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WO2015005631A1 - Mélange de résines - Google Patents

Mélange de résines Download PDF

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Publication number
WO2015005631A1
WO2015005631A1 PCT/KR2014/006088 KR2014006088W WO2015005631A1 WO 2015005631 A1 WO2015005631 A1 WO 2015005631A1 KR 2014006088 W KR2014006088 W KR 2014006088W WO 2015005631 A1 WO2015005631 A1 WO 2015005631A1
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WO
WIPO (PCT)
Prior art keywords
resin
carbon atoms
mixture
formula
alkyl group
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/KR2014/006088
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English (en)
Korean (ko)
Inventor
최은주
류진영
이종원
김경훈
최현
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.)
LG Chem Ltd
Original Assignee
LG Chem 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 LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN201480049501.7A priority Critical patent/CN105531315B/zh
Priority to US14/903,263 priority patent/US10392458B2/en
Priority claimed from KR1020140085017A external-priority patent/KR101729813B1/ko
Publication of WO2015005631A1 publication Critical patent/WO2015005631A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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 application relates to a resin mixture, a copolymer, a pellet, a method for producing a resin molded article using the same, and a resin molded article.
  • a polarizing plate is an optical functional film applied to apparatuses, such as a liquid crystal display (LCD) etc., for example.
  • apparatuses such as a liquid crystal display (LCD) etc., for example.
  • LCD liquid crystal display
  • the polarizing plate includes a polarizer which is a functional sheet capable of extracting only the light vibrating in one direction from the incident light while vibrating in various directions, and is typically a triacetyl cellulose attached to both surfaces of the polarizer by an adhesive or an adhesive. (Triacetyl Cellulose, TAC) -based protective film may be included.
  • a polarizer which is a functional sheet capable of extracting only the light vibrating in one direction from the incident light while vibrating in various directions, and is typically a triacetyl cellulose attached to both surfaces of the polarizer by an adhesive or an adhesive.
  • TAC Triacetyl Cellulose
  • a general TAC protective film is expensive and not easy to manufacture. Accordingly, an acrylic protective film or the like is used as a protective film for replacing the TAC protective film.
  • the TAC-based protective film has a hygroscopicity, it is possible to use a water-based adhesive such as a polyvinyl alcohol adhesive, but the acrylic protective film generally has a low hygroscopicity and is attached to the polarizer using an ultraviolet curable adhesive instead of the water-based adhesive. do.
  • the acrylic protective film is not excellent in the adhesive force with the polarizer, coating the primer or the like on one side or both sides of the acrylic protective film to improve the problem.
  • the present application provides resin mixtures and pellets.
  • One embodiment of the present application is a first resin; And a second resin having a difference in surface energy or melt viscosity from the first resin, wherein the second resin has 47 to 73 parts by weight of an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms; 20 to 30 parts by weight of the monomer of Formula 1; And it provides a resin mixture which is a polymer of a monomer mixture comprising 3 to 27 parts by weight of monomer of the formula (2).
  • R 1 and R 4 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms
  • Ar represents phenyl
  • R 2 represents hydrogen or -XR 6 ,
  • R 6 represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents hydrogen or together with R 5 forms a heterocycle
  • R 5 represents a heterocycle or -COOR 7 or -CONR 8 R 9 ,
  • R 7 represents hydrogen, an alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group, or a heterocycle,
  • R 8 and R 9 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or phenyl substituted with a hydroxy group.
  • R 1 and R 4 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms
  • Ar represents phenyl
  • R 2 represents hydrogen or -XR 6 ,
  • R 6 represents an alkyl group having 1 to 4 carbon atoms
  • R 3 is and represents a hydrogen, or form a heterocycle together with R 5,
  • R 5 represents a heterocycle or -COOR 7 or -CONR 8 R 9 ,
  • R 7 represents hydrogen, an alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group, or a heterocycle,
  • R 8 and R 9 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or phenyl substituted with a hydroxy group
  • Another embodiment of the present application is a core formed of a first resin; And a cell formed of the first resin and the second resin having a difference in surface energy or melt viscosity.
  • Another embodiment of the present application to melt the resin mixture to form a molten mixture; And processing the melted mixture to form a layered structure.
  • Another embodiment of the present application is to melt the pellets to form a molten mixture; And processing the melted mixture to form a layered structure.
  • Another embodiment of the present application is the first resin layer; A second resin layer formed on the first resin layer; And an interfacial layer formed between the first resin layer and the second resin layer, wherein the second resin includes an alkyl (meth) acryl having an alkyl group having 1 to 14 carbon atoms. Rate 47 to 73 parts by weight; 20 to 30 parts by weight of the monomer of Formula 1; And it provides a resin molded article which is a polymer of a monomer mixture comprising 3 to 27 parts by weight of monomer of the formula (2).
  • R 1 and R 4 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms
  • Ar represents phenyl
  • R 2 represents hydrogen or -XR 6 ,
  • R 6 represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents hydrogen or together with R 5 forms a heterocycle
  • R 5 represents a heterocycle or -COOR 7 or -CONR 8 R 9 ,
  • R 7 represents hydrogen, an alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group, or a heterocycle,
  • R 8 and R 9 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or phenyl substituted with a hydroxy group.
  • the "mixture” may be a mixture of two or more different resins.
  • the type of the mixture is not particularly limited, but may include a case in which two or more resins are mixed in one matrix, or a case in which two or more pellets are mixed.
  • Each of the resins may have different physical properties, for example, the physical properties may be surface energy, melt viscosity, or solubility parameter.
  • Melt processing means a process of melting a resin mixture at a temperature above the melting temperature (Tm) to form a melt blend, and forming a desired molded article using the melt mixture, for example, injection Molding, extrusion molding, blow molding, transfer molding, film blowing, fiber spinning, calendering thermoforming or foam molding.
  • Resin molded article means a pellet or product formed from a resin mixture, and the resin molded article is not particularly limited, but may be, for example, an automobile part, an electronic device part, a mechanical part, a functional film, a toy, or a pipe. have.
  • Layer separation may mean that a layer formed substantially by one resin is positioned or arranged on a layer formed substantially by another resin.
  • the layer formed by one resin may mean that one type of resin does not form a sea-island structure and is continuously present throughout one layer.
  • the sea-level structure means that the phase separated resin is partially distributed in the whole resin mixture.
  • substantially formed may mean that only one resin is present in one layer, or that one resin is rich.
  • the resin mixture may be separated by melt processing. Accordingly, it is possible to produce a resin molded article having a specific function, for example, excellent adhesion, without a separate process such as coating and plating. Therefore, the resin molded article can have improved adhesion and surface properties, and the production cost and time of the resin molded article can be reduced when using the resin mixture.
  • Layer separation of the resin mixture may occur due to the difference in physical properties between the first resin and the second resin and / or the molecular weight distribution of the second resin.
  • the physical properties may be, for example, surface energy, melt viscosity or solubility parameter.
  • a mixture of resins including two kinds of resins will be described, but it will be apparent to those skilled in the art that three or more kinds of resins having different physical properties can be mixed and separated by melt processing.
  • the resin mixture may include a first resin and a second resin having a surface energy difference of 0.1 to 35 mN / m at 25 ° C. from the first resin.
  • the surface energy difference between the first resin and the second resin is 0.1 to 35 mN / m, 0.1 to 30 mN / m, 0.1 to 20 mN / m, 0.1 to 15 mN / m, 0.1 to 7 mN / m at 25 °C , 1 to 35 mN / m, 1 to 30 mN / m, 2 to 20 mN / m, 3 to 15 days.
  • the second resin can easily move to the surface without the first and second resins peeling off, and the delamination phenomenon can easily occur.
  • the resin mixture of the first resin and the second resin having a surface energy difference of 0.1 to 35 mN / m at 25 ° C. may be layer separated by melt processing.
  • the first resin and the second resin may be separated by a hydrophobic difference.
  • the second resin having a lower surface energy than the first resin has high hydrophobicity, the second resin can be moved in contact with air to form a second resin layer located on the air side.
  • the first resin may be placed on the side opposite to the air while contacting the second resin. Thus, layer separation occurs between the first resin and the second resin of the resin mixture.
  • the resin mixture may be separated into two or more layers.
  • the resin mixture comprising the first resin and the second resin may have three layers, for example, a second resin layer, when two opposite surfaces of the melt processed resin mixture are exposed to air. It can be separated into a / first resin layer / a second resin layer.
  • the resin mixture may be separated into two layers, for example, a second resin layer / first resin layer.
  • the melt processed resin mixture has five layers, for example, a third resin layer / agent.
  • the layer can be separated into two resin layers / first resin layer / second resin layer / third resin layer.
  • the resin mixture may be layered in all directions to form a core-shell structure.
  • the resin mixture comprises a first resin; And a second resin having a melt viscosity difference of 0.1 to 3000 pa * s at a shear rate of 100 to 1000 s ⁇ 1 and a processing temperature of the resin mixture.
  • the difference in melt viscosity of the first resin and the second resin is 0.1 to 3000 pa * s, 1 to 2000 pa * s, 1 to 1000 pa * at a shear rate of 100 to 1000 s ⁇ 1 and a processing temperature of the resin mixture. s, 1 to 500 pa * s, 50 to 500 pa * s, 100 to 500 pa * s, 200 to 500 pa * s or 250 to 500 pa * s.
  • the second resin can easily move to the surface and the layer separation phenomenon can easily occur without the first and second resins peeling off.
  • the resin mixture of the first resin and the second resin having a melt viscosity difference of 0.1 to 3000 pa * s at a shear rate of 100 to 1000 s ⁇ 1 and a processing temperature of the resin mixture is layered due to the difference in melt viscosity after melt processing. Can be separated.
  • the first resin and the second resin may be separated by the fluidity difference.
  • the second resin having a lower melt viscosity than the first resin has high fluidity
  • the second resin can be moved in contact with air to form a second resin layer located on the air side.
  • the first resin may be placed on the side opposite to the air while contacting the second resin.
  • layer separation occurs between the first resin and the second resin of the resin mixture.
  • the melt viscosity can be measured by capillary flow, which means shear viscosity (pa * s) depending on the specific processing temperature and shear rate (/ s).
  • the 'shear rate' refers to a shear rate applied when the resin mixture is processed, and the shear rate may be adjusted between 100 and 1000 s ⁇ 1 depending on the processing method. Control of the shear rate according to the processing method will be apparent to those skilled in the art.
  • the 'processing temperature' means a temperature for processing the resin mixture.
  • the processing temperature can be adjusted according to the resin applied to melt processing such as extrusion or injection.
  • the processing temperature may be 210 to 270 ° C.
  • the first resin; And a second resin having a difference in solubility parameters from 0.001 to 10.0 (J / cm 3 ) 1/2 at 25 ° C., may be provided.
  • the difference between the solubility parameters of the first resin and the second resin is 0.001 to 10.0 (J / cm 3 ) 1/2 , 0.01 to 5.0 (J / cm 3 ) 1/2 , 0.01 to 3.0 ( J / cm 3 ) 1/2 , 0.01 to 2.0 (J / cm 3 ) 1/2 , 0.1 to 1.0 (J / cm 3 ) 1/2 , 0.1 to 10.0 (J / cm 3 ) 1/2 , 3.0 to 10.0 (J / cm 3 ) 1/2 , 5.0 to 10.0 (J / cm 3 ) 1/2 or 3.0 to 8.0 (J / cm 3 ) 1/2 .
  • solubility parameters are inherent properties of the resins which show the solubility according to the polarity of each resin molecule, and solubility parameters for each resin are generally known.
  • the difference in solubility parameter is less than 0.001 (J / cm 3 ) 1/2 , the first resin and the second resin are easily mixed, so that the layer separation phenomenon is difficult to occur easily, and the difference in solubility parameter is 10.0 (J / cm 3 ) If greater than 1/2 , the first resin and the second resin may not be bonded and may be peeled off.
  • the upper limit and / or lower limit of the difference in solubility parameters may be any value within the range of 0.001 to 10.0 (J / cm 3 ) 1/2 , and may be dependent on the physical properties of the first resin.
  • the second resin has a difference in solubility parameter between the first resin and the second resin at 25 ° C. Can be selected to be from 0.001 to 10.0 (J / cm 3 ) 1/2 .
  • the difference in solubility parameter may be selected in consideration of the miscibility of the second resin in the melt mixture of the first resin and the second resin.
  • the resin mixture of the first resin and the second resin having a solubility parameter difference of 0.001 to 10.0 (J / cm 3 ) 1/2 may be layer separated after melt processing due to the difference in solubility parameters.
  • the first resin and the second resin may be separated by the degree of miscibility.
  • the second resin having a difference in solubility parameter of 0.001 to 10 (J / cm 3 ) 1/2 at 25 ° C. relative to the first resin may not be mixed with the first resin.
  • the second resin additionally has a lower surface tension or lower melt viscosity than the first resin, the second resin can be moved in contact with air to form a second resin layer located on the air side.
  • the first resin may be placed on the side opposite to the air while contacting the second resin. Thus, layer separation occurs between the first resin and the second resin of the resin mixture.
  • the first resin is a resin mainly determining the physical properties of the desired molded article, and may be selected according to the type of the desired molded article and the process conditions used.
  • a general synthetic resin can be used without particular limitation.
  • Styrene-type resins such as an acrylonitrile butadiene styrene (ABS) resin, a polystyrene resin, an acrylonitrile styrene acrylate (ASA) resin, or a styrene-butadiene-styrene block copolymer
  • Polyolefin resins such as high density polyethylene resin, low density polyethylene resin or polypropylene resin
  • Thermoplastic elastomers such as ester-based thermoplastic elastomers or olefin-based thermoplastic elastomers
  • Polyoxyalkylene resins such as polyoxymethylene resin or polyoxyethylene resin
  • Polyester resins such as polyethylene terephthalate resins or polybutylene terephthalate resins
  • Polyvinyl chloride resins such as polyethylene terephthalate resins or polybutylene terephthalate resins
  • Polyvinyl chloride resins such as polyethylene tere
  • plastics exhibiting excellent mechanical and thermal properties may be used.
  • polyetherketone, polysulfone, polyimide and the like can be used as the engineering plastics.
  • the first resin a copolymer obtained by polymerizing acrylonitrile, butadiene, styrene and an acrylic monomer may be used.
  • the first resin is an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms;
  • it may be a polymer of a monomer mixture comprising a monomer of formula (3).
  • R 1 independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms
  • Ar represents phenyl
  • R 2 represents hydrogen or -XR 6 ,
  • R 6 represents an alkyl group having 1 to 4 carbon atoms
  • Y represents oxygen or NR 10 .
  • R 10 represents hydrogen, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.
  • the monomer of Formula 1 may be styrene or alpha-methyl styrene, and the monomer of Formula 3 may be cyclohexyl maleimide or maleic anhydride, but is not limited thereto.
  • the monomer mixture forming the polymer of the first resin is 85 to 98 parts by weight of an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms; 1 to 5 parts by weight of the monomer of Formula 1; And 3 to 10 parts by weight of the monomer of Formula 3.
  • the alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms is included in an amount of less than 85 parts by weight, the compatibility with the second resin to be described later is too bad, the peeling phenomenon on the surface of the first resin and the second resin May appear.
  • a resin exhibiting the difference in physical properties as described above in relation to the first resin and imparting good compatibility with the first resin and an adhesive can be used.
  • the second resin is the second resin
  • alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms
  • It may be a polymer of a monomer mixture including 3 to 27 parts by weight of the monomer of formula (2).
  • R 1 and R 4 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms
  • Ar represents phenyl
  • R 2 represents hydrogen or -XR 6 ,
  • R 6 represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents hydrogen or together with R 5 forms a heterocycle
  • R 5 represents a heterocyclic group or -COOR 7 or -CONR 8 R 9 represents,
  • R 7 represents hydrogen, an alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group, or a heterocycle,
  • R 8 and R 9 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or phenyl substituted with a hydroxy group.
  • R 1 and R 4 each independently represents a hydrogen or a methyl group
  • Ar represents phenyl
  • R 2 represents hydrogen or -XR 6 ,
  • R 6 represents a methyl group or an ethyl group
  • R 3 represents hydrogen or combines with R 5 to form maleic anhydride, or to form a maleimide unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms,
  • R 5 represents pyrrolidone, phthalimide, or succinimidyl group or represents —COOR 7 or —CONR 8 R 9 ,
  • R 7 here represents hydrogen, a methyl group substituted with a hydroxy group, a methyl group substituted with a hydroxy group, a lactone group or a succinimidyl group,
  • R 8 and R 9 may each independently represent hydrogen, a methyl group substituted with a hydroxy group, or phenyl.
  • the compatibility between the first resin and the second resin is a layer separation inducing factor if the compatibility is too good, the layer separation efficiency between the first resin and the second resin is reduced, if the compatibility is not very good, peel off from the surface or inside the molding Can form large domains. Therefore, proper compatibility between the first resin and the second resin is required for effective layer separation. Accordingly, in the second resin of the present application, by including a specific monomer in consideration of compatibility with the first resin in an appropriate content, the above object can be achieved.
  • the monomer mixture of the second resin is 47 to 73 parts by weight, for example, 50 to 70 parts by weight or 55 to 65 parts by weight of an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms
  • an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms By including it, the excellent compatibility with the said 1st resin can be shown.
  • the alkyl (meth) acrylate monomer having an alkyl group having 1 to 14 carbon atoms is a component included in the monomer mixture of the first resin, and is used to ensure compatibility between the first resin and the second resin. Ingredient.
  • the compound of Formula 1 is included in the monomer mixture of the second resin as a component for effectively separating the layers.
  • the compound of Formula 1 may be, for example, a component having low compatibility with the compound of Formula 3 included in the monomer mixture of the first resin, and may be included in the monomer mixture of the second resin.
  • the compound of Formula 1 may be included in the monomer mixture of the second resin, 20 to 30 parts by weight, for example, 22 to 28 parts by weight or 24 to 26 parts by weight, when included in excess of 30 parts by weight ,
  • the compatibility with the first resin is too bad, the peeling phenomenon may appear on the surface of the first resin and the second resin.
  • the compound of Formula 2 is an adhesive, for example, polyvinyl alcohol-based adhesive, hydroxyl group-containing acrylate, epoxy acrylate, urethane acrylate, oxetane acrylate, polyester acrylate or silicone-based acrylic
  • an adhesive for example, polyvinyl alcohol-based adhesive, hydroxyl group-containing acrylate, epoxy acrylate, urethane acrylate, oxetane acrylate, polyester acrylate or silicone-based acrylic
  • a component for enhancing affinity with a cationically polymerizable adhesive derived from an oligomer such as a radical polymerizable adhesive or an epoxy resin vinyl ester polymerized from a rate it may be, for example, a heterocyclic moiety or a monomer including a hydrophilic group. .
  • the monomers of formula (2) are maleic anhydride, gamma-butyrolactone (meth) acrylate, N-vinyl pyrrolidone, N-vinyl phthalimide, N-succinimidyl acrylate, norbornenelactone ( Meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, acrylamide, N-methyrol acrylamide, or N-phenyl acrylamide.
  • gamma-butyrolactone (meth) acrylate may be used as the compound of Formula 2, or gamma-butyrolactone (meth) acrylate and hydroxyethyl (meth) acrylate. Can be used together.
  • the compound of Formula 2 may be included in the monomer mixture of the second resin, 3 to 27 parts by weight, for example, 5 to 25 parts by weight or 10 to 20 parts by weight, when included in less than 3 parts by weight
  • the content of the alkyl (meth) acrylate and the monomer of the formula (1) is relatively reduced, so that the compatibility with the first resin is too bad, Peeling phenomenon may appear on the surface of the second resin or layer separation may not occur.
  • the resin molded article formed by the resin mixture When used as a protective film for a polarizing plate, it can replace a TAC-based film or an acrylic protective film that has been used in the past, in particular, in the case of a conventional acrylic protective film, the adhesiveness with the polarizer
  • the additional primer coating step on the surface of the protective film for polarizing plates can be omitted
  • it is possible to exhibit excellent adhesion with the polarizer can reduce the production time and cost, and increase the productivity.
  • the weight average molecular weight (Mw) of the second resin may be about 5,000 to 200,000.
  • the weight average molecular weight of the second resin is 10,000 to 200,000, 1.50,000 to 200,000, 20,000 to 200,000, 0.50,000 to 180,000, 0.50,000 to 150,000, 0.50,000 to 120,000, 10,000 to 180,000, 1.50,000 to 150,000, or 20,000 to 120,000.
  • the second resin having a weight average molecular weight in this range is applied to, for example, a resin mixture for melt processing, the second resin may have appropriate fluidity and layer separation may easily occur.
  • the molecular weight distribution (PDI) of the second resin may be controlled in the range of 1 to 2.5, 1 to 2.2, 1.5 to 2.5, or 1.5 to 2.2.
  • the second resin having a molecular weight distribution in this range is applied to, for example, a resin mixture for melt processing, the content of low molecular weight and / or high molecular weight which prevents occurrence of delamination in the second resin is reduced, thereby making layer separation easier. Can happen.
  • the resin mixture may include 0.1 to 50 parts by weight of the second resin based on 100 parts by weight of the first resin. In another example, the resin mixture may include 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 15 parts by weight based on 100 parts by weight of the first resin.
  • the content includes the first resin and the second resin, it is possible to induce a layer separation phenomenon, it is possible to provide an economical resin mixture by appropriately controlling the content of the second resin that is relatively expensive compared to the first resin.
  • alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms
  • R 1 and R 4 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms
  • Ar represents phenyl
  • R 2 represents hydrogen or -XR 6 ,
  • R 6 represents an alkyl group having 1 to 4 carbon atoms
  • R 3 represents hydrogen or together with R 5 forms a heterocycle
  • R 5 represents a heterocycle or -COOR 7 or -CONR 8 R 9 ,
  • R 7 represents hydrogen, an alkyl group having 1 to 4 carbon atoms substituted with a hydroxy group, or a heterocycle,
  • R 8 and R 9 represents an alkyl group or a phenyl group having 1 to 4 carbon atoms substituted with hydrogen, hydroxy, each independently.
  • the above resin mixture can be prepared into pellets by extrusion.
  • the first resin may form a core
  • the second resin may be separated from the first resin to form a shell.
  • the pellet comprises a core formed of the first resin; And 47 to 73 parts by weight of an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms having a difference in surface energy, melt viscosity or solubility parameter from the first resin; 20 to 30 parts by weight of the monomer of Formula 1; And it provides a pellet comprising a cell formed of a second resin which is a polymer of a monomer mixture comprising 3 to 27 parts by weight of the monomer of the formula (2).
  • the first resin and the second resin may have different surface energy, melt viscosity, or solubility parameters.
  • the first resin and the second resin may have a surface energy difference of 0.1 to 35 mN / m at 25 ° C .; Or at a shear rate of 100 to 1000 s ⁇ 1 and a melt temperature of 0.1 to 3000 pa * s at the processing temperature of the pellets.
  • the resin mixture or pellets described above may be melt processed to provide a resin molded article having a layered structure.
  • melting the resin mixture to form a melt blend (melt blend); And processing the melted mixture to form a layered structure.
  • a layer separation phenomenon may occur in the process of melt processing the resin mixture, and due to this layer separation phenomenon, pellets or It can have the effect of selectively coating the surface of the molded article.
  • the shell portion having a relatively low surface energy or melt viscosity during the melt processing process is located on the surface of the resin molded article mechanical properties and surface A resin molded article having improved characteristics can be provided.
  • melt processing the resin mixture may be performed under shear stress.
  • the melt processing step may be performed by an extrusion and / or injection processing method.
  • the step of melt processing the resin mixture may vary the temperature applied according to the type of the first resin and the second resin used.
  • the melt processing temperature may be controlled to about 210 to 270 ° C.
  • the method of manufacturing a resin molded article may further include curing the resultant obtained by melt processing the resin mixture, that is, the melt processed product of the resin mixture.
  • the curing can be, for example, thermosetting or UV curing.
  • the resin molded article may be further subjected to chemical or physical treatment.
  • the method of manufacturing a resin molded article may further include preparing a second resin before melting the resin mixture to form a molten mixture.
  • 2nd resin can provide a specific function, for example, the outstanding adhesiveness to the surface layer of a resin molded article. Since the contents related to the preparation of the second resin have already been described, specific details are omitted.
  • the method for producing a resin molded article may include melting a pellet to form a molten mixture; And processing the melt mixture to form a layered structure.
  • the pellet may be prepared by melt processing such as extrusion of the resin mixture described above.
  • melt processing such as extrusion of the resin mixture described above.
  • the second resin having a higher hydrophobicity than the first resin moves in contact with air to form a surface layer of the pellet.
  • One resin may be located in the center of the pellet to form a core.
  • the pellets thus prepared can be manufactured into a resin molded article by melt processing such as injection.
  • the present invention is not limited thereto, and in another example, the resin mixture may be manufactured into a resin molded article by melt processing such as direct injection or the like.
  • the resin molded article is a first resin layer, a second resin layer formed on the first resin layer and an interface layer formed between the first resin layer and the second resin layer. It may include.
  • the interface layer may include first and second resins.
  • a 1st resin layer is located inside and a 2nd resin layer is resin It may be a layered structure formed on the surface of the molded article.
  • the first resin layer mainly includes the first resin, determines physical properties of the molded article, and may be located inside the resin molded article.
  • the 'second resin layer' may mainly include the second resin, and may be positioned outside the resin molded article to impart a predetermined function to the surface of the molded article.
  • the resin molded article may include an interface layer formed between the first resin layer and the second resin layer and containing a mixture of the first resin and the second resin.
  • the interfacial layer may be formed between the separated first resin layer and the second resin layer to serve as an interface, and may include a mixture of the first resin and the second resin.
  • the blend may be in a state in which the first resin and the second resin are physically or chemically bonded, and the first resin layer and the second resin layer may be bonded through the blend.
  • the resin molded article may be formed in a structure in which the first resin layer and the second resin layer are divided by such an interface layer, and the second resin layer is exposed to the outside.
  • the molded article may include the first resin layer; Interfacial layer; And a structure in which the second resin layer is sequentially stacked, and may have a structure in which an interface and a second resin are stacked on upper and lower ends of the first resin.
  • the resin molded article may include a structure in which the interface and the second resin layer sequentially surround the first resin layer having various three-dimensional shapes, for example, spherical, circular, polyhedral, sheet, and the like.
  • the layer separation phenomenon appearing in the resin molded article seems to be due to the production of a resin molded article by applying a specific first resin and a second resin having different physical properties.
  • different physical properties include surface energy or melt viscosity. Details of such differences in physical properties are as described above.
  • the first resin layer, the interfacial layer, and the second resin layer may be identified using an SEM after etching the fracture surface using THF vapor after the specimen is subjected to a low temperature impact test.
  • the specimen is cut with a diamond knife using a microtoming device to make a smooth cross section, and then the smooth cross section is etched using a solution that can selectively dissolve the second resin better than the first resin.
  • the etched cross-section is different in the degree of melting depending on the content of the first resin and the second resin, and when the cross-section is viewed from the surface at 45 degrees using the SEM, the first resin layer, the second resin layer, The interfacial layer and the surface can be observed and the thickness of each layer can be measured.
  • 1,2-dichloroethane solution (10% by volume, in EtOH) was used as a solution for selectively dissolving the second resin, but this is illustrative and the solubility of the second resin is higher than that of the first resin.
  • the solution is not particularly limited, and those skilled in the art can appropriately select and apply a solution according to the type and composition of the second resin.
  • the interfacial layer is 1 to 95%, 10 to 95%, 20 to 95%, 30 to 95%, 40 to 95%, 50 to 95%, 60 to 95%, or the total thickness of the second resin layer and the interface layer, or It may have a thickness of 60 to 90%. If the interfacial layer is 0.01-95% of the total thickness of the second resin layer and the interfacial layer, the interfacial bonding force between the first resin layer and the second resin layer is excellent, so that peeling of both layers does not occur, and the second resin layer Due to this, the surface properties can be greatly improved. On the contrary, if the interface layer is too thin as compared to the second resin layer, the bonding force between the first resin layer and the second resin layer is low, so that peeling of both layers may occur. The effect of the improvement of properties may be insignificant.
  • the second resin layer may have a thickness of 0.01 to 30%, 0.01 to 20%, 0.01 to 10%, 0.01 to 5%, 0.01 to 3%, 0.01 to 1% or 0.01 to 0.1% relative to the total resin molded article. .
  • As the second resin layer has a thickness in a range, it is possible to impart improved adhesion to the surface of the molded article. If the thickness of the second resin layer is too thin, it may be difficult to sufficiently improve the adhesiveness of the molded article. If the thickness of the second resin layer is too thick, the physical properties of the functional resin itself may be reflected in the resin molded article, thereby changing the mechanical properties of the first resin.
  • the component of a 1st resin layer can be detected by the infrared spectroscopy IR on the surface of a 2nd resin layer.
  • the surface of the second resin layer means a surface exposed to the outside (for example, air) rather than the first resin layer.
  • the difference in physical properties between the first resin and the second resin may mean a difference in physical properties between the first resin and the second resin or a difference in physical properties between the first resin layer and the second resin layer.
  • the resin molded article can be used to provide a protective film for a polarizing plate.
  • the resin molded article may be used in place of a TAC-based protective film that has been conventionally used, and the polarizing plate may be provided with the second resin layer of the resin molded article attached to one or both sides of the polarizer.
  • the kind of the polarizer is not particularly limited, and for example, a film made by containing a polarizing component such as iodine or a dichroic dye in a film made of polyvinyl alcohol-based resin and stretching can be used.
  • polyvinyl alcohol-based resin polyvinyl alcohol, polyvinyl formal, polyvinyl acetal or saponified product of ethylene-vinyl acetate copolymer may be used.
  • the degree of polymerization of the polyvinyl alcohol-based resin may be 100 to 5,000, preferably 1,400 to 4,000.
  • the thickness of the polarizer may be appropriately selected according to the use of the liquid crystal display device and the like, and is usually formed in a thickness of 5 ⁇ m to 80 ⁇ m, but is not limited thereto.
  • the method for attaching the protective film for polarizing plates produced by the resin molded article of the present application to the polarizer is not particularly limited, and for example, polyvinyl alcohol-based adhesives or ultraviolet curable adhesives, including polyvinyl alcohol-based resins and crosslinking agents, For example, from oligomers such as radical polymerizable adhesives or epoxy resin vinyl esters polymerized from hydroxyl group-containing acrylates, epoxy acrylates, urethane acrylates, oxetane acrylates, polyester acrylates or silicone acrylates.
  • the second resin layer and the polarizer of the resin molded article can be attached by using known adhesive means such as induced cationic polymerizable adhesive.
  • the resin molded article formed by the resin mixture When used as a protective film for a polarizing plate, it can replace a TAC-based film or an acrylic protective film that has been used in the past, in particular, in the case of a conventional acrylic protective film, the adhesiveness with the polarizer
  • the second resin included in the second resin layer is represented by the above formula (2) By including the compound of, it has excellent affinity with the adhesive.
  • the second resin layer is formed by layer separation in the melt processing process, and thus, an additional primer coating step may be omitted on the surface of the protective film for polarizing plates, and excellent adhesion with the polarizer may be produced, thus producing time. And cost can be reduced, productivity can be increased.
  • Exemplary resin mixture of the present application can provide a protective film for a polarizing plate excellent in adhesion to the polarizer.
  • an additional primer coating step may be omitted on the surface of the protective film for the polarizing plate, and thus, excellent adhesion with the polarizer may be exhibited, thereby reducing production time and cost, and increasing productivity. .
  • Figure 1 shows a layered cross-sectional SEM image of the resin molded article prepared in Example 4.
  • Figure 2 shows a cross-sectional shape SEM photograph of the resin molded article prepared in Comparative Example 1.
  • haze and transmittance were measured using a haze meter HM-150 (Murakami Color Research Laboratory).
  • Melt viscosity was measured using a capillary rheometer (Capillary Rheometer 1501, Gottfert).
  • Example or Comparative Example After attaching a capillary die to the barrel (Barrel), the resin obtained in Example or Comparative Example was divided and filled three times. And, the shear viscosity (shear viscosity, pa * s) according to the shear rate (shear rate) at a processing temperature of 250?
  • the polarizing plate of width 18mm was prepared. Specifically, the polyvinyl alcohol-based resin film is stretched, dyed with iodine, and then treated with a boric acid aqueous solution, the specimen prepared in Examples and Comparative Examples as a protective film on one surface of the polarizer prepared of the specimen
  • the polarizing plate was prepared by adhering using a polyvinyl alcohol-type adhesive agent so that a 2nd resin layer may face the polarizer side.
  • a peel force of 90 ° was measured under the condition of 300 mm / min using a texture anlyze equipment (MHK). The peel force described the average value after 3 measurements.
  • the observed cross-sectional shape was evaluated according to the following criteria.
  • Example or Comparative Example the resin obtained in Example or Comparative Example was dissolved in methyl ethyl ketone solvent by 15% by weight, and then bar coated on LCD glass. Then, the coated LCD glass was pre-dried for 2 minutes in a 60 °C oven, and dried for 1 minute in a 90 °C oven.
  • a second resin was prepared in the same manner as in Preparation Example 1, except that 440 g of methyl methacrylate, 200 g of styrene, and 160 g of gamma-butyrolactone methacrylate were used as monomers.
  • a second resin was prepared in the same manner as in Preparation Example 1, except that 560 g of methyl methacrylate, 200 g of styrene, and 40 g of 2-hydroxyethyl methacrylate (2-HEMA) were used as the monomer. .
  • a second resin was prepared in the same manner as in Preparation Example 1, except that 520 g of methyl methacrylate, 200 g of styrene, and 80 g of N-vinylpyrrolidone were used as the monomer.
  • a second resin was prepared in the same manner as in Preparation Example 1, except that 400 g of methyl methacrylate, 200 g of styrene, and 40 g of gamma-butyrolactone methacrylate 160 g N-vinylpyrrolidone were used as monomers.
  • a second resin was prepared in the same manner as in Preparation Example 1, except that 600 g of methyl methacrylate and 200 g of styrene were used as monomers.
  • a second resin was prepared in the same manner as in Preparation Example 1, except that 280 g of methyl methacrylate, 200 g of styrene, and 320 g of gamma-butyrolactone methacrylate were used as monomers.
  • Second method was carried out in the same manner as in Production Example 1, except that 360 g of methyl methacrylate, 160 g of styrene 200 g gamma-butyrolactone methacrylate, and 80 g of 2-hydroxyethyl methacrylate (2-HEMA) were used as monomers. Resin was prepared.
  • a second resin was prepared in the same manner as in Preparation Example 1, except that 360 g of methyl methacrylate, 200 g of styrene, 160 g of gamma-butyrolactone methacrylate, and 80 g of N-vinyl pyrrolidone were used as monomers.
  • the pellet was extruded at a temperature of 250 ° C. in a twin screw extruder (Leistritz).
  • the pellets were manufactured using an extruder having a T-die gap of 1 t (EM EM Korea) to produce an extruded film having a film thickness of about 180 to 210 ⁇ m at a temperature of 250 ° C.
  • the extruded film was biaxially stretched in the MD and TD directions at a temperature of 135 ° C. to prepare a stretched film having a thickness of about 50 ⁇ m.
  • a specimen was prepared in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Preparation Example 2 was mixed with 90 parts by weight of the same first resin as used in Example 1.
  • a specimen was prepared in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Preparation Example 3 was mixed with 90 parts by weight of the same first resin as used in Example 1.
  • a specimen was prepared in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Preparation Example 4 was mixed with 90 parts by weight of the same first resin as used in Example 1.
  • a specimen was prepared in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Preparation Example 5 was mixed with 90 parts by weight of the same first resin as used in Example 1.
  • a specimen was prepared in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Preparation Example 6 was mixed with 90 parts by weight of the same first resin as used in Example 1.
  • Example 1 100 parts by weight of the first resin pellets used in Example 1 were dried in an oven, and the pellets were extruded in the same manner as in Example 1 to prepare an extruded film.
  • the extruded film was stretched in the same manner as in Example 1 to prepare a stretched film.
  • a specimen was prepared in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Preparation Example 7 was mixed with 90 parts by weight of the same first resin as used in Example 1.
  • a specimen was prepared in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Preparation Example 8 was mixed with 90 parts by weight of the same first resin as used in Example 1.
  • a specimen was prepared in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Preparation Example 9 was mixed with 90 parts by weight of the same first resin as used in Example 1.
  • a specimen was prepared in the same manner as in Example 1, except that 10 parts by weight of the second resin obtained in Preparation Example 10 was mixed with 90 parts by weight of the same first resin as used in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente divulgation concerne un mélange de résines, un copolymère, une pastille, un procédé de fabrication d'un article moulé en résine les utilisant, et un article moulé en résine. Le mélange de résines donné en exemple selon la présente divulgation peut former un film de protection pour lame polarisante, ledit film de protection ayant une excellente force d'adhérence à un polariseur. De plus, l'utilisation de ce mélange de résines permet l'omission d'une étape consistant à appliquer en plus un apprêt sur une surface du film de protection pour lame polarisante et la manifestation d'une excellente force d'adhérence au polariseur, réduisant ainsi le temps de production et les coûts et augmentant la productivité.
PCT/KR2014/006088 2013-07-08 2014-07-08 Mélange de résines Ceased WO2015005631A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201480049501.7A CN105531315B (zh) 2013-07-08 2014-07-08 树脂共混物
US14/903,263 US10392458B2 (en) 2013-07-08 2014-07-08 Resin blend

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2013-0079746 2013-07-08
KR20130079746 2013-07-08
KR1020140085017A KR101729813B1 (ko) 2013-07-08 2014-07-08 수지 혼합물
KR10-2014-0085017 2014-07-08

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008050536A (ja) * 2006-08-28 2008-03-06 Denki Kagaku Kogyo Kk 樹脂組成物と光学成形体
KR20100081932A (ko) * 2009-01-06 2010-07-15 주식회사 엘지화학 광학 필름 및 이를 포함하는 액정 표시 장치
KR20100104519A (ko) * 2009-03-18 2010-09-29 주식회사 엘지화학 아크릴계 공중합체 수지, 이를 포함하는 광학 필름 및 액정표시 장치
KR20110131124A (ko) * 2010-05-28 2011-12-06 주식회사 엘지화학 용융 가공 수지 성형품
KR20120038909A (ko) * 2010-10-14 2012-04-24 주식회사 엘지화학 용융 가공용 수지 혼합물
KR20120040964A (ko) * 2010-10-20 2012-04-30 주식회사 엘지화학 광학필름용 수지 조성물 및 이를 이용하여 형성된 광학필름

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008050536A (ja) * 2006-08-28 2008-03-06 Denki Kagaku Kogyo Kk 樹脂組成物と光学成形体
KR20100081932A (ko) * 2009-01-06 2010-07-15 주식회사 엘지화학 광학 필름 및 이를 포함하는 액정 표시 장치
KR20100104519A (ko) * 2009-03-18 2010-09-29 주식회사 엘지화학 아크릴계 공중합체 수지, 이를 포함하는 광학 필름 및 액정표시 장치
KR20110131124A (ko) * 2010-05-28 2011-12-06 주식회사 엘지화학 용융 가공 수지 성형품
KR20120038909A (ko) * 2010-10-14 2012-04-24 주식회사 엘지화학 용융 가공용 수지 혼합물
KR20120040964A (ko) * 2010-10-20 2012-04-30 주식회사 엘지화학 광학필름용 수지 조성물 및 이를 이용하여 형성된 광학필름

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