and cured at 150 ° C. for 3 minutes to form a polyurethane film. Obtained.
  • the obtained polyurethane film had a TB of 50 MPa, an EB of 600%, and a TR of 80 kN / m.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un ensemble de matériaux d'un film de revêtement de résine de polyuréthane présentant une excellente résistance de film, formé sur un substrat. L'ensemble de matériaux comprend un composant polyol préparé en faisant régir un polycarbonate polyol avec un polycaprolactone polyol, et un prépolymère terminé par un groupe isocyanate préparé en faisant réagir un polytétraméthylène glycol avec un polyisocyanate, le rapport massique entre le polycarbonate polyol et le polycaprolactone polyol étant supérieur ou égal à 65/35. De plus, le composant polyol peut contenir en outre un catalyseur de durcissement organométallique qui prend la forme d'une poudre fine aux températures ordinaires, et un retardateur de durcissement.
PCT/JP2010/000591 2009-03-13 2010-02-02 Ensemble de matériaux de formation d'un film de revêtement de résine de polyuréthane formé sur un substrat Ceased WO2010103719A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2010800080646A CN102317390B (zh) 2009-03-13 2010-02-02 形成于基材上的聚氨酯树脂膜材料组
KR1020117017059A KR101224777B1 (ko) 2009-03-13 2010-02-02 기재 상에 형성되는 폴리우레탄 수지 피막 재료 세트

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-060405 2009-03-13
JP2009060405A JP5429608B2 (ja) 2009-03-13 2009-03-13 基材上に形成されるポリウレタン樹脂皮膜材料セット

Publications (1)

Publication Number Publication Date
WO2010103719A1 true WO2010103719A1 (fr) 2010-09-16

Family

ID=42728019

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/000591 Ceased WO2010103719A1 (fr) 2009-03-13 2010-02-02 Ensemble de matériaux de formation d'un film de revêtement de résine de polyuréthane formé sur un substrat

Country Status (5)

Country Link
JP (1) JP5429608B2 (fr)
KR (1) KR101224777B1 (fr)
CN (1) CN102317390B (fr)
TW (1) TWI388583B (fr)
WO (1) WO2010103719A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755910A (zh) * 2013-12-27 2014-04-30 浙江华峰合成树脂有限公司 耐寒耐酒精不黄变革用聚氨酯树脂及其制法
WO2018177466A1 (fr) * 2017-03-29 2018-10-04 Mankiewicz Gebr. & Co. (Gmbh & Co. Kg) Composition de matière de revêtement, revêtements fabriqués à partir de celle-ci et leur utilisation comme protection anti-érosion
CN111247186A (zh) * 2017-11-13 2020-06-05 三井化学株式会社 聚氨酯树脂组合物、聚氨酯树脂、成型品、纤维增强塑料及纤维增强塑料的制造方法
CN116323198A (zh) * 2020-10-02 2023-06-23 大日精化工业株式会社 氨基甲酸酯预聚物、湿气固化型氨基甲酸酯热熔树脂组合物及层叠体

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI635204B (zh) * 2014-04-03 2018-09-11 展麒綠能股份有限公司 人造皮革及其製造方法
CN106519950B (zh) * 2016-11-23 2019-11-22 北京涑酷特威科技有限公司 风挡橡胶漆及其制备方法
CN115785385B (zh) * 2022-12-09 2024-09-06 江苏华大新材料有限公司 一种曲面屏手机用高透不黄变聚氨酯树脂及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62280214A (ja) * 1986-05-28 1987-12-05 Dainippon Ink & Chem Inc ポリウレタン樹脂組成物
JPS6484413A (en) * 1987-09-28 1989-03-29 Nippon Polyurethane Kogyo Kk Magnetic recording medium
JPH021718A (ja) * 1988-02-01 1990-01-08 Asahi Chem Ind Co Ltd ウレタンプレポリマー及びポリウレタン塗料組成物
JPH111549A (ja) * 1996-12-19 1999-01-06 Enichem Spa ポリカーボネートコポリエステルジオールの製造法
WO2004101640A1 (fr) * 2003-05-16 2004-11-25 Daicel Chemical Industries, Ltd. Polyurethane et film de revetement de surface en cuir synthetique dans lequel est utilise ledit polyurethane
JP2005146089A (ja) * 2003-11-13 2005-06-09 Sanyo Chem Ind Ltd ポリウレタンエマルション
JP2008006042A (ja) * 2006-06-29 2008-01-17 Cemedine Co Ltd 一液湿気硬化型靴補修剤及び靴補修方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62280214A (ja) * 1986-05-28 1987-12-05 Dainippon Ink & Chem Inc ポリウレタン樹脂組成物
JPS6484413A (en) * 1987-09-28 1989-03-29 Nippon Polyurethane Kogyo Kk Magnetic recording medium
JPH021718A (ja) * 1988-02-01 1990-01-08 Asahi Chem Ind Co Ltd ウレタンプレポリマー及びポリウレタン塗料組成物
JPH111549A (ja) * 1996-12-19 1999-01-06 Enichem Spa ポリカーボネートコポリエステルジオールの製造法
WO2004101640A1 (fr) * 2003-05-16 2004-11-25 Daicel Chemical Industries, Ltd. Polyurethane et film de revetement de surface en cuir synthetique dans lequel est utilise ledit polyurethane
JP2005146089A (ja) * 2003-11-13 2005-06-09 Sanyo Chem Ind Ltd ポリウレタンエマルション
JP2008006042A (ja) * 2006-06-29 2008-01-17 Cemedine Co Ltd 一液湿気硬化型靴補修剤及び靴補修方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755910A (zh) * 2013-12-27 2014-04-30 浙江华峰合成树脂有限公司 耐寒耐酒精不黄变革用聚氨酯树脂及其制法
CN103755910B (zh) * 2013-12-27 2016-02-03 浙江华峰合成树脂有限公司 耐寒耐酒精不黄变革用聚氨酯树脂及其制法
WO2018177466A1 (fr) * 2017-03-29 2018-10-04 Mankiewicz Gebr. & Co. (Gmbh & Co. Kg) Composition de matière de revêtement, revêtements fabriqués à partir de celle-ci et leur utilisation comme protection anti-érosion
JP2020515679A (ja) * 2017-03-29 2020-05-28 マンキービック ゲブリュダー ウント コー（ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コー カゲー） コーティング材組成物、コンポーネント、および、侵食防止用コーティングの製造方法
RU2749726C2 (ru) * 2017-03-29 2021-06-16 Манкевич Гебр. Унд Ко. (Гмбх Унд Ко. Кг) Композиция материала покрытия, полученные из нее покрытия и их применения для защиты от эрозии
US11279846B2 (en) 2017-03-29 2022-03-22 Mankiewicz Gebr. & Co. (Gmbh & Co. Kg) Coating material composition, coatings produced therefrom and the use thereof as erosion protection
CN111247186A (zh) * 2017-11-13 2020-06-05 三井化学株式会社 聚氨酯树脂组合物、聚氨酯树脂、成型品、纤维增强塑料及纤维增强塑料的制造方法
CN111247186B (zh) * 2017-11-13 2022-05-31 三井化学株式会社 聚氨酯树脂组合物、聚氨酯树脂、成型品、纤维增强塑料及纤维增强塑料的制造方法
CN116323198A (zh) * 2020-10-02 2023-06-23 大日精化工业株式会社 氨基甲酸酯预聚物、湿气固化型氨基甲酸酯热熔树脂组合物及层叠体

Also Published As

Publication number Publication date
CN102317390A (zh) 2012-01-11
JP2010215679A (ja) 2010-09-30
JP5429608B2 (ja) 2014-02-26
CN102317390B (zh) 2013-12-11
TWI388583B (zh) 2013-03-11
KR101224777B1 (ko) 2013-01-21
TW201033239A (en) 2010-09-16
KR20110097981A (ko) 2011-08-31

Similar Documents

Publication Publication Date Title
CA1130495A (fr) Enduit thermocurable, et methode d'enduction de substrats
US6852418B1 (en) Composite structure with one or several polyurethane layers, method for their manufacture and use thereof
JP5429608B2 (ja) 基材上に形成されるポリウレタン樹脂皮膜材料セット
EP2838954B1 (fr) Compositions adhésives et procédés
US20060069225A1 (en) Adhesive compositions containing blocked polyurethane prepolymers
JPH01104612A (ja) ポリウレタン水性分散液
KR20060126402A (ko) 말론산 디이소프로필로 블록된 폴리이소시아네이트 및일액형 코팅 조성물에 있어서의 그 용도
KR20090132495A (ko) 우레탄 형성성 조성물, 폴리올 조성물, 및 우레탄 수지의 제조 방법
US20220002469A1 (en) Polyol compositions and methods
KR102859107B1 (ko) 일액형 폴리우레탄 전구중합체 조성물
WO2014002838A1 (fr) Composition de formation de résine de polyuréthane et résine de polyuréthane
EP1735363A1 (fr) Allophanates de polyethers resistant a la decoloration
US20230026948A1 (en) Polyol compositions and methods
JP7135642B2 (ja) 無溶剤系反応硬化性ポリウレタン樹脂組成物、該樹脂組成物を用いた成形体、及びコーティング剤
US12054576B2 (en) Adhesives based on carbodimide chemistry
JP2021516278A (ja) 接着剤組成物
KR101225580B1 (ko) 사이즈제용 수성 폴리우레탄 분산액 및 그 제조방법, 및 이를 포함하는 유리섬유 사이즈제
WO2006104111A1 (fr) Composition de résine à base d'eau modifiée
US20120264840A1 (en) Method to form a polyurethane material
JP5482892B2 (ja) ポリウレタン樹脂形成性組成物
WO2019137859A1 (fr) Compositions de revêtement à deux constituants
WO2010113464A1 (fr) Composition d'accrochage pour le revêtement d'une matière plastique
JP4959120B2 (ja) 液状ブロック化ウレタンプレポリマー
TWI906317B (zh) 多元醇組合物及方法
JP2000169542A (ja) 難燃性ポリウレタン樹脂組成物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080008064.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10750479

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20117017059

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10750479

Country of ref document: EP

Kind code of ref document: A1