CN109476899A - Resin combination and the film being made of the resin combination - Google Patents

Resin combination and the film being made of the resin combination Download PDF

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Publication number
CN109476899A
CN109476899A CN201780045521.0A CN201780045521A CN109476899A CN 109476899 A CN109476899 A CN 109476899A CN 201780045521 A CN201780045521 A CN 201780045521A CN 109476899 A CN109476899 A CN 109476899A
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mass
resin combination
methyl
copolymer
hour
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Granted
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CN201780045521.0A
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CN109476899B (en
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松本真典
野口哲央
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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    • 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
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • 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
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • 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
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Polarising Elements (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The film for providing a kind of resin combination and being made of the resin combination, is difficult to happen birefringent, heat resistance, film-strength, excellent heat stability.According to the present invention, a kind of resin combination is provided, by 17~31 mass % of aromatic vinyl monomer unit (A), 38~63 mass % of (methyl) acrylate monomeric units (B), 4~14 mass % of unsaturated dicarboxylic anhydride monomer unit (C), 4~25 mass % of conjugated diene monomeric unit (D) is constituted, the absolute value of the value of following formula 1 is 0.005 or less, formula 1:- 0.10 × [A] -0.004 × [B]+0.10 × [C]+0.09 × [D], [A] in formula 1, [B], [C], [D] successively indicates aromatic vinyl monomer unit (A), (methyl) acrylate monomeric units (B), unsaturated dicarboxylic anhydride monomer unit (C), mass ratio in the resin combination of conjugated diene monomeric unit (D) , [A]+[B]+[C]+[D]=1.

Description

Resin combination and the film being made of the resin combination
Technical field
The present invention relates to be difficult to happen birefringent, heat resistance, film-strength, the resin combination of excellent heat stability and by this The film that resin combination is constituted.
Background technique
Transparent resin can be used for the various uses such as the component, food containers, groceries of household appliances.In recent years, from it is Lightness, From the aspect of productivity, cost, multi-purpose phase difference film, the polarizer protecting film, counnter attack made in liquid crystal display device of transparent resin Penetrate the optical component of film, diffusion disk, light guide sheet etc..
Liquid crystal display device is by clipping the liquid crystal cell of the formation such as transparent electrode, liquid crystal layer, colour filter with sheet glass and setting Set its two sides two polarizing films composition, the two sides of polarizing film use be used to protect surface by TAC (triacetate fiber Element) film constitute polarizer protecting film.
In order to realize liquid crystal display wide viewing angle range uniformity, it is desirable to polarizer protecting film do not have it is birefringent, still Due to TAC film slightly have it is birefringent, so in the presence of that birefringent problem can occur to the incident light of tilted direction.In addition, adjoint The enlargement of display, existing can be because birefringent distribution occurs for the deviation of external stress, the problem of contrast can decline, so Wish to be less likely to occur in polarizer protecting film birefringent variation caused by external stress.
As optical film resin, it is known to make methyl methacrylate, maleic anhydride and it is styrene copolymerized obtained from Copolymer resins (such as patent document 1).In addition, as birefringent small resin, it is known to make glutarimide resinoid (such as Patent document 2) or methyl methacrylate and N-phenyl maleimide, N-N-cyclohexylmaleimide copolymerization obtained from altogether Poly resin (such as patent document 3).
Existing technical literature
Patent document
1 international patent application WO2014/021264 of patent document
Patent document 2 Japanese Unexamined Patent Publication, 2006-No. 337493 bulletins
Patent document 3 Japanese Unexamined Patent Publication, 2013-No. 109285 bulletins
Summary of the invention
(solving the problems, such as)
The resin recorded in patent document 1 has carried out being used to increase film although excellent in terms of heat resistance and the transparency Birefringent resin design after forming, therefore purposes is restricted.Although the resin optics recorded in patent document 2 and 3 is special Property it is excellent, but the film-strength after shaping is not big enough, therefore purposes is restricted.
The purpose of the present invention is to provide the resin groups for being difficult to happen birefringent, heat resistance, film-strength, excellent heat stability The film for closing object and being made of the resin combination.
(solution to the problem)
Main points of the invention are as follows.
(1), a kind of resin combination includes: 17~31 mass % of aromatic vinyl monomer unit (A), (methyl) acrylic acid 38~63 mass % of ester monomer unit (B), 4~14 mass % of unsaturated dicarboxylic anhydride monomer unit (C), conjugate diene monomer list Member (D) 4~25 mass %, the absolute value of the value of following formula 1 be 0.005 hereinafter,
Formula 1:- 0.10 × [A] -0.004 × [B]+0.10 × [C]+0.09 × [D],
Wherein, [A] in formula 1, [B], [C], [D] successively indicate aromatic vinyl monomer unit (A), (methyl) acrylate The quality of monomeric unit (B), unsaturated dicarboxylic anhydride monomer unit (C), conjugated diene monomeric unit (D) in resin combination Than [A]+[B]+[C]+[D]=1.
(2), the resin combination as described in (1) includes:
By aromatic vinyl monomer unit (A), (methyl) acrylate monomeric units (B), unsaturated dicarboxylic anhydride monomer list 20~80 mass parts of copolymer (I) that first (C) is constituted；
0~60 mass parts of polymer (II) being made of (methyl) acrylate monomeric units (B)；And
By the copolymer grafted of aromatic vinyl monomer unit (A) and (methyl) acrylate monomeric units (B) to by being conjugated 5~60 mass parts of graft copolymer (III) made of the polymer that diene monomer unit (D) is constituted.
(3), the resin combination as described in (2), copolymer (I) includes: 20~80 matter of aromatic vinyl monomer unit (A) Measure %, 5~70 mass % of (methyl) acrylate monomeric units (B), 10~25 matter of unsaturated dicarboxylic anhydride monomer unit (C) Measure %.
(4), the resin combination as described in (2) or (3), the optical path length in 12 mass % chloroformic solutions of copolymer (I) The mist degree of 10mm is 2% or less.
(5), (1)~(4) any one of as described in resin combination, based on the total of the ASTM D1003 2mm thickness measured Light transmittance is 88% or more.
(6), a kind of film, contain (1)~(5) any one of described in resin combination.
(7), the film as described in (6) is used as polarizer protecting film.
(invention effect)
Birefringent, heat resistance, film-strength, the resin group of excellent heat stability are difficult to happen according to the present invention it is possible to provide Close object and the film containing the resin combination.
Specific embodiment
<term explanation>
In the specification of the present application, symbol "~" refer to " more than " and " following ", for example, the record of " A~B " refer to A or more, B with Under.
In the following, detailed description of embodiments of the present invention.
As the aromatic vinyl monomer unit (A) that can be used in resin combination of the invention, it can enumerate and be derived from The unit of following monomers: styrene, o-methyl styrene, m-methyl styrene, p-methylstyrene, 2,4-dimethyl benzene second The various phenylethylenes of alkene, ethyl styrene, p-tert-butylstyrene, α-methyl styrene, α-methyl-p-methylstyrene etc. Monomer.Wherein, preferably styrene units.One kind both can be used in these aromatic vinyl monomer units (A), can also incite somebody to action It is used in combination.
As (methyl) acrylate monomeric units (B) that can be used in resin combination of the invention, source can be enumerated In the unit of following monomers: methyl methacrylate, ethyl methacrylate, n-BMA, methacrylic acid 2- The various methacrylate monomers of ethylhexyl, two ring pentyl ester of methacrylic acid, isobornyl methacrylate etc., Yi Jibing E pioic acid methyl ester, ethyl acrylate, n-butyl acrylate, the own ester of 2-methyl of acrylic acid, 2-ethylhexyl of acrylic acid, decyl acrylate Deng various acrylate monomers.Wherein, preferably methyl methacrylate units.These (methyl) acrylate monomeric units (B) one kind both can be used, can also be used in combination of two or more.
As the unsaturated dicarboxylic anhydride monomer unit (C) that can be used in resin combination of the invention, source can be enumerated In the unit of the various anhydride monomers of maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride etc..Wherein, preferably maleic acid Acid anhydride unit.One kind both can be used in unsaturated dicarboxylic anhydride monomer unit (C), can also be used in combination of two or more.
As the conjugated diene monomeric unit (D) that can be used in resin combination of the invention, can enumerate derived from 1,3- Butadiene (butadiene), 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadienes, The unit of the monomer with conjugated double bond of 1,3-hexadiene, 2-methylpentadienes etc..Wherein, preferably butadiene unit.This One kind both can be used in a little conjugated diene monomeric units (D), can also be used in combination of two or more.
Resin combination of the invention is also possible in resin combination not hinder the range of invention effect to include In addition to aromatic vinyl monomer unit (A), (methyl) acrylate monomeric units (B), unsaturated dicarboxylic anhydride monomer unit (C) unit of other vinyl monomers and other than conjugated diene monomeric unit (D), preferably 5 mass % or less.As other The unit of vinyl monomer can enumerate the unit derived from following monomers: the vinyl cyanide base list of acrylonitrile, methacrylonitrile etc. Body, the vinyl carboxylic acid monomer of acrylic acid, methacrylic acid etc., N-methylmaleimido, N-ethyl maleimide, N-fourth The N of base maleimide, N-N-cyclohexylmaleimide etc.-alkyl maleimide monomer, N-phenyl maleimide, N-first The various monomers of the N of base phenyl maleimide, N-chlorophenylmaleimide etc.-aryl maleimide monomer etc..In addition to Aromatic vinyl monomer unit (A), (methyl) acrylate monomeric units (B), unsaturated dicarboxylic anhydride monomer unit (C) and Other than conjugated diene monomeric unit (D), other vinyl monomers included in resin combination units, be also possible to by It is used in combination.
The structural unit of resin combination of the invention is preferably 17~31 matter of aromatic vinyl monomer unit (A) Measure %, 38~63 mass % of (methyl) acrylate monomeric units (B), 4~14 matter of unsaturated dicarboxylic anhydride monomer unit (C) Measure %, 4~25 mass % of conjugated diene monomeric unit (D)；More preferably, 18~25 matter of aromatic vinyl monomer unit (A) Measure %, 45~60 mass % of (methyl) acrylate monomeric units (B), 4~12 matter of unsaturated dicarboxylic anhydride monomer unit (C) Measure %, 10~20 mass % of conjugated diene monomeric unit (D).
If aromatic vinyl monomer unit (A) used in resin combination is 17 mass % or more, can obtain To being difficult to happen birefringent, the good resin combination of the transparency；It is available to be more difficult to occur if it is 18 mass % or more Birefringent, transparent better resin combination, so being preferred.If aromatic vinyl monomer unit (A) is 31 matter % is measured hereinafter, then available be difficult to happen birefringent, the good resin combination of heat resistance；If it is 25 mass % hereinafter, It is then available to be more difficult that birefringent, the better resin combination of heat resistance occurs, so being preferred.
It, can be with if (methyl) acrylate monomeric units (B) used in resin combination are 38 mass % or more It obtains being difficult to happen birefringent, the good resin combination of heat resistance；It is available to be more difficult to send out if it is 45 mass % or more Raw birefringent, the better resin combination of heat resistance, so being preferred.If (methyl) acrylate monomeric units (B) are 63 mass % are hereinafter, then available be difficult to happen birefringent resin combination；If it is 60 mass % hereinafter, can then obtain To being more difficult that birefringent resin combination occurs, so being preferred.
If unsaturated dicarboxylic anhydride monomer unit (C) used in resin combination is 4 mass % or more, can obtain To the good resin combination of heat resistance, so being preferred.If unsaturated dicarboxylic anhydride monomer unit (C) is 14 mass % Hereinafter, then available be difficult to happen birefringent, good thermal stability resin combination；If 12 mass % hereinafter, if can To obtain being more difficult occurring birefringent, the better resin combination of thermal stability, so being preferred.
If conjugated diene monomeric unit used in resin combination (D) is 4 mass % or more, available to be difficult to Birefringent, the good resin combination of film-strength occurs；If it is 10 mass % or more, it is available be more difficult to occur it is two-fold It penetrates, the better resin combination of film-strength, so being preferred.If conjugated diene list amount unit (D) be 25 mass % hereinafter, It is then available to be difficult to happen birefringent, the good resin combination of heat resistance；If it is 20 mass % hereinafter, then available It is more difficult that birefringent, the better resin combination of heat resistance occurs, so being preferred.
Resin combination of the invention, it is preferred that the absolute value of the value of formula 1, which is 0.005 or less,.Wherein, in formula 1 [A], [B], [C], [D] successively indicate aromatic vinyl monomer unit (A), (methyl) acrylate monomeric units (B), insatiable hunger With the mass ratio of monomeric dicarboxylic acid anhydride's unit (C), conjugated diene monomeric unit (D) in resin combination, [A]+[B]+[C]+ [D]=1.
(formula 1) -0.10 × [A] -0.004 × [B]+0.10 × [C]+0.09 × [D]
Resin combination of the invention, due to aromatic vinyl monomer unit (A), (methyl) acrylate monomeric units (B), each ingredient of unsaturated dicarboxylic anhydride monomer unit (C) and conjugated diene monomeric unit (D) is cancelled out each other birefringent, and can It is smaller with the absolute value for obtaining the value of formula 1, it is more difficult to happen birefringent resin combination, so being preferred.If formula 1 The absolute value of value be 0.003 hereinafter, then available be more difficult that birefringent resin combination occurs, so being preferred；Such as The absolute value of the value of fruit formula 1 is 0.001 hereinafter, then available will also be more difficult that birefringent resin combination occurs, so being Preferably.
Resin combination of the invention, preferably comprises following components: by aromatic vinyl monomer unit (A), (methyl) The copolymer (I) that acrylate monomeric units (B), unsaturated dicarboxylic anhydride monomer unit (C) are constituted is 20~80 mass parts, by The polymer (II) that (methyl) acrylate monomeric units (B) are constituted is 0~60 mass parts, by by aromatic vinyl monomer list The copolymer grafted of first (A) and (methyl) acrylate monomeric units (B) composition conjugated diene monomeric unit (D) to being made of Polymer and the graft copolymer (III) that is formed is 5~60 mass parts, it is highly preferred that copolymer (I) is 20~40 mass parts, Polymer (II) is 25~50 mass parts, and graft copolymer (III) is 10~45 mass parts.
If copolymer used in resin combination (I) is 20 mass parts or more, available heat resistance is good Resin combination, so being preferred.If copolymer (I) be 80 below the mass, available good thermal stability Resin combination, so being preferred；If 40 below the mass, the available better resin combination of thermal stability, So being preferred.
If polymer used in resin combination (II) be 0 mass parts more than, it is available be difficult to happen it is two-fold It penetrates, the resin combination of good thermal stability；More than 25 mass parts, it is available be more difficult to occur it is birefringent, hot steady Qualitative better resin combination, so being preferred.If polymer (II) be 60 below the mass, it is available to be difficult to Birefringent resin combination occurs；Below the mass if it is 50, available to be more difficult that birefringent resin combination occurs Object, so being preferred.
If graft copolymer used in resin combination (III) is 5 mass parts or more, available to be difficult to happen Birefringent, the good resin combination of film-strength；It is available to be more difficult that birefringent, film occurs more than 10 mass parts The better resin combination of intensity, so being preferred.If it is graft copolymer (III) be 60 below the mass, can be with Obtain the resin combination for being difficult to happen birefringent, heat resistance and good thermal stability；It below the mass if it is 45, can be with It obtains being more difficult to occur birefringent, heat resistance and the better resin combination of thermal stability, so being preferred.
Resin combination of the invention, if each comfortable 23 DEG C of copolymer (I), polymer (II), graft copolymer (III) Under relative to d line refractive index be n1, n2, n3, copolymer (I), polymer (II), graft copolymer (III) respective quality Than for w1, w2, w3, then it is preferred that the absolute value of the value of formula 2, which is 0.005 or less,.
(formula 2) n1 × w1/ (w1+w2)+n2 × w2/ (w1+w2)-n3
If the absolute value of the value of formula 2 be 0.005 hereinafter, if the available good resin combination of the transparency, so being excellent Choosing, more preferably 0.003 hereinafter, still more preferably 0.001 or less.Since copolymer (I) and polymer (II) mix, So by the product that copolymer (I) and polymer (II) are mixed to get be it is transparent, can be by reducing copolymer (I) and gather The refringence of product and graft copolymer (III) that object (II) is mixed to get is closed to keep the transparency.
Order by merging for copolymer (I), polymer (II), graft copolymer (III) each ingredient, does not limit especially System, it can be cited for example that by whole components simultaneously mix method, two kinds of ingredients be pre-mixed after mixed again with another ingredient The method etc. of conjunction.In addition, such mixing can be implemented with existing well known method.
As the method that whole components are mixed simultaneously, uniaxial or twin shaft melt extruder can be used for example, add Copolymer (I), polymer (II), each ingredient of graft copolymer (III) and various additives are added to carry out melting mixing.As with Uniaxial or twin shaft melt extruder can be used for example copolymer (I) and polymer in the method for another ingredient mixing (II) after being pre-mixed, uniaxial or twin shaft melt extruder and graft copolymer (III) melting mixing are reused.This When, various additives can also be added and carry out melting mixing.
As the aromatic vinyl monomer unit (A) that can be used in copolymer (I), can enumerate derived from following monomers Unit: styrene, o-methyl styrene, m-methyl styrene, p-methylstyrene, 2,4-dimethyl styrenes, ethylo benzene second The various styrene monomers of alkene, p-tert-butylstyrene, α-methyl styrene, α-methyl-p-methylstyrene etc..Wherein, Preferably styrene units.One kind both can be used in these aromatic vinyl monomer units (A), can also be by two or more groups It closes and uses.
As (methyl) acrylate monomeric units (B) that can be used in copolymer (I), can enumerate derived from following monomers Unit: methyl methacrylate, ethyl methacrylate, n-BMA, 2-ethylhexyl of methacrylic acid, first The various methacrylate monomers and methyl acrylate of base dicyclopentanyl acrylate, isobornyl methacrylate etc., third Various the third of olefin(e) acid ethyl ester, n-butyl acrylate, the own ester of 2-methyl of acrylic acid, 2-ethylhexyl of acrylic acid, decyl acrylate etc. Olefin(e) acid ester monomer.Wherein, preferably methyl methacrylate units.These (methyl) acrylate monomeric units (B) both can be with Using one kind, can also be used in combination of two or more.
As the unsaturated dicarboxylic anhydride monomer unit (C) that can be used in copolymer (I), can enumerate derived from maleic acid The unit of the various anhydride monomers of acid anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride etc..Wherein, preferably maleic anhydride units. One kind both can be used in unsaturated dicarboxylic anhydride monomer unit (C), can also be used in combination of two or more.
Copolymer (I) is also possible to include in the copolymer in addition to aromatic vinyl with the range for not hindering invention effect It is other other than base monomeric unit (A), (methyl) acrylate monomeric units (B) and unsaturated dicarboxylic anhydride monomer unit (C) The unit for the vinyl monomer that can be copolymerized, preferably 5 mass % or less.List as other vinyl monomers that can be copolymerized Member can enumerate the unit derived from following monomers: the cyanided vinyl monomer of acrylonitrile, methacrylonitrile etc., acrylic acid, methyl The vinyl carboxylic acid monomer of acrylic acid etc., N-methylmaleimido, N-ethyl maleimide, N-butyl maleimide, The N of N-N-cyclohexylmaleimide etc.-alkyl maleimide monomer, N-phenyl maleimide, N-aminomethyl phenyl Malaysia acyl The various monomers of the N of imines, N-chlorophenylmaleimide etc.-aryl maleimide monomer etc..Other second that can be copolymerized The unit of alkenyl monomer is also possible to be used in combination of two or more.
The structural unit of copolymer (I) is 20~80 mass % of aromatic vinyl monomer unit (A), (methyl) propylene 5~70 mass % of acid ester monomer unit (B), 10~25 mass % of unsaturated dicarboxylic anhydride monomer unit (C)；More preferably, fragrant Fragrant 45~70 mass % of race's vinyl monomer unit (A), 7~40 mass % of (methyl) acrylate monomeric units (B), unsaturation 10~23 mass % of monomeric dicarboxylic acid anhydride's unit (C).In addition, the structural unit of so-called copolymer, is with defined analysis method There is distribution (hereinafter, the distribution is known as to form distribution) in the assay value measured, expression is the group actually in structural unit At the average value of distribution.
If aromatic vinyl monomer unit (A) used in copolymer (I) is 20 mass % or more, available Thermal stability increase, the formed body when forming to resin combination with good appearance；If it is 45 mass % More than, then available thermal stability further increases, has better appearance when forming to resin combination Formed body, so being preferred.If aromatic vinyl monomer unit (A) be 80 mass % hereinafter, if with polymer (II) Intermiscibility increase, the transparency of resin combination is good；If it is 70 mass % hereinafter, the then intermiscibility with polymer (II) It further increases, the transparency of resin combination is good, so being preferred.
If (methyl) acrylate monomeric units (B) used in copolymer (I) are 5 mass % or more, and it polymerize The intermiscibility of object (II) increases, and the transparency of resin combination is good；If it is 7 mass % or more, with polymer (II) Intermiscibility further increases, and the transparency of resin combination is more preferable, so being preferred.(if methyl) acrylate monomer list First (B) is 70 mass % hereinafter, then available thermal stability increases, has when forming to resin combination well Appearance formed body；If it is 40 mass % hereinafter, then available thermal stability further increase, to resin combination into Formed body with better appearance when row forming, so being preferred.
If unsaturated dicarboxylic anhydride monomer unit (C) used in copolymer (I) is 10 mass % or more, heat resistance Well, increase with the intermiscibility of polymer (II), the transparency of resin combination is good, so being preferred.If unsaturated Monomeric dicarboxylic acid anhydride's unit (C) is 25 mass % hereinafter, then available thermal stability increases, resin combination is formed Formed body with good appearance when processing, moreover, the intermiscibility with polymer (II) increases, the transparency of resin combination Well；If it is 23 mass % hereinafter, then available thermal stability further increases, processing is formed to resin combination When the formed body with more good appearance, moreover, increasing with the intermiscibility of polymer (II), the transparency of resin combination is good It is good, so being preferred.
Mist when optical path length 10mm in 12 mass % chloroformic solutions of the copolymer (I) measured based on JIS K -7136 Degree is preferred for 2% or less.If mist degree be 2% hereinafter, if due to copolymer (I) composition distribution it is small, with polymer (II) composition of immiscible unsaturated dicarboxylic anhydride monomer unit (C) mostly is few, it is possible to keep and polymer (II) The transparency of intermiscibility, resin combination is good, so being preferred.In addition, mist degree is that handle is adjusted to copolymer in chloroform In be filled into the quartzy square box of optical path length 10mm measurement for the solution of 12 mass % and use haze meter according to JIS K -7136 The measured value that (the HAZEGUARD II of Toyo Seiki company manufacture) is measured.
The polymerization methods of copolymer (I) are not particularly limited, it can be by well known to polymerisation in solution, bulk polymerization etc. Method manufacture, more preferably polymerisation in solution.It is few that solvent used in polymerisation in solution is never easy to produce by-product, adverse effect Viewpoint consideration, preferably non-polymerization solvent.It as the type of solvent, is not particularly limited, such as can enumerate: acetone, methyl The ketone of ethyl ketone, methyl iso-butyl ketone (MIBK), acetophenone etc.；The ethers of tetrahydrofuran, Isosorbide-5-Nitrae-dioxanes etc.；Toluene, ethylo benzene, two The aromatic hydrocarbon etc. of toluene, chlorobenzene etc., from the viewpoint of monomer, the solubility of copolymer, solvent recovery easness, preferably Methyl ethyl ketone, methyl iso-butyl ketone (MIBK).Relative to obtained 100 mass parts of copolymerization object amount, the additive amount of solvent is preferably 10~ 100 mass parts, more preferably 30~80 mass parts.It is viscous from control reaction speed and polymer fluid more than 10 mass parts Be from the perspective of degree it is suitable, below the mass if it is 100, in terms of obtaining desired weight average molecular weight (Mw) It is suitable.
Polymerization technique can be intermittence type polymerization method, semibatch polymerization, any mode in continuous polymerization, from From the perspective of obtaining desired molecular weight ranges and the transparency, preferably intermittence type polymerization method.
Polymerization is not particularly limited, from the viewpoint of it can be manufactured well by simple process productivity, Preferably radical polymerization.It as polymerization initiator, is not particularly limited, such as dibenzoyl peroxide, mistake can be used Aoxidize t-butyl perbenzoate, 1,1-bis- (tert-butyl hydroperoxide)-2-hexahydrotoluenes, isopropyl peroxide single carbon tert-butyl acrylate, Peroxidating-2-ethylhexanate, peroxide acetic acid butyl ester, dicumyl peroxide, 3,3-two (tert-butyl hydroperoxides) The well known organic peroxide of ethyl butyrate etc., the double methyl propionitrile of azobis isobutyronitrile, azo bis cyclohexane formonitrile HCN, azo, The well known azo-compound of the double methylbutyronitriles of azo etc..These polymerization initiators are also possible to be used in combination of two or more. Wherein, it is preferable to use the organic peroxide that 10 hours half life temperatures are 70~110 DEG C.
Transparent good copolymer (I) in order to obtain, it is necessary to enter while the control for carrying out keeping composition distribution reduced Row polymerization especially requires the production formed with the unsaturated dicarboxylic anhydride monomer unit (C) immiscible with polymer (II) mostly The few mode of object is polymerize.Since aromatic vinyl monomer and unsaturated dicarboxylic anhydride monomer are total with very strong interaction Poly- property, so in a manner of corresponding with the polymerization speed of aromatic vinyl monomer and (methyl) acrylate monomer continuously in batches Unsaturated dicarboxylic anhydride monomer and/or aromatic vinyl monomer are added, moreover, in batches also according to polymerization speed appropriate adjustment The method for adding flow is suitable.If one side appropriate adjustment polymerization temperature, polymerization time and polymerization initiator additive amount, one Side controls polymerization speed, then can more accurately reduce the composition distribution of copolymer, so being suitable.
Moreover, the method for adjusting molecular weight, in addition to adjustment polymerization temperature, polymerization time and polymerization initiator additive amount In addition, it can also be realized by adjusting amount of solvent and chain-transferring agent additive amount.As chain-transferring agent, do not limit especially System, can be used for example n-dodecyl mercaptan, tert-dodecylmercaotan, 2, well known to 4-diphenyl-1-amylenes of-4-methyl etc. Chain-transferring agent.
After polymerization, it can according to need and hindered phenol compound, lactone compound, Phosphorus is added in polymer fluid The resistance to light stabilizer such as heat-resisting stabilizing agent, hindered amine compound, the benzotriazole compound of compound, sulphur class compound etc., The additives such as lubricant, plasticizer, colorant, antistatic agent, mineral oil.Relative to whole 100 mass parts of monomeric unit, add Dosage is preferably less than 0.2 mass parts.These additives both can be used alone, and can also be used in combination of two or more.
Method for recycling copolymer (I) from polymer fluid, is not particularly limited, well known devolatilization skill can be used Art.For example, the following methods can be used: polymer fluid is continuously supplied into twin shaft devolatilization extruder with gear pump, to polymer solvent, Unreacted monomer etc. carries out devolatilization processing.In addition, for the devolatilization ingredient comprising polymer solvent, unreacted monomer etc., with condensation Device etc. makes it condense and recycle, and is refined with destilling tower to condensate liquid, polymer solvent can recycle as a result,.
As (methyl) acrylate monomeric units (B) that can be used in polymer (II), can enumerate derived from following lists The unit of body: methyl methacrylate, ethyl methacrylate, n-BMA, 2-ethylhexyl of methacrylic acid, Various methacrylate monomers and the methyl acrylates, third such as two ring pentyl ester of methacrylic acid, isobornyl methacrylate The various propylene such as olefin(e) acid ethyl ester, n-butyl acrylate, the own ester of 2-methyl of acrylic acid, 2-ethylhexyl of acrylic acid, decyl acrylate Acid ester monomer.Wherein, preferably methyl methacrylate units.These (methyl) acrylate monomeric units (B) can both make With one kind, it is also possible to be used in combination of two or more.
For copolymer (II), it is also possible to include in the copolymer in addition to (methyl) with the range for not hindering invention effect The unit of other vinyl monomers that can be copolymerized other than acrylate monomeric units (B), preferably 5 mass % or less.Make For the unit of other vinyl monomers that can be copolymerized, the unit derived from following monomers: the aromatic series of styrene etc. can be enumerated Vinyl monomer, the cyanided vinyl monomer of acrylonitrile, methacrylonitrile etc., the vinyl carboxylic of acrylic acid, methacrylic acid etc. Acid monomers, N-methylmaleimido, N-ethyl maleimide, N-butyl maleimide, N-N-cyclohexylmaleimide Deng N-alkyl maleimide monomer, N-phenyl maleimide, N-methylphenylmaleimide, N-chlorphenyl Malaysia acyl The various monomers of the N of imines etc.-aryl maleimide monomer etc..The unit of other vinyl monomers that can be copolymerized can also To be used in combination of two or more.
The polymerization methods of copolymer (II) are not particularly limited, it can be by bulk polymerization, polymerisation in solution, suspended poly- The manufacture of method well known to conjunction, the suspended polymerization of ontology-, emulsion polymerization etc., but impurity is few in order to obtain, the good polymer of form and aspect (II), bulk polymerization or polymerisation in solution are preferred.Moreover, the polymerization technique of polymer (II) can be intermittence type polymerization, Any mode in semibatch polymerization, continuous polymerization, but from the point of view of productivity, preferably continuous polymerization.
In the polymerization methods using continuous polymerization as copolymer (II), the structure of reactor is preferably that handle is thoroughly mixed The structure that type reactor (CSTR) and plug-flow type reactor (PFR) are connected together in series.Alternatively, it is also possible to according to purpose It is different and CSTR, PFR it is each 1 or it is multiple connect, but the number of CSTR is preferably 1~2, and especially 1 is More preferably.The number of PFR is preferably that 1~3, especially 1 are preferred.
In the polymerization methods using polymerisation in solution as polymer (II), the solvent used is not particularly limited, From the viewpoint of calm facile degree, dissolubility etc., for instance that acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), benzene second The ketone of ketone etc.；The ethers of tetrahydrofuran, Isosorbide-5-Nitrae-dioxanes etc.；The aromatic hydrocarbon of toluene, ethylo benzene, dimethylbenzene, chlorobenzene etc.；N, The solvent etc. of N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidones etc., wherein from the molten of polymer (II) From the viewpoint of dissolubility in agent, preferably toluene, ethylo benzene.For the additive amount of these solvents, it is not also specifically limited, It is preferably, in 5~25 mass parts in the range of 1~30 mass parts relative to 100 mass parts of total amount of monomeric compound It is preferred in range.
The polymerization of polymer (II) is not particularly limited, be manufactured well from simple process productivity can be passed through From the viewpoint of, arbitrary radical polymerization initiator can be used in preferably free radical polymerization.
Radical polymerization initiator used in polymerization for polymer (II), is not particularly limited, such as can adopt With the well known peroxide of azo-compound, organic peroxide, inorganic peroxide, hydrogen peroxide etc..Wherein, from reaction From the viewpoint of control is easy and is easy to get, it is preferred to use the double methyl of azobis isobutyronitrile, azo bis cyclohexane formonitrile HCN, azo The well known azo-compound of the double methylbutyronitriles of propionitrile, azo etc.；Dibenzoyl peroxide, peroxidized t-butyl perbenzoate, 1, 1-bis- (tert-butyl hydroperoxide)-2-hexahydrotoluenes, isopropyl peroxide single carbon tert-butyl acrylate, peroxidating-2-thylhexoic acid uncle Butyl ester, peroxide acetic acid butyl ester, cumyl peroxide, 3, the well known of 3-two (tert-butyl hydroperoxide) ethyl butyrates etc. have Machine peroxide.
In the polymerization of polymer (II), radical polymerization initiator both be can be used alone, can also will be two or more It is applied in combination.From the viewpoint of the reaction speed of polymerization, aggregate rate control, in the manufacture of existing styrene resin Commonly radical polymerization initiator is preferred, specifically, the azo for the use of 10 hour half life temperature being 70~120 DEG C Close object, organic peroxide is preferred.
It for the usage amount of radical polymerization initiator, is not particularly limited, 100 matter of total amount relative to monomeric compound Part is measured, the use of 0.001~0.1 mass parts is preferred, is preferred especially with 0.002~0.03 mass parts.
It is 0.001 matter if total amount 100 mass parts of the usage amount of radical polymerization initiator relative to monomeric compound Part or 0.002 mass parts or more are measured, then available enough polymerization speeds, it is possible to keep good productivity.Such as Total amount 100 mass parts of the usage amount of fruit radical polymerization initiator relative to monomeric compound are 0.1 mass parts or 0.03 Below the mass, then it can inhibit polymerization speed, become easy reaction controlling, it is possible to make the molecular weight of polymer (II) Control becomes easy.
Arbitrary chain-transferring agent can be used in the polymerization of polymer (II).The chain-transferring agent used is not limited especially System, but from be easy to get, molecular weight control be easy etc. from the viewpoint of, specifically, n-dodecyl mercaptan, uncle ten can be used Dialkyl group mercaptan, 2, the chain-transferring agent of 4-diphenyl-1-amylenes of-4-methyl etc..In addition, about chain-transferring agent, it both can be independent It uses, can also be used in combination of two or more.
The usage amount of chain-transferring agent, as long as in the range of obtaining the target molecular weight of polymer (II), without special Limitation, but relative to 100 mass parts of the total amount of monomeric compound, it the use of 0.05~2.0 mass parts is preferably, especially relatively It the use of 0.2~0.8 mass parts is preferred in 100 mass parts of total amount of monomeric compound.If the usage amount of chain-transferring agent For more than 0.05 mass parts and 2.0 below the mass, then the mesh of (methyl) acrylic acid esters co-polymer (B) can be readily derived Mark molecular weight.
It for the polymerization temperature of polymer (II), is not particularly limited, reaction temperature when using continuous polymerization, in CSTR It is preferred for 110 DEG C~160 DEG C, is especially preferred in the range of 120 DEG C~140 DEG C.In addition, anti-in PFR Answering temperature to be for 120 DEG C~170 DEG C is especially preferred in the range of 130 DEG C~150 DEG C preferably.If so, Reaction is easy to control, furthermore, it is possible to obtain forming uniform polymer (II).
Method for removing the volatile ingredient of solvent, unreacted monomer used in the polymerization of polymer (II) etc., It is not particularly limited, well known method can be used, but the use of the method for devolatilization slot is wherein preferred.Use devolatilization slot When, it is preferably that it is preferred for being especially held in 240 DEG C or less that the temperature of molten resin, which is maintained at 260 DEG C or less,.If Resin temperature is suppressed to 260 DEG C or 240 DEG C hereinafter, can then inhibit depolymerization caused by the heat deterioration of polymer (II), is obtained To the excellent polymer of form and aspect (II).In addition, the method for adjustment about resin temperature, can by adjusting devolatilization slot temperature into Row.
The heat deterioration when processing of polymer (II), the good form and aspect of maintenance in order to prevent, can be used arbitrary freedom Base agent for capturing.Free radical scavenger is not particularly limited, phenol compound, organophosphorus compound, organic can be enumerated The antioxidant of sulphur class compound, aminated compounds etc..These free radical scavengers both can be used alone, can also be by two kinds Combination of the above uses.These free radical scavengers, due in exhaust screw formula extruder styrene-maleimide It is subjected to significant thermal history in the process of volatile component devolatilization in copolymer, so in order to be maintained as free radical scavenger Function, with heat resistance, thermal stability compound be particularly preferred.Such as 1% heating loss temperature be more than 300 DEG C Free radical scavenger is more preferred.It is preferred to the product of polymerization addition free radical scavenger after polymerization.If It is added before polymerization or in polymerization, then polymerization speed is low sometimes.
As the conjugated diene monomeric unit (D) that can be used in resin combination of the invention, can enumerate derived from 1,3- Butadiene (butadiene), 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadienes, The unit of the monomer with conjugated double bond of 1,3-hexadiene, 2-methylpentadienes etc..Wherein, preferably butadiene unit.This One kind both can be used in a little conjugated diene monomeric units (D), can also be used in combination of two or more.
As the aromatic vinyl monomer unit (A) that can be used in graft copolymer (III), can enumerate derived from following The unit of monomer: styrene, o-methyl styrene, m-methyl styrene, p-methylstyrene, 2,4-dimethyl styrenes, second The various styrene monomers of base styrene, p-tert-butylstyrene, α-methyl styrene, α-methyl-p-methylstyrene etc.. Wherein, preferably styrene units.One kind both can be used in these aromatic vinyl monomer units (A), can also be by two kinds Combination of the above uses.
As (methyl) acrylate monomeric units (B) that can be used in graft copolymer (III), it can enumerate and be derived from down State the unit of monomer: methyl methacrylate, ethyl methacrylate, n-BMA, 2-ethyl of methacrylic acid The various methacrylate monomers and acrylic acid of own ester, two ring pentyl ester of methacrylic acid, isobornyl methacrylate etc. Methyl esters, ethyl acrylate, n-butyl acrylate, the own ester of 2-methyl of acrylic acid, 2-ethylhexyl of acrylic acid, decyl acrylate etc. Various acrylate monomers.Wherein, preferably methyl methacrylate units.These (methyl) acrylate monomeric units (B) Both one kind can be used, can also be used in combination of two or more.
For graft copolymer (III), in the range of not hindering The effect of invention, also may include in addition to conjugated diene Other other than monomeric unit (D), aromatic vinyl monomer unit (A), (methyl) acrylate monomeric units (B) can be total to The unit of poly- vinyl monomer, preferably 5 mass % or less.It, can as the unit of other vinyl monomers that can be copolymerized To enumerate: the cyanided vinyl monomer from acrylonitrile, methacrylonitrile etc., the vinyl carboxylic of acrylic acid, methacrylic acid etc. Acid monomers, N-methylmaleimido, N-ethyl maleimide, N-butyl maleimide, N-N-cyclohexylmaleimide Deng N-alkyl maleimide monomer, N-phenyl maleimide, N-methylphenylmaleimide, N-chlorphenyl Malaysia acyl The unit of the various monomers such as the N of imines etc.-aryl maleimide monomer.The unit of other vinyl monomers that can be copolymerized It is also possible to be used in combination of two or more.
Graft copolymer (III) is made by aromatic vinyl monomer unit (A), (methyl) acrylate monomeric units (B) constitute copolymer be combined into the polydiene shaped polymer being made of conjugated diene monomeric unit (D), include The copolymer of poplar bundles structure.Moreover, in graft copolymer (III) be included in be graft-polymerized when as by-product generate, Not with polydiene shaped polymer grafting, by aromatic vinyl monomer unit (A) and (methyl) acrylate monomer list The copolymer that first (B) is constituted.There are polydiene shaped polymer, by making aromatic series second with well known method Alkenyl monomer unit (A), (methyl) acrylate monomeric units (B) polymerization obtain graft copolymer (III).
The polydiene shaped polymer that can be used in graft copolymer (III) can enumerate polybutadiene, fourth two The conjugation of alkene-styrol copolymer, butadiene-acrylonitrile copolymer, polyisoprene, styrene-isoprene copolymer etc. The hydrogen additive of polydiene and they, they both can be used alone, and can also be used in combination of two or more.Wherein, Preferably polybutadiene.
The polymerization methods of graft copolymer (III) are not particularly limited, it can be poly- using such as bulk polymerization, solution Method well known to conjunction, suspended polymerization, the suspended polymerization of ontology-, emulsion polymerization etc., but wherein emulsion polymerization method is preferred.
It for the polymerization of graft copolymer (III), is not particularly limited, but good from simple process productivity can be passed through From the viewpoint of manufacturing well, arbitrary radical polymerization initiator is can be used in preferably free radical polymerization.
For radical initiator used in graft copolymer (III), it is bicyclic that azobis isobutyronitrile, azo can be used The azo-compound of hexane formonitrile HCN etc.；Dibenzoyl peroxide, peroxidized t-butyl perbenzoate, peroxidating-2-thylhexoic acid uncle Butyl ester, peroxide acetic acid butyl ester, cumyl peroxide, 3, the organic peroxy of 3-two (tert-butyl hydroperoxide) ethyl butyrates etc. Compound；Or the inorganic peroxide of hydrogen peroxide, potassium peroxydisulfate, Ammonium Persulfate 98.5 etc., but wherein using inorganic peroxide, Organic peroxide is preferably, using inorganic peroxide, the organic peroxide together reducing agent with ferrous sulfate etc. The redox type initiators being composed are preferred.In addition, in the polymerization of graft copolymer (III), radical polymerization Closing initiator may be used alone, used in two or more.
It for the usage amount of radical polymerization initiator, is not particularly limited, 100 matter of total amount relative to monomeric compound Part is measured, the use of 0.1~0.5 mass parts is preferred, is preferred especially with 0.5~3.5 mass parts.
If the usage amount of radical polymerization initiator, relative to by polydiene shaped polymer, aromatic ethenyl It is 100 mass parts of total amount of the monomeric compound of monomeric unit (A) and (methyl) acrylate monomeric units (B) composition, is 0.1 It is more than mass parts, then available enough polymerization speeds, it is possible to keep good productivity.If free radical polymerization is drawn Total amount 100 mass parts of the usage amount of agent relative to monomeric compound are sent out, below the mass for 3.5, then can inhibit polymerization speed Degree, reaction controlling become easy.
Arbitrary chain-transferring agent can be used in the polymerization of graft copolymer (III).Do not have to the chain-transferring agent used Especially limitation, but from be easy to get, molecular weight control be easy etc. from the viewpoint of, specifically, dodecyl sulphur can be used Alcohol, tert-dodecylmercaotan, 2, the chain-transferring agent of 4-diphenyl-1-amylenes of-4-methyl etc..Chain-transferring agent both can individually make With can also be used in combination of two or more.
It for the polymerization temperature of graft copolymer (III), is not particularly limited, reaction temperature when using emulsion polymerization, From the viewpoint of improving polymerization rate, maintaining good productivity, preferably 50 DEG C or more, 55 DEG C or more are particularly preferred 's.In addition, from the viewpoint of the yield of the coagulum or attachment reduced in aggregation container, the good productivity of maintenance, 98 DEG C or less are preferably, and 90 DEG C or less are particularly preferred.
In resin combination, in a range that does not hinder the effect of the present invention, can also be compounded stabilizer, plasticizer, Lubricant, antioxidant, ultraviolet absorbing agent, light stabilizer, colorant etc..
The total light transmittance for the 2mm thickness of resin combination of the invention measured based on ASTM D1003 is 88% or more, Preferably 89% or more, more preferably 90% or more.If the total light transmittance of 2mm thickness is 88% or more, after forming With the excellent transparency.In addition, total light transmittance is to use haze meter (Japanese electricity Se industrial group system based on ASTM D1003 NDH -1001DP the type made), to emission forming machine (IS -50EPN of Toshiba Machine Co. Ltd's manufacture) is used, in barrel temperature 230 DEG C, the value that is measured of the mirror surface piece of the long 90mm that shapes under 40 DEG C of mold temperature of molding condition, width 55mm, thickness 2mm.
Resin combination of the invention is as polarizer protecting film in use, phase difference (Re) is pressed in the face calculated with formula 3 100 μm conversion, preferably 30nm hereinafter, more preferably 20nm hereinafter, further preferably be 10nm or less；The thickness phase calculated with formula 4 Potential difference (Rth) by 100 μm conversion, preferably 20nm hereinafter, more preferably 10nm hereinafter, further preferably be 5nm or less.If in face Phase difference (Re) is 30nm or less, thickness phase difference (Rth) is 20nm hereinafter, then using in the polarizing film of liquid crystal display device When the film, will not occur liquid crystal display device contrast it is low equal the problem of, so being suitable.
(formula 3) Re=(nx-ny) × d
(formula 4) Rth={ 2-nz of (nx+ny) ÷ } × d
In addition, in above-mentioned formula, nx, ny and nz are that refractive index is maximum direction as X-axis, vertical with X-axis in using face respectively Direction as Y-axis, film thickness direction as Z axis when each axis direction refractive index, d is film thickness.
It for the manufacturing method of film, is not particularly limited, melting extrusion film forming process, solution curtain coating forming process can be used Deng well known forming method.As an example of birefringent small film is obtained, the flexible roller using elastically deformable can be enumerated Method.In addition, though unstretching film can be used, but the stretching film stretching can be used to improve film-strength also Film.For the drawing process of film, be not particularly limited, as be uniaxially stretched can for example, by roller stretching method, tentering pulling method, Free width uniaxial stretching method obtains stretched film；As it is biaxial stretch-formed can be for example, by being formed by roller stretching and tentering stretching combinations Gradually biaxial stretching process, using the biaxial stretching process of tubular stretching obtain stretched film.
The absolute value of the photoelastic coefficient of resin combination of the invention is preferably 5.0 × 10–12Pa–1Hereinafter, more preferably 3.0×10–12Pa–1Hereinafter, being further preferably 1.0 × 10–12Pa–1.It is birefringent caused by external force if photoelastic coefficient is sufficiently small Variation reduce, and be less likely to occur forming when residual mechanical stress caused by it is birefringent, so forming it is intracorporal it is birefringent distribution subtract It is small, therefore in the polarizing film for liquid crystal display device, Birefringence Fringes will not be generated, show the contrast of picture peripheral portion It will not reduce, light leakage will not occur, so being preferred.
Photoelastic coefficient can be by measuring film using measuring difference of phases device in the state of applying tensile stress to film Face in phase difference (Re) acquire.If phase difference (Re) is Re (f), test film width in the face in the state of applying load f For w, then photoelastic coefficient C is C=d Re (f)/df × w, so by the value that finds out phase difference in face (Re) relative to examination The slope for testing the load of piece application can calculate.In addition, in the present invention, measuring difference of phases device measures corporation using prince KOBRA-the WR made applies stress with the digital force gauge Z2S-DPU -50N that happy motor company manufactures.
It for the adjusting method of the photoelastic coefficient of resin combination of the invention, is not particularly limited, can use group At than adjusting, because the type of monomer is different, some has positive contribution to the photoelastic coefficient of resin combination, and some has negative tribute It offers, so photoelastic coefficient can be made to offset by suitably adjusting these compositions, reduce its absolute value.Such as using to light Coefficient of elasticity has the styrene of positive contribution, butadiene, and has the methyl methacrylate of negative contribution, maleic anhydride, can be with Photoelastic coefficient is offseted, its absolute value is reduced.
(embodiment)
(1) manufacture of copolymer (I)
<Production Example of I -1>
It is prepared for being dissolved in 20% obtained in methyl iso-butyl ketone (MIBK) in such a way that maleic anhydride becomes 25 mass % concentration in advance Maleic anhydride solution and by tert-butyl hydroperoxide-2-ethylhexoate become 2 mass % in a manner of be diluted in methyl iso-butyl ketone (MIBK) Obtained in 2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution, for polymerizeing.
25% maleic anhydride solution 1.76kg, styrene 11.8kg, methyl-prop are put into autoclave of 50 liters with blender E pioic acid methyl ester 3.8kg, tert-dodecylmercaotan 16g after replacing gas phase portion with nitrogen, last 40 minutes while stirring and heat up To 90 DEG C.Heating back keeps 90 DEG C of sides to start that 25% maleic anhydride solution, 2% t-butyl peroxy is separately and continuously added batch-wise Change-2-thylhexoic acid ester solutions.Since 25% maleic anhydride solution be by the 4th hour speed is added batch-wise being added batch-wise Only it is 1.98kg/ hours, be 1.58kg/ hours until the 7th hour from the 4th hour, was until the 10th hour from the 7th hour 0.79kg/ hours, the mode for being 0.26kg/ hours until the 13rd hour from the 10th hour, change be added batch-wise by stages Speed, it is total to be added to 15.81kg.2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution, speed is added batch-wise from batches The side that it is 0.12kg/ hours that addition, which started until the 7th hour, was 0.19kg/ hours until the 13rd hour from the 7th hour Formula changes speed is added batch-wise by stages, total to be added to 1.98kg.Polymerization temperature, by the 7th hour since being added batch-wise Until kept for 90 DEG C, then last 6 hours with 4 DEG C/h of heating rate and be warming up to 114 DEG C, and keep at 114 DEG C 1 small When, terminate polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -1) of pellet shape.Pass through C -13NMR Method has carried out composition analysis to obtained copolymer (I -1).Using SYSTEM -21Shodex (manufacture of Showa electrician company), make With the detector of column, differential refractive index that 3 PL gel MIXED-B are connected in series, use tetrahydrofuran as solvent, benefit Standard curve is made with standard polystyren (PS) (PL corporation), is determined under conditions of 40 DEG C of temperature, 2 mass % of concentration Weight average molecular weight (Mw).Obtained copolymer (I -1) is dissolved into chloroform and makes 12 mass % chloroformic solutions, is filled into light path The quartzy square box of the measurement of length 10mm is based on K -7136 JIS, and using haze meter, (Toyo Seiki company is manufactured HAZEGUARD II) determine the mist degree of optical path length 10mm in 12 mass % chloroformic solutions.Use emission forming machine (Toshiba Mechanology Inc. manufacture IS -50EPN), 230 DEG C of barrel temperature, 40 DEG C of mold temperature molding condition under injection molding it is long The mirror surface piece of 90mm, width 55mm, thickness 2mm are based on ASTM D1003, and using haze meter, (Japanese electricity Se industrial group is manufactured NDH -1001DP type), determine the total light transmittance of 2mm thickness.The formed body that thickness 2mm is made by compression moulding, uses love The Abbe formula index meter (DR-M2) that (ATAGO) company manufactures of delaying determines refractive index.The composition analysis knot of copolymer (I -1) Fruit, molecular weight determination, the total light transmittance measurement result of 2mm thickness mirror surface piece and detecting refractive index result are shown in table 1.
<Production Example of I -2>
25% maleic anhydride solution has been prepared as with the Production Example of (I-1) and 2%-2-ethylhexanate of peroxidating is molten Liquid, for polymerizeing.
25% maleic anhydride solution 1.76kg, styrene 14kg, metering system are put into autoclave of 50 liters with blender Sour methyl esters 1.6kg, tert-dodecylmercaotan 16g after replacing gas phase portion with nitrogen, last 40 minutes while stirring and are warming up to 96℃.Heating back keeps 96 DEG C of sides to start that 25% maleic anhydride solution, 2% t-butyl peroxy is separately and continuously added batch-wise Change-2-thylhexoic acid ester solutions.Since 25% maleic anhydride solution be by the 4th hour speed is added batch-wise being added batch-wise Only it is 1.98kg/ hours, be 1.58kg/ hours until the 7th hour from the 4th hour, was until the 10th hour from the 7th hour 0.79kg/ hours, the mode for being 0.26kg/ hours until the 13rd hour from the 10th hour, change be added batch-wise by stages Speed, it is total to be added to 15.81kg.2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution, speed is added batch-wise from batches The side that it is 0.18kg/ hours that addition, which started until the 7th hour, was 0.29kg/ hours until the 13rd hour from the 7th hour Formula changes speed is added batch-wise by stages, total to be added to 3.0kg.Polymerization temperature, by the 7th hour since being added batch-wise Until kept for 96 DEG C, then last 6 hours with 4 DEG C/h of heating rate and be warming up to 120 DEG C, and keep at 120 DEG C 1 small When, terminate polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -2) of pellet shape.It is total to what is obtained Polymers (I -2) has been carried out similarly composition analysis with (I -1), determine molecular weight, the mist degree in 12 mass % chloroformic solutions, The total light transmittance and refractive index of 2mm thickness mirror surface piece.Measurement result is shown in table 1.
<Production Example of I -3>
It is prepared for being dissolved in 10% obtained in methyl iso-butyl ketone (MIBK) in such a way that maleic anhydride becomes 10 mass % concentration in advance Maleic anhydride solution, for polymerizeing.It is molten that 2%-2-ethylhexanate of peroxidating has been prepared as with the Production Example of (I-1) Liquid, for polymerizeing.
10% maleic anhydride solution 2.4kg, styrene 9.6kg, metering system are put into autoclave of 50 liters with blender Sour methyl esters 8.0kg, tert-dodecylmercaotan 16g after replacing gas phase portion with nitrogen, last 40 minutes while stirring and are warming up to 88℃.Heating back keeps 88 DEG C of sides to start that 10% maleic anhydride solution, 2% t-butyl peroxy is separately and continuously added batch-wise Change-2-thylhexoic acid ester solutions.Since 10% maleic anhydride solution be by the 4th hour speed is added batch-wise being added batch-wise Only it is 2.43kg/ hours, be 2.31kg/ hours until the 7th hour from the 4th hour, was until the 10th hour from the 7th hour 1.3kg/ hours, the mode for being 0.36kg/ hours until the 13rd hour from the 10th hour, change speed is added batch-wise by stages Degree, it is total to be added to 21.63kg.2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution, speed is added batch-wise from adding in batches The mode that begin until the 7th hour be 0.09kg/ hours, was 0.15kg/ hours until the 13rd hour from the 7th hour is increased, Change by stages and speed is added batch-wise, it is total to be added to 1.53kg.Since polymerization temperature be by the 7th hour being added batch-wise 88 DEG C are only kept, then 6 hours is lasted with 5 DEG C/h of heating rate and is warming up to 118 DEG C, and kept for 1 hour at 118 DEG C, Terminate polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -3) of pellet shape.It is total to what is obtained Polymers (I -3) has been carried out similarly composition analysis with (I -1), determine molecular weight, the mist degree in 12 mass % chloroformic solutions, The total light transmittance and refractive index of 2mm thickness mirror surface piece.Measurement result is shown in table 1.
<Production Example of I -4>
25% maleic anhydride solution has been prepared as with the Production Example of (I-1) and 2%-2-ethylhexanate of peroxidating is molten Liquid, for polymerizeing.
25% maleic anhydride solution 1.92kg, styrene 2.0kg, metering system are put into autoclave of 50 liters with blender Sour methyl esters 8.2kg, tert-dodecylmercaotan 16g after replacing gas phase portion with nitrogen, last 40 minutes while stirring and are warming up to 88℃.Heating back keeps 88 DEG C of sides to start that styrene, 25% maleic anhydride solution, 2% tertiary fourth is separately and continuously added batch-wise Base peroxidating-2-thylhexoic acid ester solution.Since styrene until the 11st hour be so that speed is added batch-wise being added batch-wise Mode is added batch-wise within 0.45kg/ hours, total to be added to 4.95kg.25% maleic anhydride solution, be added batch-wise speed from point It is 2.59kg/ hours that batch addition, which started until the 4th hour, from the 4th hour until the 7th hour be 1.73kg/ hours, from the 7 hours until the 10th hour be 0.4kg/ hours, the mode that was 0.17kg/ hours until the 13rd hour from the 10th hour, Change by stages and speed is added batch-wise, it is total to be added to 17.26kg.2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution, It is 0.06kg/ hours until the 7th hour since being added batch-wise so that speed is added batch-wise, hour is from the 7th hour to the 13rd Only it is 0.1kg/ hours modes, changes speed is added batch-wise by stages, it is total to be added to 1.02kg.Polymerization temperature, from point It criticizes addition to start until the 7th hour to be kept for 88 DEG C, then lasts 6 hours with 5 DEG C/h of heating rate and be warming up to 118 DEG C, And it is kept for 1 hour at 118 DEG C, terminates polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -4) of pellet shape.It is total to what is obtained Polymers (I -4) has been carried out similarly composition analysis with (I -1), determine molecular weight, the mist degree in 12 mass % chloroformic solutions, The total light transmittance and refractive index of 2mm thickness mirror surface piece.Measurement result is shown in table 1.
<Production Example of I -5>
It is prepared for being dissolved in 20% obtained in methyl iso-butyl ketone (MIBK) in such a way that maleic anhydride becomes 20 mass % concentration in advance Maleic anhydride solution, for polymerizeing.It is molten that 2%-2-ethylhexanate of peroxidating has been prepared as with the Production Example of (I-1) Liquid, for polymerizeing.
20% maleic anhydride solution 1.7kg, styrene 15.6kg, metering system are put into autoclave of 50 liters with blender Sour methyl esters 1.0kg, tert-dodecylmercaotan 16g after replacing gas phase portion with nitrogen, last 40 minutes while stirring and are warming up to 96℃.Heating back keeps 96 DEG C of sides to start that 20% maleic anhydride solution, 2% t-butyl peroxy is separately and continuously added batch-wise Change-2-thylhexoic acid ester solutions.Since 20% maleic anhydride solution be by the 4th hour speed is added batch-wise being added batch-wise Only it is 1.91kg/ hours, be 1.53kg/ hours until the 7th hour from the 4th hour, was until the 10th hour from the 7th hour 0.77kg/ hours, the mode for being 0.26kg/ hours until the 13rd hour from the 10th hour, change be added batch-wise by stages Speed, it is total to be added to 15.32kg.2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution, speed is added batch-wise from batches The side that it is 0.18kg/ hours that addition, which started until the 7th hour, was 0.29kg/ hours until the 13rd hour from the 7th hour Formula changes speed is added batch-wise by stages, total to be added to 3.0kg.Polymerization temperature, by the 7th hour since being added batch-wise Until kept for 96 DEG C, then last 6 hours with 4 DEG C/h of heating rate and be warming up to 120 DEG C, and keep at 120 DEG C 1 small When, terminate polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -5) of pellet shape.It is total to what is obtained Polymers (I -5) has been carried out similarly composition analysis with (I -1), determine molecular weight, the mist degree in 12 mass % chloroformic solutions, The total light transmittance and refractive index of 2mm thickness mirror surface piece.Measurement result is shown in table 1.
<Production Example of I -6>
It has been prepared as 10% maleic anhydride solution with the Production Example of (I -3), has been prepared as with the Production Example of (I -1) 2% peroxidating-2-ethylhexanate solution, for polymerizeing.
10% maleic anhydride solution 2.0kg, styrene 1.2kg, metering system are put into autoclave of 50 liters with blender Sour methyl esters 13.8kg, tert-dodecylmercaotan 16g after replacing gas phase portion with nitrogen, last 40 minutes while stirring and heat up To 88 DEG C.Heating back keeps 88 DEG C of sides to start that styrene, 10% maleic anhydride solution, 2% uncle is separately and continuously added batch-wise Butyl peroxy-2-thylhexoic acid ester solution.Styrene, speed is added batch-wise since being added batch-wise until the 11st hour It is added batch-wise for 0.27kg/ hours modes, it is total to be added to 2.97kg.10% maleic anhydride solution, be added batch-wise speed from It is added batch-wise that start until the 4th hour be 2.7kg/ hours, from the 4th hour until the 7th hour be 1.8kg/ hours, from 7 hours until the 10th hour be 0.42kg/ hours, the mode that was 0.18kg/ hours until the 13rd hour from the 10th hour, Change by stages and speed is added batch-wise, it is total to be added to 18.0kg.2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution, with Be added batch-wise speed since being added batch-wise until the 7th hour for 0.06kg/ hours, from the 7th hour until the 13rd hour For 0.1kg/ hours modes, changes speed is added batch-wise by stages, it is total to be added to 1.02kg.Polymerization temperature, from batches Addition starts until the 7th hour to be kept for 88 DEG C, then lasts 6 hours with 5 DEG C/h of heating rate and be warming up to 118 DEG C, and And kept for 1 hour at 118 DEG C, terminate polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -6) of pellet shape.It is total to what is obtained Polymers (I -6) has been carried out similarly composition analysis with (I -1), determine molecular weight, the mist degree in 12 mass % chloroformic solutions, The total light transmittance and refractive index of 2mm thickness mirror surface piece.Measurement result is shown in table 1.
<Production Example of I -7>
25% maleic anhydride solution has been prepared as with the Production Example of (I-1) and 2%-2-ethylhexanate of peroxidating is molten Liquid, for polymerizeing.
25% maleic anhydride solution 1.92kg, styrene 14.0kg, methyl-prop are put into autoclave of 50 liters with blender E pioic acid methyl ester 1.2kg, tert-dodecylmercaotan 16g after replacing gas phase portion with nitrogen, last 40 minutes while stirring and heat up To 96 DEG C.Heating back keeps 96 DEG C of sides to start that 25% maleic anhydride solution, 2% t-butyl peroxy is separately and continuously added batch-wise Change-2-thylhexoic acid ester solutions.Since 25% maleic anhydride solution be by the 4th hour speed is added batch-wise being added batch-wise Only it is 2.16kg/ hours, be 1.73kg/ hours until the 7th hour from the 4th hour, was until the 10th hour from the 7th hour 0.86kg/ hours, the mode for being 0.29kg/ hours until the 13rd hour from the 10th hour, change be added batch-wise by stages Speed, it is total to be added to 17.28kg.2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution, speed is added batch-wise from batches The side that it is 0.21kg/ hours that addition, which started until the 7th hour, was 0.34kg/ hours until the 13rd hour from the 7th hour Formula changes speed is added batch-wise by stages, total to be added to 3.51kg.Polymerization temperature, by the 7th hour since being added batch-wise Until kept for 96 DEG C, then last 6 hours with 4 DEG C/h of heating rate and be warming up to 120 DEG C, and keep at 120 DEG C 1 small When, terminate polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -7) of pellet shape.It is total to what is obtained Polymers (I -7) has been carried out similarly composition analysis with (I -1), determine molecular weight, the mist degree in 12 mass % chloroformic solutions, The total light transmittance and refractive index of 2mm thickness mirror surface piece.Measurement result is shown in table 1.
<Production Example of I -8>
25% maleic anhydride solution has been prepared as with the Production Example of (I-1) and 2%-2-ethylhexanate of peroxidating is molten Liquid, for polymerizeing.
25% maleic anhydride solution 2.24kg, styrene 13.4kg, methyl-prop are put into autoclave of 50 liters with blender E pioic acid methyl ester 10.0kg, tert-dodecylmercaotan 16g after replacing gas phase portion with nitrogen, last 40 minutes while stirring and rise Temperature is to 94 DEG C.Heating back keeps 94 DEG C of sides to start that 25% maleic anhydride solution, 2% tert-butyl mistake is separately and continuously added batch-wise Aoxidize-2-thylhexoic acid ester solutions.25% maleic anhydride solution, speed is added batch-wise since being added batch-wise by the 4th hour Until be 2.52kg/ hours, be 2.02kg/ hours until the 7th hour from the 4th hour, from the 7th hour until the 10th hour The mode for being 0.34kg/ hours until the 13rd hour for 1.01kg/ hours, from the 10th hour, changes add in batches by stages Acceleration, it is total to be added to 20.19kg.2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution, be added batch-wise speed from point The side that start until the 7th hour be 0.18kg/ hours for batch addition, was 0.29kg/ hours until the 13rd hour from the 7th hour Formula changes speed is added batch-wise by stages, total to be added to 3.0kg.Polymerization temperature, by the 7th hour since being added batch-wise Until kept for 94 DEG C, then last 6 hours with 4 DEG C/h of heating rate and be warming up to 118 DEG C, and keep at 118 DEG C 1 small When, terminate polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -8) of pellet shape.It is total to what is obtained Polymers (I -8) has been carried out similarly composition analysis with (I -1), determine molecular weight, the mist degree in 12 mass % chloroformic solutions, The total light transmittance and refractive index of 2mm thickness mirror surface piece.Measurement result is shown in table 1.
<Production Example of I -9>
It has been prepared as 10% maleic anhydride solution with the Production Example of (I -3), has been prepared as with the Production Example of (I -1) 2% peroxidating-2-ethylhexanate solution, for polymerizeing.
10% maleic anhydride solution 1.6kg, styrene 18.4kg, tertiary dodecane are put into autoclave of 50 liters with blender Base mercaptan 16g after replacing gas phase portion with nitrogen, lasts 40 minutes while stirring and is warming up to 96 DEG C.Heat up back holding 96 DEG C side starts that 10% maleic anhydride solution, 2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution is separately and continuously added batch-wise. Since 10% maleic anhydride solution be 1.62kg/ hours until the 4th hour being added batch-wise, from the 4th so that speed is added batch-wise Hour is 1.2kg/ hours until the 7th hour, was 0.96kg/ hours until the 10th hour from the 7th hour, from the 10th hour The mode for being 0.48kg/ hours until the 13rd hour, changes speed is added batch-wise by stages, total to be added to 14.4kg. Since 2% tert-butyl hydroperoxide-2-thylhexoic acid ester solution until the 7th hour be so that speed is added batch-wise being added batch-wise 0.3kg/ hours, the mode for being 0.48kg/ hours until the 13rd hour from the 7th hour, change speed is added batch-wise by stages Degree, it is total to be added to 4.98kg.Polymerization temperature, since being added batch-wise until the 7th hour keep 96 DEG C, then with 4 DEG C/it is small When heating rate last 6 hours and be warming up to 120 DEG C, and kept for 1 hour at 120 DEG C, terminate polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -9) of pellet shape.It is total to what is obtained Polymers (I -9) has been carried out similarly composition analysis with (I -1), determine molecular weight, the mist degree in 12 mass % chloroformic solutions, The total light transmittance and refractive index of 2mm thickness mirror surface piece.Measurement result is shown in table 1.
<Production Example of I -10>
It has been prepared as 10% maleic anhydride solution with the Production Example of (I -3), has been prepared as with the Production Example of (I -1) 2% peroxidating-2-ethylhexanate solution, for polymerizeing.
10% maleic anhydride solution 1.6kg, styrene 1.8kg, metering system are put into autoclave of 120 liters with blender Sour methyl esters 14.6kg, tert-dodecylmercaotan 16g after replacing gas phase portion with nitrogen, last 40 minutes while stirring and heat up To 88 DEG C.Heating back keeps 88 DEG C of sides to start that styrene, 10% maleic anhydride solution, 2% uncle is separately and continuously added batch-wise Butyl peroxy-2-thylhexoic acid ester solution.Styrene, speed is added batch-wise since being added batch-wise until the 11st hour It is added batch-wise for 0.18kg/ hours modes, it is total to be added to 1.98kg.10% maleic anhydride solution, be added batch-wise speed from Be added batch-wise to start until the 4th hour be 2.16kg/ hours, from the 4th hour until the 7th hour be 1.44kg/ hours, from 7th hour until the 10th hour be 0.34kg/ hours, the side that was 0.14kg/ hours until the 13rd hour from the 10th hour Formula changes speed is added batch-wise by stages, total to be added to 14.4kg.2%-2-ethylhexoate of tert-butyl hydroperoxide is molten Since liquid be 0.06kg/ hours until the 7th hour being added batch-wise, from the 7th hour to the 13rd hour so that speed is added batch-wise Until be 0.1kg/ hour modes, change speed is added batch-wise by stages, amount to and be added to 1.02kg.Polymerization temperature, from It is added batch-wise and starts until the 7th hour to be kept for 88 DEG C, then last 6 hours with 5 DEG C/h of heating rate and be warming up to 118 DEG C, and kept for 1 hour at 118 DEG C, terminate polymerization.
Polymer fluid is fed continuously into twin shaft devolatilization extruder using gear pump, to methyl iso-butyl ketone (MIBK) and micro unreacted Monomer etc. carries out devolatilization processing, and linear extrusion is simultaneously cut off, to obtain the copolymer (I -10) of pellet shape.It is total to what is obtained Polymers (I -10) has been carried out similarly composition analysis with (I -1), determine molecular weight, the mist degree in 12 mass % chloroformic solutions, The total light transmittance and refractive index of 2mm thickness mirror surface piece.Measurement result is shown in table 1.
[table 1]
ST in ※ table indicates that styrene monomer, MMA indicate that methyl methacrylate monomer, MAH indicate maleic anhydride monomer.
(2) manufacture of polymer (II)
<Production Example of II -1>
20 liters of volume with blender are thoroughly mixed type reactor, 40 liters of volume of tower plug-flow type reactor, band in advance The devolatilization slot of hot device, which is connected in series, to be constituted.Including 98 mass parts of methyl methacrylate, 2 mass parts of ethyl acrylate, ethyl 1,1-two (t-butyl peroxy) hexamethylenes are further mixed in the mixed solution of 18 mass parts of benzene, and (Nof Corp. manufactures PERHEXA C) 0.02 mass parts, n-dodecyl mercaptan (THIOKALCOL 20 of KAO. Corp. SA's manufacture) 0.3 mass parts, 3- (3,5-- 4-hydroxy phenyl of di-t-butyl) propionic acid n-octadecane alcohol ester (Ciba (Ciba Specialty Chemicals) The IRGANOX 1076 of company's manufacture) 0.1 mass parts, material solution is made.The material solution has been controlled with the importing of 6kg per hour It makes and is thoroughly mixed type reactor at 120 DEG C of temperature.It is carried out in addition, being thoroughly mixed type reactor with the mixing speed of 200rpm Stirring.Then it is continuously taken out reaction solution from the type reactor of being thoroughly mixed, importing is adjusted to arrive towards flow direction with 130 DEG C The tower plug-flow type reactor of 150 DEG C of temperature gradient.The reaction solution is heated with preheater on one side, imports control on one side into temperature In 240 DEG C of degree, the devolatilization slot of pressure 1.0kPa, the volatile ingredient of unreacted monomer etc. is removed.The resin liquid is taken out with gear pump, Linear extrusion is simultaneously cut off, to obtain (II -1) of pellet shape.The polymer (II -1) made is at 450 DEG C of furnace temperature Thermal decomposition, with gas chromatography decomposition gasometry, has carried out composition analysis.Utilize SYSTEM -21Shodex (Showa electrician Company's manufacture), using the detector of column, differential refractive index that 3 PL gel MIXED-B are connected in series, use tetrahydrofuran As solvent, standard curve is made using standard polystyren (PS) (PL corporation), in 40 DEG C of temperature, 2 mass % of concentration Under the conditions of determine weight average molecular weight (Mw).Using emission forming machine (IS -50EPN of Toshiba Machine Co. Ltd's manufacture), in machine barrel 230 DEG C of temperature, 40 DEG C of mold temperature molding condition under the long 90mm of injection molding, width 55mm, thickness 2mm mirror surface piece, be based on ASTM D1003 determines the total of 2mm thickness using haze meter (NDH -1001DP type of Japanese electricity Se industrial group manufacture) Light rate.The formed body of thickness 2mm, the Abbe formula index meter (DR-M2) manufactured using ATAGO company are made by compression moulding Determine refractive index.The composition analysis result of polymer (II -1), molecular weight determination, 2mm thickness mirror surface piece total light transmission Rate measurement result and detecting refractive index result are shown in table 2.
[table 2]
MMA in ※ table indicates that methyl methacrylate monomer, EA indicate acrylic acid ethyl ester monomer.
(3) manufacture of graft copolymer (III)
<Production Example of III -1>
Pure water 64kg, potassium oleate 1680g, potassium rosinate 160g, sodium carbonate 1.2kg, over cure are added to 200 liters of volume of autoclaves Sour potassium 400g, under stiring uniform dissolution.Then butadiene 80kg, tert-dodecylmercaotan 320g, divinylbenzene 160g are added, Exist while stirring 60 DEG C and polymerize 20 hours, further heat up temperature 70 C, places 10 hours, polymerization terminates, and obtains Content of polybutadiene rubber latex.
Obtained content of polybutadiene rubber latex is weighed 36kg (converting with solid component), is added in 200 liters of volume of autoclave, Pure water 80kg is added, is warming up to temperature 50 C under the stream of nitrogen gas that exists while stirring.Here, addition ferrous sulfate 1.5g, Sodium ethylene diamine tetracetate 3g, sodium formaldehyde sulfoxylate 100g are dissolved in aqueous solution obtained in pure water 2kg, respectively last 5 hours and continuously add Add the mixture comprising styrene 5.7kg, methyl methacrylate 18.3kg, tert-dodecylmercaotan 54g, and hydrogen peroxide Diisopropylbenzene (DIPB) 108g is distributed to solution obtained in 5% oleic acid aqueous solutions of potassium 8kg.After addition, temperature is raised to 70 DEG C, then Di-isopropylbenzene hydroperoxide 27g is added, is then placed 2 hours, polymerization terminates, and has obtained graft copolymer latex.
Antioxidant is added to obtained graft copolymer latex, is diluted to solid component with pure water to heat up after 15 mass % It to temperature 60 C, is vigorously stirred on one side, dilute sulfuric acid is added on one side and is precipitated, after becoming slurry condition, temperature continues to be raised to 90 DEG C, it solidified, be dehydrated, washed, dried, obtained powdered graft copolymer (III -1).Obtained (III -1) is molten Lodine chloride is added into chloroform in solution, and after the double bond in polybutadiene is reacted, potassium iodide, which is added, becomes remaining lodine chloride Iodine determines the polybutadiene amount in D -1 by carrying out back titration with sodium thiosulfate.In turn, the polymer made is in furnace It is thermally decomposed at 450 DEG C of temperature, with gas chromatography decomposition gasometry, measures methyl methacrylate/styrene structure Ratio calculates the composition of (III -1) from polybutadiene amount and methyl methacrylate/styrene structural ratio.In turn, pass through Compression moulding makes the formed body of thickness 2mm, and the Abbe formula index meter (DR-M2) manufactured using ATAGO company determines folding Penetrate rate.The composition analysis result and detecting refractive index result of (III -1) are shown in table 3.
<Production Example of III -2>
Pure water 64kg, potassium oleate 1680g, potassium rosinate 160g, sodium carbonate 1.2kg, over cure are added to 200 liters of volume of autoclaves Sour potassium 400g, under stiring uniform dissolution.Then butadiene 72kg, styrene 8kg, tert-dodecylmercaotan 320g, two are added Ethenylbenzene 300g exists 60 DEG C while stirring and polymerize 20 hours, further heat up temperature 70 C, places 10 hours, polymerization Terminate, has obtained content of polybutadiene rubber latex.
Obtained content of polybutadiene rubber latex is weighed 36kg (converting with solid component), is added in 200 liters of volume of autoclave, Pure water 80kg is added, is warming up to temperature 50 C under the stream of nitrogen gas that exists while stirring.Here, addition ferrous sulfate 1.5g, Sodium ethylene diamine tetracetate 3g, sodium formaldehyde sulfoxylate 100g are dissolved in aqueous solution obtained in pure water 2kg, respectively last 5 hours and continuously add Add the mixture comprising styrene 7.7kg, methyl methacrylate 16.3kg, tert-dodecylmercaotan 54g, and hydrogen peroxide Diisopropylbenzene (DIPB) 108g is distributed to solution obtained in 5% oleic acid aqueous solutions of potassium 8kg.After addition, temperature is raised to 70 DEG C, then Di-isopropylbenzene hydroperoxide 27g is added, is then placed 2 hours, polymerization terminates, and has obtained graft copolymer latex.
Antioxidant is added to obtained graft copolymer latex, is diluted to solid component with pure water to heat up after 15 mass % It to temperature 60 C, is vigorously stirred on one side, dilute sulfuric acid is added on one side and is precipitated, after becoming slurry condition, temperature continues to be raised to 90 DEG C, it solidified, be dehydrated, washed, dried, obtained powdered graft copolymer (III -2).Obtained (III -2) is molten Lodine chloride is added into chloroform in solution, and after the double bond in polybutadiene is reacted, potassium iodide, which is added, becomes remaining lodine chloride Iodine determines the polybutadiene amount in D -1 by carrying out back titration with sodium thiosulfate.In turn, the polymer made is in furnace It is thermally decomposed at 450 DEG C of temperature, with gas chromatography decomposition gasometry, measures methyl methacrylate/styrene structure Ratio calculates the composition of (III -2) from polybutadiene amount and methyl methacrylate/styrene structural ratio.In turn, pass through Compression moulding makes the formed body of thickness 2mm, and the Abbe formula index meter (DR-M2) manufactured using ATAGO company determines folding Penetrate rate.The composition analysis result and detecting refractive index result of (III -2) are shown in table 3.
<Production Example of III -3>
Pure water 64kg, potassium oleate 1680g, potassium rosinate 160g, sodium carbonate 1.2kg, over cure are added to 200 liters of volume of autoclaves Sour potassium 400g, under stiring uniform dissolution.Then butadiene 60kg, styrene 20kg, tert-dodecylmercaotan 320g, two are added Ethenylbenzene 400g exists 60 DEG C while stirring and polymerize 20 hours, further heat up temperature 70 C, places 10 hours, polymerization Terminate, has obtained content of polybutadiene rubber latex.
Obtained content of polybutadiene rubber latex is weighed 36kg (converting with solid component), is added in 200 liters of volume of autoclave, Pure water 80kg is added, is warming up to temperature 50 C under the stream of nitrogen gas that exists while stirring.Here, addition ferrous sulfate 1.5g, Sodium ethylene diamine tetracetate 3g, sodium formaldehyde sulfoxylate 100g are dissolved in aqueous solution obtained in pure water 2kg, respectively last 5 hours and continuously add Add the mixture comprising styrene 10.1kg, methyl methacrylate 13.9g, tert-dodecylmercaotan 54g, and hydrogen peroxide Diisopropylbenzene (DIPB) 108g is distributed to solution obtained in 5% oleic acid aqueous solutions of potassium 8kg.After addition, temperature is raised to 70 DEG C, then Di-isopropylbenzene hydroperoxide 27g is added, is then placed 2 hours, polymerization terminates, and has obtained graft copolymer latex.
Antioxidant is added to obtained graft copolymer latex, is diluted to solid component with pure water to heat up after 15 mass % It to temperature 60 C, is vigorously stirred on one side, dilute sulfuric acid is added on one side and is precipitated, after becoming slurry condition, temperature continues to be raised to 90 DEG C, it solidified, be dehydrated, washed, dried, obtained powdered graft copolymer (III -3).Obtained (III -3) is molten Lodine chloride is added into chloroform in solution, and after the double bond in polybutadiene is reacted, potassium iodide, which is added, becomes remaining lodine chloride Iodine determines the polybutadiene amount in D -1 by carrying out back titration with sodium thiosulfate.In turn, the polymer made is in furnace It is thermally decomposed at 450 DEG C of temperature, with gas chromatography decomposition gasometry, measures methyl methacrylate/styrene structure Ratio calculates the composition of (III -3) from polybutadiene amount and methyl methacrylate/styrene structural ratio.In turn, pass through Compression moulding makes the formed body of thickness 2mm, and the Abbe formula index meter (DR-M2) manufactured using ATAGO company determines folding Penetrate rate.The composition analysis result and detecting refractive index result of (III -3) are shown in table 3.
[table 3]
St in ※ table indicates that styrene monomer, MMA indicate that methyl methacrylate monomer, Bd indicate divinylic monomer.
<embodiment comparative example>
By copolymer (I) (I -1)~(I -10) recorded in above-mentioned Production Example and polymer (II) (II -1) and graft copolymer (III) after (III -1)~(III -3) is with the mixing of ratio (quality %) shown in 4~table of table 5, with biaxial extruder (Toshiba's machine Tool corporation TEM -35B) at 240 DEG C of barrel temperature melting mixing is carried out, and pellet is formed, obtain resin combination.
Resin group is calculated from the composition and compounding ratio of each ingredient of copolymer (I), polymer (II) and graft copolymer (III) Close the composition of object.Evaluation below has been carried out to the resin combination.Evaluation result is shown in table in 4~table 5.
Pellet exists the T mould by using 40mm Φ single axle extruding machine and 300mm width after 70 DEG C of dry 4 hours It is cooling with chill roll after the laminar molten resin squeezed out at 260 DEG C is connect with flexible roll-in, obtain wide 250mm, thickness 100 ± 5 μm of unstretching film.
(phase difference (Re), thickness phase difference (Rth) in face)
Unstretching film is cut into long 100mm, width 20mm, has carried out free end single shaft under the following conditions with uniaxial stretching device It stretches.
Distance between clamp: 50mm
Draft temperature :+10 DEG C of vicat softening temperature
The waste heat time: 5 minutes
Tensile speed: 12.5mm/ minutes
Stretching distance: 12.5mm
About phase difference (Re) in the face of stretched film and thickness phase difference (Rth), the birefringent of film is determined with device below.
Measuring difference of phases: prince measures the KOBRA-WR of company's manufacture
Measure wavelength: 590nm
(photoelastic coefficient)
If using unstretching film, be applied with load f in the state of face in phase difference (Re) be Re (f), test film width is W, then photoelastic coefficient is d Re (f)/df × w, so being applied by the value for finding out phase difference in face (Re) relative to test film The slope of the load added, has calculated photoelastic coefficient.
Measuring difference of phases: prince measures the KOBRA-WR of company's manufacture
Measure wavelength: 590nm
Stress determination: the digital force gauge Z2S-DPU -50N of happy motor company manufacture
(total light transmittance and mist degree)
It obtains using emission forming machine (IS -50EPN of Toshiba Machine Co. Ltd's manufacture), in 230 DEG C of barrel temperature, mold temperature 40 DEG C molding condition under shape long 90mm, width 55mm, thickness 2mm test film.Based on ASTM D1003, haze meter (day is used NDH -1001DP the type of this electricity Se industrial group manufacture), total light transmittance and mist degree are determined to the test film.
(vicat softening temperature)
Based on JIS K7206, the test of 10mm × 10mm, thickness 4mm are used with 50 methods (load 50N, 50 DEG C/h of heating rate) Piece determines vicat softening temperature.In addition, the HDT&VSPT experimental rig that measuring machine is manufactured using Toyo Seiki manufacturing company. The above are qualifications for 110 DEG C of vicat softening temperature.
(folding strength)
About the folding strength of film, folding strength is determined under the following conditions using unstretching film.Folding strength is 100 times The above are qualifications.
Device name: MIT-D FOLDING ENDURANCE TESTER (manufacture of Toyo Seiki company)
It loads (tension): 500g weight
Bending speed: 175 beats/min
Bending angle: each 45 degree of left and right
Bending device tip radius: 0.38mm
Test film width: 15mm
(thermal stability)
Using emission forming machine the IS -50EPN of manufacture (Toshiba Machine Co. Ltd), in 250 DEG C of barrel temperature, 60 DEG C of mold temperature Under molding condition, 50, sample of the cylindric formed products of diameter 30mm, high 50mm are made, by visual observations, make an inventory of generation The sample number of bad order caused by the thermal decomposition of silver grey, Air-pollution From Combustion, coloring, bubble etc., to carry out resin combination The Evaluation of Thermal Stability of object.Evaluation criteria is as described below.
◎: the sample number of bad order is 0
Zero: the sample number of bad order is 1~4
△: the sample number of bad order is 5~9
×: the sample number of bad order is 10 or more
[table 4]
[table 5]
(I -1)~(I -8) of copolymer (I) of the invention and (II -1) of polymer (II) and graft copolymer (III) The obtained resin combination of (III -1)~(III -3) compounding be all difficult to happen birefringent, heat resistance, film-strength, thermal stability It is excellent.
Formula 1 is unsatisfactory for the birefringent very big of 1~comparative example of comparative example 2 of the scope of the present invention.Formula 1 and conjugated diene monomeric unit Be unsatisfactory for the comparative example 3 of the scope of the present invention it is birefringent it is big, film-strength is poor.Use unsaturated carboxylic acid anhydrides monomeric unit discontented The poor heat resistance of the comparative example 4 of (I -9) of sufficient the scope of the present invention.Aromatic vinyl monomer unit has been used to be unsatisfactory for this hair 5 transparency of comparative example of (I -10) of bright range, thermal stability are poor.
(industrial availability)
According to the present invention it is possible to provide the resin group for being difficult to happen birefringent, heat resistance, film-strength, excellent heat stability The film for closing object and being made of the resin combination.

Claims (7)

1. a kind of resin combination, it includes:
17~31 mass % of aromatic vinyl monomer unit (A),
38~63 mass % of (methyl) acrylate monomeric units (B),
4~14 mass % of unsaturated dicarboxylic anhydride monomer unit (C) and
4~25 mass % of conjugated diene monomeric unit (D),
The absolute value of the value of following formula 1 be 0.005 hereinafter,
Formula 1:- 0.10 × [A] -0.004 × [B]+0.10 × [C]+0.09 × [D],
[A], [B], [C], [D] in formula 1 successively indicate aromatic vinyl monomer unit (A), (methyl) acrylate monomer The mass ratio of unit (B), unsaturated dicarboxylic anhydride monomer unit (C), conjugated diene monomeric unit (D) in resin combination,
[A]+[B]+[C]+[D]=1.
2. resin combination according to claim 1, it includes:
20~80 mass parts of copolymer (I), the copolymer (I) is by aromatic vinyl monomer unit (A), (methyl) acrylic acid Ester monomer unit (B), unsaturated dicarboxylic anhydride monomer unit (C) are constituted；
0~60 mass parts of polymer (II), the polymer (II) are made of (methyl) acrylate monomeric units (B)；And
5~60 mass parts of graft copolymer (III), the graft copolymer (III) passes through will be by aromatic vinyl monomer list The copolymer grafted of first (A) and (methyl) acrylate monomeric units (B) composition conjugated diene monomeric unit (D) to being made of Polymer and constitute.
3. resin combination according to claim 2, wherein the copolymer (I) includes:
20~80 mass % of aromatic vinyl monomer unit (A),
5~70 mass % of (methyl) acrylate monomeric units (B) and
The copolymer of 10~25 mass % of unsaturated dicarboxylic anhydride monomer unit (C).
4. resin combination according to claim 2 or 3, wherein
The mist degree of optical path length 10mm of the copolymer (I) in 12 mass % chloroformic solutions is 2% or less.
5. resin combination according to any one of claims 1 to 4, wherein
Total light transmittance based on the ASTM D1003 2mm thickness measured is 88% or more.
6. a kind of film contains resin combination according to any one of claims 1 to 5.
7. film according to claim 6 is used as polarizer protecting film.
CN201780045521.0A 2016-07-22 2017-07-03 Resin composition and film made of the same Active CN109476899B (en)

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