CN110167981A - Copolymer and resin combination - Google Patents

Copolymer and resin combination Download PDF

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Publication number
CN110167981A
CN110167981A CN201880006664.5A CN201880006664A CN110167981A CN 110167981 A CN110167981 A CN 110167981A CN 201880006664 A CN201880006664 A CN 201880006664A CN 110167981 A CN110167981 A CN 110167981A
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methyl
copolymer
polymer
resin combination
unit
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CN110167981B (en
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中西秀高
井本慎也
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/48—Isomerisation; Cyclisation
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • 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
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Abstract

The invention discloses a kind of copolymers, the copolymer be containing: there is polymer chain (A) from alkadienes and/or the unit of alkene and have the unit on the unit and main chain for coming from (methyl) acrylic monomer with ring structure polymer chain (B) copolymer, it is characterized in that, in the polymer chain (B), the content ratio of the unit from (methyl) acrylate is 45 mass % or more, 98 mass % or less.

Description

Copolymer and resin combination
Technical field
The present invention relates to copolymer, the resin combination containing the copolymer, optical thin film, the polarisations formed by them The preparation method of plate, image display device and the copolymer, the copolymer contain: having and come from alkadienes and/or alkene Unit polymer chain, and with from (methyl) acrylic monomer unit and main chain on ring structure unit Polymer chain.
Background technique
Transparent resin be widely used in optical lens, prism, reflecting mirror, CD, optical fiber, liquid crystal display sheet material, film, The optical material of light guide plate etc..As such transparent resin, (methyl) acrylic resin, but (methyl) were widely used in the past Acrylic resin is likely difficult to obtain heat resistance and mechanical strength simultaneously.For example, (methyl) acrylic resin can pass through Ring structure is imported in main chain to improve heat resistance (patent document 1 etc.) while maintaining the transparency, but by leading in main chain Enter ring structure, resin itself becomes hard and brittle and is easily broken, and when processing film has the mechanical strength of folding strength etc. to reduce Trend.Here, the method for the intensity as raising (methyl) acrylic resin, is disclosed in patent document 2 and pass through twin shaft Extend the method for assigning intensity, the method for the low flexible resin of cooperation glass transition temperature is disclosed in patent document 3.So And in the case where extending imparting intensity with twin shaft, there are problems that intensity is caused to generate anisotropy due to extension ratio etc..Separately Outside, in the case where cooperating flexible resin, it is difficult to while guaranteeing the transparency, it still has room for improvement.It is disclosed in patent document 4 The copolymer of (methyl) acrylic polymer is grafted on polyolefin, but due to the glass transition temperature of such graft copolymer It spends that low, heat resistance is insufficient, still has room for improvement.In turn, in the case where transparent resin being suitable for optical material, in resin When containing gel compound, the reason of becoming foreign matter and bad order, and lowly related with preparation efficiency, therefore undesirable contain Such gel compound.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-171464 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2005-162835 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2007-100044 bulletin
Patent document 4: Japanese Unexamined Patent Publication 5-295183 bulletin
Summary of the invention
The present invention is completed in view of the situation, it is intended that providing not only in well balanced mode with excellent The transparency, mechanical strength, heat resistance, and the few copolymer of generation of gel compound, the resin combination containing the copolymer Object, and the method for preparing such copolymer.
The present invention includes invention below.
[1] a kind of copolymer, the copolymer contain: the polymer chain with the unit from alkadienes and/or alkene (A) and with from (methyl) acrylic monomer unit and main chain on ring structure unit polymer chain (B), which is characterized in that
In the polymer chain (B), the content ratio of the unit from (methyl) acrylate is 45 mass % The above 98 mass % or less.
[2] copolymer recorded according to [1], wherein polymer chain (B) is the polymer being grafted on polymer chain (A) Chain.
[3] copolymer recorded according to [1] or [2], wherein the ring structure is lactone ring structure and/or maleimide Amine structure.
[4] copolymer recorded according to any one of [1]-[3], wherein described to come from the polymer chain (B) Total content ratio of the unit with ring structure is 90 mass % on the unit and the main chain of (methyl) acrylic monomer More than.
[5] a kind of resin combination, which is characterized in that the resin combination contains any one of [1]-[4] record Copolymer and (methyl) acrylic polymer.
[6] resin combination recorded according to [5], wherein (methyl) acrylic polymer has described come from The unit of (methyl) acrylic monomer.
[7] resin combination recorded according to [5] or [6], wherein (methyl) acrylic polymer has described With the unit of ring structure on main chain.
[8] resin combination recorded according to any one of [5]-[7], wherein the resin combination is respectively 100 DEG C or more and less than 100 DEG C have glass transition temperature.
[9] resin combination recorded according to any one of [5]-[8], wherein the resin combination is in chloroform Insoluble component be 10 mass % or less.
[10] a kind of optical thin film, the optical thin film contain 1]-any one of [4] copolymer for recording or [5]- Any one of [9] resin combination recorded.
[11] a kind of polarizer, the polarizer include the optical thin film that [10] are recorded.
[12] a kind of image display device, the image display device include the optical thin film that [10] are recorded.
[13] a kind of preparation method of copolymer is the preparation method for the copolymer that any one of [1]-[4] are recorded, It is characterized in that, the preparation method includes following process,
In the presence of polymer (P1) with the unit from alkadienes and/or alkene, (methyl) propylene will be contained The process that the monomer component of monomer in acrylic monomer and ring structure with polymeric double bond is polymerize.
[14] a kind of preparation method of copolymer is the preparation method for the copolymer that any one of [1]-[4] are recorded, It is characterized in that, the preparation method includes following process,
In the presence of polymer (P1) with the unit from alkadienes and/or alkene, (methyl) propylene will be contained The process that the monomer component of acrylic monomer is polymerize, and
What is formed in the polymerization process has the master of the polymer chain of the unit from (methyl) acrylic monomer The process of ring structure is formed on chain.
[15] preparation method for the copolymer recorded according to [13], wherein the preparation method further include: by the polymerization work The process that the resin solution that sequence obtains is filtered.
[16] preparation method for the copolymer recorded according to [14], wherein the preparation method further include: by the ring structure The process that the resin solution that formation process obtains is filtered.
Copolymer of the invention and the resin combination containing the copolymer not only have in well balanced mode excellent The good transparency, mechanical strength, heat resistance, and when preparing gel compound generation it is few.In addition, preparation side according to the present invention The generation of method, available gel compound is few, and has the excellent transparency, mechanical strength, resistance in well balanced mode Hot copolymer.
Specific embodiment
(1. copolymer)
Copolymer of the invention contains with alkadienes or olefin polymer chain (A) and with the (first of ring structure Base) acrylate copolymer chain (B).Copolymer of the invention not only has the excellent transparency, machinery in well balanced mode Intensity (for example, impact strength etc.), heat resistance, and when preparing gel compound generation it is few.Hereinafter, by copolymer of the invention Referred to as " copolymer (P) ".
Copolymer (P) is containing alkadienes or olefin polymer chain (A) and with (methyl) acroleic acid polymerization of ring structure Structure made of object chain (B) copolymerization.The form of copolymerization does not limit, preferably on alkadienes or olefin polymer chain (A) It has been grafted the graft copolymer of (methyl) the acrylate copolymer chain (B) with ring structure.Hereinafter, alkadienes or alkene are birdsed of the same feather flock together It closes object chain (A) and is referred to as " polymer chain (A) ", (methyl) the acrylate copolymer chain (B) with ring structure is referred to as " polymerization Object chain (B) ".
(methyl) acrylate copolymer chain (B) with ring structure usually provides hard and crisp resin, and makes itself and diene Hydrocarbon or olefin polymer chain (A) copolymerization, it is available to have both heat resistance by suitably controlling the composition of polymer chain (B) With the copolymer (P) of mechanical strength.In addition, when preparation, it is possible to reduce the generation of gel compound.The copolymer (P) obtained in this way, Although having alkadienes or olefinic component, it may have high transparency.In addition, by copolymer (P) and (methyl) acrylic Object mixing will not damage these characteristics, since favorable dispersibility is without damaging the transparency.
When forming film by copolymer (P), even if not implementing the orientation process of extended spot reason etc., available high intensity yet And the film of high-fire resistance.Therefore, the film with desired optical characteristics can be readily derived.For example, due to having height Isotropism film and low phase-contrast film can be efficiently formed in intensity, high-fire resistance, high transparency.On the other hand, due to Ring structure can easily show anisotropy, therefore by the orientation process of extension processing etc., can also form phase difference Film.In addition, when optical thin film is made, it is possible to reduce foreign matter and bad order.
It is illustrated for the polymer chain (A) contained in copolymer (P).Polymer chain (A), which at least has, comes from diene The unit of hydrocarbon and/or alkene.Unit from alkadienes and/or alkene works in copolymer (P) as soft component.Pass through Contain the unit from alkadienes and/or alkene, it can be ensured that the transparency of copolymer (P), and improve the machinery of copolymer Intensity (such as impact strength etc.), reduces hard brittleness.
As alkadienes, it is preferable to use 1,3-butadiene (alias: butadiene), 2- methyl-1,3- butadiene (alias: different Pentadiene), 1,3- pentadiene, 1,4- pentadiene, 1,5- hexadiene, 2,5- dimethyl -1,5- hexadiene (alias: diisobutylene) Deng alkadiene hydrocarbon, wherein more preferably 1,3-butadiene, 2- methyl-1, the conjugated diene of 3- butadiene, 1,3-pentadiene etc. Hydrocarbon.As alkene, it is preferable to use ethylene, propylene, 1- butylene, isobutene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1- ten The monoolefine of tetraene, 1- octadecylene etc., wherein more preferably carbon-to-carbon double bond is located at α alkene, that is, alpha-olefins.These alkadienes With the carbon number of alkene, preferably 2 or more, more preferably 3 or more, it is additionally preferred to for 20 hereinafter, more preferably 10 hereinafter, further Preferably 6 or less.Unit from alkadienes and/or alkene is defined as being formed by these alkadienes and/or olefinic polymerization Unit.Unit from alkene is not limited by the unit that the (co) polymerization of alkene is actually formed, can also be by coming from diene The unit of hydrocarbon is hydrogenated and is formed.
Polymer chain (A) includes such as polyethylene, polypropylene, PB Polybutene-1, ethylene-propylene copolymer in backbone structure The alkene (co) polymer of object, ethylene-butene copolymer etc.；Polyisoprene, polybutadiene, isoprene-butadiene copolymerization The alkadienes (co) polymer of object etc.；The alkene of ethylene-propylene-diene copolymer, isobutylene-isoprene copolymer etc. with The copolymer of alkadienes.As alkene (co) polymer, preferably alpha-olefin (co) polymer, as alkadienes (co) polymerization Object, preferably conjugated diene (co) polymer, as the copolymer of alkene and alkadienes, preferably alpha-olefin and conjugated diene The copolymer of hydrocarbon.In them, more preferably the alpha-olefin of polyisoprene, isobutylene-isoprene copolymer etc. and conjugation two Copolymer or polyethylene, the polypropylene of alkene.
In polymer chain (A), other than the unit from alkadienes and/or alkene, can also have from other not It is saturated the unit of monomer.Other unsaturated monomers are the compound with polymeric double bond, and there is no particular limitation, such as The vinyl esters of vinyl acetate, vinyl propionate etc. can be enumerated；(methyl) acrylic acid, maleic anhydride, (methyl) acrylic acid first The unsaturated carboxylic acid and its ester of ester, (methyl) ethyl acrylate etc.；Styrene, vinyltoluene, methoxy styrene, Alpha-Methyl The aromatic ethenyl compound of styrene, 2- vinylpyridine etc.；Vinyltrimethoxysilane, γ-(methyl) acryloyl The vinyl silanes etc. of oxygroup propylmethoxysilane etc..Polymer chain (A) can be these other unsaturated monomers and diene The copolymer of hydrocarbon and/or alkene.The content ratio of unit from alkadienes and/or alkene in polymer chain (A), such as preferably It is still more preferably 55 for 30 mass % or more, more preferably 40 mass % or more, further preferably 50 mass % or more Quality % or more, it is additionally preferred to be 90 mass % hereinafter, more preferably 86 mass % hereinafter, further preferably 83 mass % with Under.
In the case that polymer chain (A) has the unit from other unsaturated monomers, polymer chain (A) can be diene The random copolymer of hydrocarbon and/or alkene and other unsaturated monomers, or block copolymer can also be graft copolymerization Object.In them, it is suitble to from the viewpoint of playing the function as soft component from the unit from alkadienes and/or alkene, preferably For block copolymer.In this case, polymer chain (A) is containing poly- with the unit from alkadienes and/or alkene Close the polymer chain of object block (a1) and the polymer blocks (a2) with the unit from other unsaturated monomers.
Polymer chain (A) is the polymer containing the polymer blocks (a2) with the unit from other unsaturated monomers In the case where chain, from it is easy to ensure that copolymer (P) mechanical strength and from the viewpoint of improving the transparency, polymer blocks (a2) it is preferably made of the unit from aromatic vinyl monomer.In this case, in polymer chain (A), polymer Block (a1) works as soft component, and polymer blocks (a2) work as hard component.
The aromatic vinyl monomer of polymer blocks (a2) is provided, as long as being bonded with the chemical combination of vinyl on aromatic rings Object, there is no particular limitation, for example, can enumerate styrene, vinyltoluene, methoxy styrene, α-methylstyrene, The styrene monomer of alpha-hydroxymethyl styrene, α-hydroxyethylbenzene ethylene etc.；The Ppolynuclear aromatic hydrocarbon ring second of 2- vinyl naphthalene etc. Alkenyl monomer；The heteroaromatic vinyl of N- vinyl carbazole, 2- vinylpyridine, vinyl imidazole, vinyl thiophene etc. Monomer etc..In them, preferably styrene monomer.In styrene monomer, includes not only styrene, be also included within styrene Polymeric double bond carbon or phenyl ring on be bonded with the styrene derivative of arbitrary substituent group and can enumerate alkane as the substituent Base, alkoxy, hydroxyl, halogen radical, amino, nitro, sulfonic group etc..The alkyl and alkoxy being bonded with styrene, preferably carbon Number 1-4, more preferably carbon number 1-2, in the alkyl and alkoxy being bonded with styrene, at least part of hydrogen atom can be by hydroxyl Base or halogen radical replace.
As containing with the polymer blocks (a1) from alkadienes and/or the unit of alkene and with from aromatic series The polymer chain (A) of the polymer blocks (a2) of the unit of vinyl monomer, such as Styrene-Butadiene block copolymerization can be enumerated Object, Styrene-Butadiene-Styrene Block Copolymer, Styrene-Butadiene-Styrene Block Copolymer hydride (such as Styrene-ethylene/butylene-styrene block copolymer, styrene-butadiene/butylene-styrene block copolymer), benzene second Alkene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-isoprene-phenylethene Hydride (such as styrene-ethylene/propylene-styrene block copolymer) of block copolymer etc..
Polymer chain (A) contains with the polymer blocks (a1) from alkadienes and/or the unit of alkene and has In the case where the polymer blocks (a2) of the unit of aromatic vinyl monomer, the polymer blocks of preferred polymers chain (A) (a1) two sides are bonded with polymer blocks (a2).Polymer chain (A) with this configuration, polymer chain (A) are used as elastomer It works, can be further improved the mechanical strength of copolymer.In this case, polymer chain (A) can be total for three block Polymers, or segmented copolymer can also be star block copolymer, from the characteristic for being easy to control polymer chain (A), And it is easy to import from the viewpoint of polymer chain (B) into copolymer (P), preferably triblock copolymer.
Polymer chain (A) contains with the polymer blocks (a1) from alkadienes and/or the unit of alkene and has In the case where the polymer blocks (a2) of the unit of aromatic vinyl monomer, polymer blocks (a1) are coming from alkadienes And/or on the basis of the unit of alkene, can also further have the unit from other unsaturated monomers.As at this moment its His unsaturated monomer, such as the vinyl esters that vinyl acetate, vinyl propionate can be enumerated etc.；(methyl) acrylic acid, maleic acid The unsaturated carboxylic acid and its ester of acid anhydride, (methyl) methyl acrylate, (methyl) ethyl acrylate etc.；Styrene, vinyltoluene, first The aromatic ethenyl compound of oxygroup styrene, α-methylstyrene, 2- vinylpyridine etc.；Vinyl trimethoxy silicon The vinyl silanes etc. of alkane, γ-(methyl) acryloxypropyl methoxy silane etc..Polymer blocks (a1) can be these The copolymer of other unsaturated monomers and alkadienes and/or alkene.In addition, polymer blocks (a1) are preferably comprised from alkadienes And/or the unit of alkene is as principal component, in 100 mass % of polymer blocks (a1), the list from alkadienes and/or alkene The content ratio of member is preferably 50 mass % or more, more preferably 60 mass % or more, further preferably 70 mass % or more. Polymer blocks (a1) substantially can be only made of the unit from alkadienes and/or alkene, for example, from alkadienes and/or The unit of alkene can be 99 mass % or more.
Polymer chain (A) contains with the polymer blocks (a1) from alkadienes and/or the unit of alkene and has In the case where the polymer blocks (a2) of the unit of aromatic vinyl monomer, polymer blocks (a2) are coming from aromatic series On the basis of the unit of vinyl monomer, it can also further contain the unit from other unsaturated monomers.At this moment as Other unsaturated monomers, such as the vinyl esters that vinyl acetate, vinyl propionate can be enumerated etc.；(methyl) acrylic acid, Malaysia The unsaturated carboxylic acid and its ester of acid anhydrides, (methyl) methyl acrylate, (methyl) ethyl acrylate etc.；Styrene, vinyltoluene, The aromatic ethenyl compound of methoxy styrene, α-methylstyrene, 2- vinylpyridine etc.；Vinyl trimethoxy silicon The vinyl silanes etc. of alkane, γ-(methyl) acryloxypropyl methoxy silane etc..Polymer blocks (a2) can be these The copolymer of other unsaturated monomers and aromatic vinyl monomer.In addition, polymer blocks (a2) are preferably comprised from fragrance The unit of race's vinyl monomer is as principal component, in 100 mass % of polymer blocks (a2), from aromatic vinyl monomer The content ratio of unit is preferably 70 mass % or more, more preferably 80 mass % or more, further preferably 90 mass % with On.Polymer blocks (a2) substantially can be only made of the unit from aromatic vinyl monomer, such as from aromatic series The unit of vinyl monomer can be 99 mass % or more.
In polymer chain (A), the content ratio of polymer blocks (a2) is preferably 10 mass % or more, and more preferably 14 Quality % or more, further preferably 17 mass % or more, it is additionally preferred to be 55 mass % hereinafter, more preferably 50 mass % with Under, further preferably 45 mass % or less.Polymer chain (A) has soft component and hard group in well balanced mode as a result, Point, it is easy while ensuring the mechanical strength of copolymer (P), improves the transparency.From the viewpoint of same, polymer chain (A) in, the content ratio of polymer blocks (a1) is preferably 45 mass % or more, more preferably 50 mass % or more, further Preferably 55 mass % or more, it is additionally preferred to be 90 mass % hereinafter, more preferably 86 mass % are hereinafter, further It is preferred that 83 mass % or less.
The weight average molecular weight of polymer chain (A), preferably 0.1 ten thousand or more, more preferably 0.5 ten thousand or more, further preferably It is 10,000 or more, is still more preferably 30,000 or more, it is additionally preferred to for 500,000 hereinafter, more preferably 300,000 hereinafter, further excellent 200,000 are selected as hereinafter, being still more preferably 100,000 or less.By making the weight average molecular weight of polymer chain (A) in such range It is interior, it is easy to ensure that the intensity and the transparency of copolymer (P).
It is illustrated for the polymer chain (B) contained in copolymer (P).Polymer chain (B), which at least has, comes from (first Base) acrylic monomer unit, and have ring structure.Polymer chain (B) is preferably grafted on polymer chain (A), therefore, Copolymer (P) is graft copolymer, and the grafted chain as the graft copolymer preferably has polymer chain (B).Pass through polymer Chain (B), can be improved the transparency of copolymer (P).
Unit (hereinafter also referred to " (methyl) acrylic acid list from (methyl) acrylic monomer of polymer chain (B) Member "), it can be imported into polymer chain (B) by polymerization (methyl) acrylic monomer.(methyl) acrylic monomer contains (methyl) acrylic acid and its derivative, the position α of (methyl) acrylic monomer or β can be bonded with alkyl (preferably carbon number The alkyl of 1-4), at least part of the hydrogen atom of the alkyl can be replaced by hydroxyl or halogen radical.From (methyl) acrylic acid There is no particular limitation for the form of carboxylic acid group contained by the unit of class monomer, can enumerate the shape of free acid, ester, salt, amide etc. State.
In polymer chain (B), as (methyl) acrylic acid units, at least there is the unit from (methyl) acrylate. As (methyl) acrylate of the unit from (methyl) acrylate is provided, the ester bond in (methyl) acrylic acid can be enumerated Be bonded on oxygen atom straight-chain, branched or cricoid aliphatic alkyl, aromatic hydrocarbyl (methyl) acrylate.
As (methyl) acrylate with straight-chain or branched aliphatic alkyl, (methyl) acrylic acid can be enumerated Methyl esters, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, the positive fourth of (methyl) acrylic acid Ester, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid 2- ethyl hexyl Ester, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) acrylic acid heptadecane base ester, (methyl) third (methyl) alkyl acrylate of olefin(e) acid stearyl etc..The alkyl of (methyl) alkyl acrylate, preferably C1-18 alkane Base, more preferably C1-12 alkyl.In addition, in the present specification, the record of " C1-18 " or " C1-12 " respectively indicate " carbon number 1- 18 ", " carbon number 1-12 ".
As (methyl) acrylate with cricoid aliphatic alkyl, (methyl) acrylic acid cyclopropyl ester, (first can be enumerated Base) acrylic acid ring butyl ester, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate etc. (methyl) acrylate base Ester；Crosslinking ring type (methyl) acrylate of (methyl) isobornyl acrylate etc. etc..The ring of (methyl) acrylate base ester Alkyl, preferably C3-20 naphthenic base, more preferably C3-12 naphthenic base.
As (methyl) acrylate with aromatic hydrocarbyl, (methyl) phenyl acrylate, (methyl) propylene can be enumerated Sour toluene ester, (methyl) acrylic acid diformazan phenyl ester, (methyl) acrylic acid naphthalene ester, (methyl) acrylic acid dinaphthalene ester, (methyl) propylene (methyl) benzyl acrylate of sour anthryl ester etc.；(methyl) acrylic acid aralkyl ester of (methyl) benzyl acrylate etc.；(first Base) phenoxyethyl acrylate etc. (methyl) acrylic acid aryloxy group alkyl base ester etc..The aryl of (methyl) benzyl acrylate, it is excellent It is selected as C6-20 aryl, more preferably C6-14 aryl.The aralkyl of (methyl) acrylic acid aralkyl ester, preferably C6-10 aryl C1-4 alkyl.The aryloxy alkyl of (methyl) acrylic acid aryloxy group alkyl base ester, preferably C6-10 aryloxy group C1-4 alkyl, it is more excellent It is selected as phenoxy group C1-4 alkyl.
(methyl) acrylate can have the substituent group of hydroxyl, halogen radical, alkoxy, epoxy group etc..As such (methyl) acrylate can enumerate (methyl) acrylic acid hydroxy alkyl ester of (methyl) 2-hydroxyethyl acrylate etc.；(methyl) third (methyl) acrylic acid alkyl halide base ester of olefin(e) acid chloromethyl ester, (methyl) acrylic acid 2- chloromethyl ester etc.；(methyl) acrylic acid 2- methoxy (methyl) alkoxyalkyl acrylate of base ethyl ester etc.；(methyl) acrylic acid epoxy of (methyl) glycidyl acrylate etc. Base Arrcostab etc..The alkyl of (methyl) acrylic acid hydroxy alkyl ester and (methyl) acrylic acid epoxy base Arrcostab, preferably C1-12 alkane Base.The alkoxyalkyl of (methyl) alkoxyalkyl acrylate, preferably C1-12 alkoxy C 1-12 alkyl.
Other than (methyl) acrylic acid units, polymer chain (B) on main chain with ring structure unit (below Referred to as " ring structure unit ").By polymer chain (B) there is ring structure on main chain, the heat-resisting of copolymer (P) can be improved Property.Furthermore it is also possible to it is expected improve solvent resistance, surface hardness, followability, oxygen and vapor barrier property, various optics Characteristic.In turn, when copolymer (P) or the resin combination for containing the copolymer (P) being used as film or sheet material, height can be improved Dimensional stability and shape stability under warm high humidity.By extending the film formed in this way, it can produce and carry out autohemagglutination The big phase difference for closing the ring structure of object chain (B) can be used as phase-contrast film use.Due to this feature, can will be copolymerized Object (P) or the resin combination for containing the copolymer (P) are used as phase-contrast film or being polarized with phase-contrast film function The optical thin film of device protective film etc..
The ring structure of the main chain of polymer chain (B), can be by some or all packets of (methyl) acrylic monomer It includes in ring structure, or the ring structure being directed respectively into (methyl) acrylic monomer.By (methyl) acrylic compounds list In the case that body some or all include in ring structure, for example, can be by the way that adjacent be come from (methyl) propylene 2 carboxylic acid group acid anhydrides, imidizates of the unit of acrylic monomer etc. and connect.In addition, adjacent comes from (methyl) propylene In the case where the group of a hydrogen atom containing protic with hydroxyl or amino etc. in the unit of acrylic monomer, this comes (methyl) acrylic compounds list is come from another from the group of the hydrogen atom containing protic of the unit of (methyl) acrylic monomer The carboxylic acid group of the unit of body is condensed, and can also form ring structure.It is led respectively with the unit from (methyl) acrylic monomer In the case where entering ring structure, such as can be total by the monomer with polymeric double bond in (methyl) acrylic monomer and ring structure It is poly-.
Ring structure can be appointing in 4 ring structures, 5 ring structures, 6 ring structures, 7 ring structures, 8 ring structures etc. It anticipates one kind, preferably 5 ring structures or 6 ring structures.
As ring structure, from the viewpoint of the heat resistance of copolymer (P), lactone ring structure, cyclic annular acyl can be preferably enumerated Imine structure (such as maleimide structure, glutarimide structure etc.), cyclic acid anhydride structure (such as maleic anhydride structure, Glutaric anhydride structure etc.) etc..1 kind of these ring structure can only be contained in the main chain of polymer chain (B), can also containing 2 kinds with On.In them, it is preferably selected from lactone ring structure, maleimide structure, maleic anhydride structure, glutarimide structure and penta 2 At least one of acid anhydride structure.
In the case that polymer chain (B) contains ring structure of the lactone ring structure as main chain, the ring element number of lactone ring structure There is no particular limitation, for example, can for 4 member rings into 8 member rings any one.In addition, the sight of the excellent in stability from ring structure Point, lactone ring structure are preferably 5 member rings or 6 member rings, more preferably 6 member rings.
As lactone ring structure, such as structure disclosed in Japanese Unexamined Patent Publication 2004-168882 bulletin can be enumerated etc., calmly Lactone ring structure is easily imported, it is specifically, high from the polymerization yield of presoma (polymer before lactone cyclization), forerunner can be improved Lactonic ring containing ratio in the cyclized condensation reaction of body, the polymer conduct that can will have the unit from (methyl) acrylate The reason of presoma etc. is set out, and the structure of following formula (1) expression is preferably shown.In following formula (1), R1、R2And R3It is respectively independent Ground indicates hydrogen atom or substituent group.
[chemical formula 1]
R as formula (1)1、R2And R3Substituent group, the organic residue of alkyl etc. can be enumerated, such as can enumerate and arbitrarily contain The alkyl etc. of the C1-20 of oxygen atom.As the alkyl, saturations or undersaturated straight chain shape, branched or cricoid rouge can be enumerated Fat race alkyl, aromatic hydrocarbyl.As aliphatic alkyl, such as the C1-20 that methyl, ethyl, n-propyl, isopropyl can be enumerated etc. Alkyl；The C2-20 alkenyl of vinyl, acrylic etc.；C3-20 naphthenic base of cyclopenta, cyclohexyl etc. etc..As aromatic hydrocarbon Base, such as the C6-20 aryl that phenyl, tolyl, xylyl, naphthalene, xenyl can be enumerated etc.；The C7- of benzyl, phenethyl etc. 20 aralkyl etc..These alkyl can contain oxygen atom, and specifically, more than one for the hydrogen atom that alkyl has can be selected from The group of at least one of hydroxyl, carboxyl, ether and ester group replaces.
For example, can be by by the ester group of the adjacent unit from (methyl) acrylate, and with hydroxyl or amino Deng the hydrogen atom containing protic group the unit from (methyl) acrylic monomer the hydrogen atom containing protic group Cyclizative condensation imports lactone ring structure in polymer chain (B).
In the lactone ring structure of formula (1), from the sight for being easy to get the small copolymer of excellent heat resistance, birefringence (P) From the point of view of point, preferably R1And R2Respectively stand alone as hydrogen atom or C1-20 alkyl, R3For hydrogen atom or methyl；More preferable R1And R2 Respectively stand alone as hydrogen atom or methyl, R3For hydrogen atom or methyl.
Lactone ring structure can be for example, by that will have (methyl) the acrylic monomer A of hydroxyl and (methyl) acrylic compounds After monomer B polymerization (being preferably copolymerized) is to import hydroxyl and ester group or carboxyl in strand, make these hydroxyls and ester group Or dealcoholysis or cyclodehydration condensation occur between carboxyl and is formed.As polymeric composition, (methyl) acrylic compounds with hydroxyl Monomer A be it is necessary, (methyl) acrylic monomer B include the monomer A.Monomer B can be consistent with monomer A, can also not Unanimously.When monomer B is consistent with monomer A, i.e. the homopolymerization of monomer A.
As (methyl) acrylic monomer A with hydroxyl, 2- (methylol) acrylic acid, 2- (ethoxy) third can be enumerated Olefin(e) acid, 2- (methylol) alkyl acrylate are (for example, 2- (methylol) methyl acrylate, 2- (methylol) ethyl acrylate, 2- (methylol) isopropyl acrylate, 2- (methylol) n-butyl acrylate, 2- (methylol) tert-butyl acrylate), 2- (hydroxyl second Base) alkyl acrylate (for example, 2- (ethoxy) methyl acrylate, 2- (ethoxy) ethyl acrylate) etc., it is preferable that it can lift 2- (methylol) acrylic acid or 2- (methylol) alkyl acrylate as the monomer with Hydroxy-propenyl part out.Especially It is preferred that showing 2- (methylol) methyl acrylate, 2- (methylol) ethyl acrylate.
As (methyl) acrylic monomer B, it is however preferred to have the monomer of vinyl and ester group or carboxyl, such as can enumerate (methyl) acrylic acid, (methyl) alkyl acrylate are (for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) N-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate etc.), (first Base) benzyl acrylate (for example, (methyl) phenyl acrylate, (methyl) benzyl acrylate etc.), 2- (hydroxyalkyl) alkyl acrylate Base ester is (for example, 2- (methylol) acrylic acid alkyl of 2- (methylol) methyl acrylate, 2- (methylol) ethyl acrylate etc. Ester, 2- (ethoxy) alkyl acrylate of 2- (ethoxy) methyl acrylate etc.) etc..
The lactone ring structure that polymer chain (B) can be indicated only containing a kind of formula (1), it is possible to have two or more.
In the case that polymer chain (B) has the ring structure of maleic anhydride structure or maleimide structure as main chain, As maleic anhydride structure or maleimide structure, the structure of following formula (2) expression is preferably shown.In following formula (2), R4 And R5Each independently represent hydrogen atom or methyl, R6Indicate hydrogen atom or substituent group, X1Indicate that oxygen atom or nitrogen are former Son, X1N1=0, X when for oxygen atom1N1=1 when for nitrogen-atoms.
[chemical formula 2]
R as formula (2)6Substituent group, alkyl etc. can be enumerated, such as any substituent group with halogen etc. can be enumerated The alkyl of C1-20.As the alkyl, saturations or undersaturated straight chain shape, branched or cricoid aliphatic alkyl, virtue can be enumerated Fragrant race's alkyl.As aliphatic alkyl, such as the C1-6 alkyl that methyl, ethyl, n-propyl, isopropyl can be enumerated etc.；Vinyl, The C2-6 alkenyl of acrylic etc.；C3-20 naphthenic base of cyclopenta, cyclohexyl etc. etc..As aromatic hydrocarbyl, such as can enumerate The C6-20 aryl of phenyl, tolyl, xylyl, naphthalene, xenyl etc.；C7-20 aralkyl of benzyl, phenethyl etc. etc..This A little alkyl can have the substituent group of halogen etc..
X1It is maleic anhydride structure by the ring structure that formula (2) is shown when for oxygen atom.For example, by by maleic anhydride It is copolymerized with (methyl) acrylic monomer (for example, (methyl) acrylate etc.), maleic anhydride structure can be directed into polymerization Object chain (B).
X1When for nitrogen-atoms, the ring structure that formula (2) is shown is maleimide structure.Such as by by maleimide with (methyl) acrylic monomer (for example, (methyl) acrylate) copolymerization, can imported into polymer for maleimide structure In chain (B).As maleimide structure, such as N unsubstituted maleimide structures, N- methyl maleimide can be enumerated Amine structure, n-ethylmaleimide structure, N- N-cyclohexylmaleimide structure, N-phenylmaleimide structure, N- naphthalene Base maleimide structure, N- benzyl maleimide structure etc..In addition, as the maleimide of maleimide structure is provided N unsubstituted maleimides, N- methylmaleimido, n-ethylmaleimide, N- cyclohexyl horse can be used in amine Come acid imide, N-phenylmaleimide, N- naphthalene maleimide, N- benzyl maleimide etc..
Polymer chain (B) is with X1In the case where maleimide structure for nitrogen-atoms, from being easy to get heat resistance From the viewpoint of the copolymer (P) excellent, birefringence is small, preferably R4And R5For hydrogen atom, R6For C3-20 naphthenic base or C6- 20 aromatic series bases (aryl, aralkyl etc.)；More preferable R4And R5For hydrogen atom, R6For cyclohexyl or phenyl.
The ring structure that polymer chain (B) can be indicated only with a kind of formula (2), it is possible to have two or more.
In the case that polymer chain (B) has the ring structure of glutarimide structure or glutaric anhydride structure as main chain, As glutarimide structure or glutaric anhydride structure, the structure of following formula (3) expression is preferably shown.In following formula (3), R7 And R8Each independently represent hydrogen atom or alkyl, R9Indicate hydrogen atom or substituent group, X2Indicate that oxygen atom or nitrogen are former Son, X2N2=0, X when for oxygen atom2N2=1 when for nitrogen-atoms.
[chemical formula 3]
In formula (3), as R7And R8Alkyl, can preferably enumerate straight-chain or branched alkyl, such as first can be enumerated Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, positive heptan The C1-8 alkyl etc. of base, different heptyl, n-octyl, 2- ethylhexyl etc..In addition, from excellent heat resistance, birefringence is easy to get From the viewpoint of small copolymer (P), R7And R8It is preferred that respectively standing alone as hydrogen atom or C1-4 alkyl, more preferably hydrogen atom Or methyl.
R as formula (3)9Substituent group, alkyl etc. can be enumerated, such as any substituent group with halogen etc. can be enumerated The alkyl of C1-20.As the alkyl, saturations or undersaturated straight chain shape, branched or cricoid aliphatic alkyl, virtue can be enumerated Fragrant race's alkyl.As aliphatic alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth can be enumerated The C1-10 alkyl of base, n-pentyl, isopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, 2- ethylhexyl etc.； The C2-10 alkenyl of vinyl, acrylic etc.；C3-12 naphthenic base of cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc. etc..Make For aromatic hydrocarbyl, such as the C6-20 that phenyl, tolyl, xylyl, naphthalene, xenyl, binaphthyl, anthryl can be enumerated etc. Aryl；C7-20 aralkyl of benzyl, phenethyl etc. etc..These alkyl arbitrarily have the substituent group of halogen etc..In them, calmly It is easy to get to from the viewpoint of the small copolymer of excellent heat resistance, birefringence (P), R9Preferably C1-4 alkyl, C3-7 naphthenic base, C6-20 aryl perhaps C7-20 aralkyl more preferably methyl, cyclohexyl, phenyl or tolyl.
X2When for oxygen atom, ring structure shown in formula (3) is glutaric anhydride structure.For example, by the way that adjacent is come from (first Base) acrylic monomer unit 2 carboxylic acid group acid anhydrides, glutaric anhydride structure can be imported into polymer chain (B) In.
X2When for nitrogen-atoms, ring structure shown in formula (3) is glutarimide structure.For example, by the way that adjacent is come from 2 carboxylic acid group imidizates of the unit of (methyl) acrylic monomer, or by the way that adjacent is come from (methyl) propylene The ester group cyclizative condensation of the amide groups of the unit of amide and the unit from (methyl) acrylate, can be by glutarimide knot Structure is imported into polymer chain (B).
In the ring structure of formula (3), come from the viewpoint for being easy to get the small copolymer of excellent heat resistance, birefringence (P) It sees, preferably R7And R8Respectively stand alone as hydrogen atom or methyl, R9For C1-10 alkyl, C3-12 naphthenic base or C6-20 aromatic series Base；More excellent R7And R8Respectively stand alone as hydrogen atom or methyl, R9For C1-4 alkyl, C3-7 naphthenic base, C6-20 aryl or C7- 20 aralkyl；Further preferred R7And R8Respectively stand alone as hydrogen atom or methyl, R9For methyl, cyclohexyl, phenyl or toluene Base；Particularly preferred R7And R8Respectively stand alone as hydrogen atom or methyl, R9For cyclohexyl or phenyl.
The ring structure that polymer chain (B) can be indicated only with a kind of formula (3), it is possible to have two or more.
In above explained ring structure, copolymer (P) or the resin combination containing the copolymer (P) are suitable for optics When film, from the viewpoint of assigning good surface hardness, solvent resistance, followability, barrier properties, optical characteristics, preferably The ring structure unit of polymer chain (B) contains lactone ring structure and/or maleimide structure.Optical thin film is phase-contrast film In the case where, positive phase difference can be assigned, from the having good stability of phase difference characteristics from the viewpoint of, more preferable polymer chain (B) ring structure unit contains lactone ring structure.
Polymer chain (B) can further have the unit from other unsaturated monomers.Other unsaturated monomers, as long as It is the compound with polymeric double bond, there is no particular limitation, such as vinyl acetate, vinyl propionate can be enumerated etc. Vinyl esters；The aromatic series of styrene, vinyltoluene, methoxy styrene, α-methylstyrene, 2- vinylpyridine etc. Vinyl compound；The vinyl silicon of vinyltrimethoxysilane, γ-(methyl) acryloxypropyl methoxy silane etc. Alkane etc..For example, being easily adjusted the refraction of copolymer (P) when polymer chain (B) has the unit from aromatic vinyl monomer Rate and phase difference characteristics.The details of aromatic vinyl monomer, the aromatic vinyl monomer of reference polymer blocks (a2) Explanation.In addition, polymer chain (B) is preferably random total in the case that polymer chain (B) is formed by monomer component of more than two kinds Polymers.
In polymer chain (B), the content ratio of the unit from (methyl) acrylate of copolymer (P) is 45 matter Measure % or more 98 mass % or less.The content ratio of unit in polymer chain (B) from (methyl) acrylate is 45 matter When measuring % or more, polymerization can inhibit the generation of gel compound when forming polymer chain (B), be easy copolymer (P) being used for light Learn purposes.In addition, being also easy to improve the mechanical strength of copolymer (P).The list of (methyl) acrylate is come from polymer chain (B) When the content ratio of member is 98 mass % or less, the copolymer (P) of available excellent heat resistance.It is come from polymer chain (B) The content ratio of the unit of (methyl) acrylate, preferably 50 mass % or more, more preferably 55 mass % or more, further Preferably 60 mass % or more, it is additionally preferred to be 97 mass % or less.
The content ratio of ring structure unit in polymer chain (B), preferably 2 mass % or more, more preferably 3 mass % More than, further preferably 5 mass % or more, it is additionally preferred to be 50 mass % hereinafter, more preferably 45 mass % are hereinafter, into one Step is preferably 40 mass % or less.The content ratio of adjustment ring structural unit in this way, it is easier in well balanced mode Improve both heat resistance and the mechanical strength of copolymer (P).In addition, the content ratio of ring structure unit described herein, refers to The containing ratio of the unit with ring structure contained on the main chain of polymer chain (B), such as refer to what above-mentioned formula (1)-(3) indicated The content ratio of structure.
In polymer chain (B), total content ratio of (methyl) acrylic acid units and ring structure unit, preferably 90 matter Measure % or more, more preferably 93 mass % or more, further preferably 95 mass % or more.It is easy to improve copolymer (P) as a result, The transparency and heat resistance.In addition, total content ratio of unit and ring structure unit from (methyl) acrylate is preferred Also in such range.
Polymer chain (B) is preferably grafted on polymer chain (A).Polymer chain (B) can come from polymer chain (A) The bonding of the unit of alkadienes and/or alkene, in addition can also be with the unit from alkadienes and/or alkene of polymer chain (A) Unit bonding in addition.In the case where the former, polymer chain (B) can be with polymer chain (A) from alkadienes and/or alkene Unit Direct Bonding, can also be bonded by linker.
Situation of polymer chain (B) Direct Bonding on the unit from alkadienes and/or alkene of polymer chain (A) Under, (methyl) acrylic acid units or ring structure unit Direct Bonding the coming from polymer chain (A) of preferred polymers chain (B) On the unit of alkadienes and/or alkene.Polymer chain (B) can be bonded in the main chain of the unit from alkadienes and/or alkene Carbon atom on, can also be bonded on the main chain as substituent group (side chain) bonding alkyl carbon atom on.It polymerize in this way When object chain (B) is bonded on polymer chain (A), it is easy to get the few copolymer of gel compound (P).
Polymer chain (B) passes through the feelings that linker is bonded with the unit from alkadienes and/or alkene of polymer chain (A) Under condition, linker preferably has selected from ester bond (- CO-O-), urethane bond (- NH-CO-O-) and ehter bond (- O-) at least One kind, the linker can also have the organic group of the divalent of methylene or hydroxy methylene etc..
Polymer chain (B) is bonded on the unit other than the unit from alkadienes and/or alkene of polymer chain (A) In the case of, for example, polymer chain (A) contain with polymerizable functional group (polymeric double bond) unit, polymer chain (B) with should The polymerizable functional group of unit is bonded or polymer chain (A) is other than the unit from alkadienes and/or alkene, can also To pass through the linker and polymer chain (B) key of ester bond (- CO-O-), urethane bond (- NH-CO-O-), ehter bond (- O-) etc. It closes.The linker can further have the organic group of the divalent of methylene or hydroxy methylene etc..
It is grafted on each embodiment on polymer chain (A) for above explained polymer chain (B), in following copolymerization It is described in detail in the explanation of the preparation method of object (P).
There is no particular limitation for the content ratio of ring structure unit in copolymer (P), in copolymer (P), ring structure list Member content ratio, such as preferably 1 mass % or more, more preferably 3 mass % or more, further preferably 5 mass % with On, it is additionally preferred to it is 60 mass % hereinafter, more preferably 50 mass % are hereinafter, further preferably 40 mass % or less.Pass through The content ratio for adjusting the ring structure unit in copolymer (P) in this way, can be easy to improve copolymer in well balanced mode (P) heat resistance or the transparency, mouldability, mechanical strength etc..
In the case that copolymer (P) has ring structure unit of the lactone ring structure as polymer chain (B), it is copolymerized from improving From the viewpoint of the heat resistance and the transparency of object (P), the content ratio of the lactone ring structure in copolymer (P), such as preferably 1 Quality % or more, more preferably 3 mass % or more, further preferably 5 mass % or more, it is additionally preferred to for 60 mass % with Under, more preferably 50 mass % are hereinafter, further preferably 40 mass % or less.From the viewpoint of same, copolymer (P) tool In the case where having the ring structure unit of maleic anhydride structure and/or maleimide structure as polymer chain (B), copolymer (P) content ratio of these ring structures in, such as preferably 1 mass % or more, more preferably 3 mass % or more, further Preferably 5 mass % or more, it is additionally preferred to be 60 mass % hereinafter, more preferably 50 mass % are hereinafter, further preferably 40 Quality % or less.Copolymer (P) has the ring knot of glutarimide structure and/or glutaric anhydride structure as polymer chain (B) In the case where structure unit, the content ratio of these ring structures in copolymer (P), such as preferably 1 mass % or more, more preferably For 3 mass % or more, further preferably 5 mass % or more, it is additionally preferred to be 60 mass % hereinafter, more preferably 50 mass % Hereinafter, further preferably 40 mass % or less.
The weight average molecular weight of copolymer (P), preferably 0.2 ten thousand or more, more preferably 0.5 ten thousand or more, further preferably 3 Ten thousand or more, it is still more preferably 50,000 or more, particularly preferably 70,000 or more, it is additionally preferred to for 1,000,000 hereinafter, more preferably 50 Ten thousand hereinafter, further preferably 300,000 hereinafter, still more preferably be 200,000 or less.By making dividing equally in copolymer (P) again Son is measured in such range, and the molding processibility of copolymer (P) improves, and is easy to improve the intensity of obtained molded product.
The weight average molecular weight of copolymer (P), preferably 1.1 times or more of the weight average molecular weight of polymer chain (A), more preferably It is 1.2 times or more, more preferably 1.3 times or more, it is additionally preferred to for 20 times hereinafter, more preferably 12 times hereinafter, further preferably For 10 times hereinafter, being still more preferably 7 times hereinafter, particularly preferably 5 times or less.Thus, it is possible in well balanced mode Assign copolymer (P) transparency, mechanical strength, each characteristic of heat resistance.
The refractive index of copolymer (P) is preferably the value with the refractive index close of polymer chain (A), thus it is easy to ensure that copolymerization The transparency of object (P).Specifically, the specific refractivity of the refractive index of copolymer (P) and polymer chain (A) are preferably smaller than 0.1, more Preferably 0.05 hereinafter, further preferably 0.02 or less.Polymer chain (A) from the viewpoint of same, in copolymer (P) Refractive index be preferably value with the refractive index close of polymer chain (B), specifically, the refractive index of polymer chain (A) with polymerize The specific refractivity of object chain (B) is preferably smaller than 0.1, more preferably 0.05 hereinafter, further preferably 0.02 or less.
Copolymer (P) preferably has glass transition temperature at 100 DEG C or more and less than 100 DEG C respectively.In addition, will 100 DEG C or more of glass transition temperature is known as " glass transition temperature of high temperature side ", by the glass transition less than 100 DEG C Temperature is known as " glass transition temperature of low temperature side ".Copolymer (P) can have the glass transition temperature of multiple high temperature sides, Also it can have the glass transition temperature of multiple low temperature sides.Copolymer (P) by the glass transition temperature with high temperature side, The heat resistance of copolymer (P) improves, and whens copolymer (P) being in addition shaped to film etc., will not soften at high temperature, Ke Yiti High molding processibility.The resistance to punching of copolymer (P) can be improved by the glass transition temperature with low temperature side in copolymer (P) Hitting property.The glass transition temperature of copolymer (P) high temperature side, preferably 113 DEG C or more, more preferably 116 DEG C or more, further Preferably 120 DEG C or more.The glass transition temperature of copolymer (P) low temperature side, preferably smaller than 50 DEG C, more preferably less than 20 DEG C, It is further preferably no larger than 0 DEG C, is still more preferably less than -20 DEG C.
Copolymer (P) can be by carrying out addition for the monomer component for forming polymer chain (B) on polymer chain (A) It polymerize and prepares.Thus, the preparation method of copolymer (P) preferably includes: having the unit from alkadienes and/or alkene In the presence of polymer (hereinafter referred to as " raw polymer (P1) "), will containing (methyl) acrylic monomer monomer component into The process (polymerization process) of row polymerization, thus, it is possible to which the monomer component and polymerizable raw material of (methyl) acrylic monomer will be contained Object (P1) carries out addition polymerization.In this case, the monomer component containing (methyl) acrylic monomer can for example pass through The method and raw polymer (P1) of following any one carry out addition polymerization: (1) with raw polymer (P1) from diene The method of the unit Direct Bonding of hydrocarbon and/or alkene, the list from alkadienes and/or alkene of (2) and raw polymer (P1) The method of the polymerizable functional group bonding of the linker that has of side chain of member, or (3) and raw polymer (P1) come from two The method for the polymerizable functional group bonding that the side chain of unit other than the unit of alkene and/or alkene has.In this case, Obtained copolymer is graft copolymer.Furthermore in the present specification, " raw polymer (P1) " is also referred to as " polymer (P1)”。
Raw polymer (P1) can at least have the unit from alkadienes and/or alkene, can also further have Unit from other unsaturated monomers.The unit from alkadienes and/or alkene of raw polymer (P1) with come from other The details of the unit of unsaturated monomer, unit referring to above-mentioned polymer chain (A) from alkadienes and/or alkene and comes from The explanation of the unit of other unsaturated monomers.In unit from alkadienes and/or alkene, a part of hydrogen atom can be by chlorine Change.Raw polymer (P1) can be to contain polymer blocks (a1) and tool with the unit from alkadienes and/or alkene There is a block copolymer of the polymer blocks (a2) of the unit from other unsaturated monomers, polymer blocks (a2) can also be by Unit from aromatic vinyl monomer is constituted.These details are also referred to the explanation of above-mentioned polymer chain (A).This Outside, in the method for above-mentioned (2), raw polymer (P1) have the unit from alkadienes and/or alkene side chain on have Polymerizable functional group linker, the unit in the method for above-mentioned (3), other than the unit from alkadienes and/or alkene Side chain on have polymerizable functional group.
The weight average molecular weight of raw polymer (P1) is preferably 0.1 ten thousand or more, and more preferably 0.5 ten thousand or more, it is further excellent 10,000 or more are selected as, is still more preferably 30,000 or more, it is additionally preferred to for 500,000 hereinafter, more preferably 300,000 hereinafter, further Preferably 200,000 hereinafter, be still more preferably 100,000 or less.By making the weight average molecular weight of raw polymer (P1) in this way In the range of, the mouldability of copolymer (P) improves, it is easy to ensure that the intensity and the transparency of copolymer (P).In addition, with (first is contained Base) acrylic monomer monomer component polymerization reaction when, the generation of crosslinked and gel compound can be inhibited.
In polymerization process, raw polymer (P1) can be used only a kind, and also two or more kinds may be used.The case where the latter Under, it is easily adjusted the average molecular weight and double bond amount as resin combination.
Monomer component used in the formation of polymer chain (B), other than (methyl) acrylic monomer, as offer The monomer etc. in ring structure with polymeric double bond also can be used in the monomer of ring structure unit.For example, being formed on main chain has In the case where the polymer chain (B) of maleimide structure, it is preferable to use with the monomer of polymeric double bond in ring structure.Or Person, in the case where carrying out ring structure formation process after polymerization process, can be used can form ring structure in this process Monomer is as monomer component.Alternatively, it is also possible to use other unsaturated monomers in addition to this.The details of these monomer components, Referring to (methyl) acrylic monomer of the above-mentioned polymer chain (B) of formation, the monomer for assigning polymer chain (B) ring structure, shape At the explanation of other unsaturated monomers of polymer chain (B).
Hereinafter, gathering for the monomer component containing (methyl) acrylic monomer is carried out addition with raw polymer (P1) Conjunction method, the method that above-mentioned (1)-(3) are described in detail.
Above-mentioned (1) will containing (methyl) acrylic monomer monomer component and raw polymer (P1) come from two In the method for the unit Direct Bonding of alkene and/or alkene, the monomer component of (methyl) acrylic monomer will be contained, with raw material Polymer (P1) is bonded from the unit of alkadienes and/or alkene.In this case, raw polymer (P1) come from two The unit of alkene and/or alkene preferably has the double bond from alkadienes.Monomer containing (methyl) acrylic monomer at Point, it can be bonded with the double bond from alkadienes of the main chain of raw polymer (P1), carbon that can also be adjacent with the double bond is former Sub-key is closed.Alternatively, polymer chain (B) can also be bonded as substituent group (side chain) on the main chain of raw polymer (P1) Double bond bonding from alkadienes, carbon atom bonding that can also be adjacent with the double bond.In above-mentioned arbitrary situation, what is obtained is total to Polymers (P) is the polymer of the unit Direct Bonding from alkadienes and/or alkene of polymer chain (B) and polymer chain (A). In the method, (alkene is double for the double bond preferably having the unit from alkadienes and/or alkene of raw polymer (P1) Key) vinyl site, allylic sites etc. high activity hydrogen seize, it is possible thereby to generate free radical in the site, make to be formed The monomer component addition polymerization of polymer chain (B).
The monomer component of (methyl) acrylic monomer will be contained in above-mentioned (2), with coming from for raw polymer (P1) In the method for the polymerizable functional group bonding for the linker having on the side chain of the unit of alkadienes and/or alkene, the linker It is bonded with polymerizable functional group (polymeric double bond), and with the side chain from alkadienes and/or the unit of alkene.What is obtained is total to Polymers (P) is to be bonded polymer chain (B) with the unit from alkadienes and/or alkene of polymer chain (A) by linker Polymer.
Other than polymerizable functional group (polymeric double bond), linker preferably have selected from ester bond, urethane bond, At least one of ehter bond can also further have the organic group of the divalent of methylene or hydroxy methylene etc..With in this way Linker raw polymer (P1), can by make with the unit from alkadienes and/or alkene and have provide The polymer (hereinafter referred to as " raw polymer (P2) ") of the functional group of ester bond, urethane bond or ehter bond, with have and this The functional group of functional group reactions and compound (hereinafter referred to as " the free-radical polymerised chemical combination with polymerizable functional group Object ") reaction obtain.
The functional group of ester bond, urethane bond or ehter bond is provided, is referred to by anti-with free-radical polymerised compound The functional group of the key of above-mentioned any one should be formed, and specifically, it is preferable to which carboxyl or its anhydride group, epoxy group, hydroxyl, different can be enumerated Cyanic acid ester group etc..In order to import these functional groups in raw polymer (P2), the unsaturation with these functional groups can be made Compound is with the polymer with the unit from alkadienes and/or alkene (for example, used in the preparation method of above-mentioned (1) Raw polymer (P1)) it reacts, which carries out usually using radical initiator.
As the unsaturated compound with carboxyl or its anhydride group, (methyl) acrylic acid, fumaric acid, maleic acid can be enumerated And its unsaturated carboxylic acid and its acid anhydrides of acid anhydrides, itaconic acid and its acid anhydrides, crotonic acid and its acid anhydrides, citraconic acid and its acid anhydrides etc. Deng.
As the unsaturated compound with epoxy group, the list of (methyl) glycidyl acrylate, maleic acid can be enumerated With 2-glycidyl ester, the list of itaconic acid and 2-glycidyl ester, the list of allyl succinic acid and 2-glycidyl ester, to benzene second The unsaturated carboxylic acid ethylene oxidic ester of the ethylene oxidic ester of olefinic carboxylic acid etc.；Allyl glycidyl ether, 2- methacrylic shrink The glycidol ether of glycerin ether, styrene-p- glycidol ether etc.；To glycidyl styrene；3,4- epoxy-1-butylene, The epoxy olefins of 3,4- epoxy -3-methyl-1-butene etc.；Vinylcyclohexene list oxide etc..
As the unsaturated compound with hydroxyl, 2- ethoxy (methyl) acrylate, 2- hydroxypropyl (first can be enumerated Base) acrylate, 2- hydroxyl butyl (methyl) acrylate etc. hydroxyalkyl (methyl) acrylate；N- methylol (methyl) propylene Amide；2- hydroxyethylmethacry,ate -6- hexanol addition polymer；The enol of 2- propylene -1- alcohol etc.；2- propine -1- alcohol etc. Alkynol；Hydroxyvinyl ether etc..
As the unsaturated compound with isocyanate group, (methyl) acrylic acid 2- ethyl isocyanate, methyl can be enumerated Acryloyl isocyanates etc..
Free-radical polymerised compound, have polymerizable functional group (polymeric double bond) while, also have with carboxyl or The reactive functional group of its anhydride group, epoxy group, hydroxyl or isocyanate group.As reactive functional groups, such as can enumerate Hydroxyl, epoxy group, isocyanate group, carboxyl.
As the free-radical polymerised compound of the hydroxyl with reactive functional groups, 2- ethoxy (methyl) third can be enumerated Hydroxyalkyl (methyl) acrylate of olefin(e) acid ester, 2- hydroxypropyl (methyl) acrylate, 2- hydroxyl butyl (methyl) acrylate etc.； N- methylol (methyl) acrylamide；2- hydroxyethylmethacry,ate -6- hexanol addition polymer；The alkene of 2- propylene -1- alcohol etc. Alcohol；The alkynol of 2- propine -1- alcohol etc.；Hydroxyvinyl ether etc..
As the free-radical polymerised compound of the epoxy group with reactive functional groups, the contracting of (methyl) acrylic acid can be enumerated Water glyceride, the list of maleic acid and 2-glycidyl ester, the list of itaconic acid and 2-glycidyl ester, allyl succinic acid list and 2-glycidyl ester, the ethylene oxidic ester to the unsaturated carboxylic acid of the ethylene oxidic ester of styrene carboxylic acid etc.；Allyl glycidyl is sweet The glycidol ether of oily ether, 2- methacrylic glycidol ether, styrene-p- glycidol ether etc.；To glycidyl benzene Ethylene；The epoxy olefins of 3,4- epoxy-1-butylene, 3,4- epoxy -3-methyl-1-butene etc.；Vinylcyclohexene list oxide Deng.
As the free-radical polymerised compound of the isocyanate group with reactive functional groups, (methyl) propylene can be enumerated Sour 2- ethyl isocyanate, methacryl isocyanates etc..
As the free-radical polymerised compound of the carboxyl with reactive functional groups, (methyl) acrylic acid etc. can be enumerated Unsaturated acids；The carboxyalkyl vinyl ethers etc. of carboxyethyl vinyl ethers, carboxylic propyl vinyl ether etc..
In the case that the functional group that raw polymer (P2) has is carboxyl or its anhydride group, as free-radical polymerisedization The reactive functional groups for closing object, preferably show hydroxyl, epoxy group and isocyanate group.In them, particularly preferably there is hydroxyl Free-radical polymerised compound.In this case, pass through the anti-of raw polymer (P2) and free-radical polymerised compound The raw polymer (P1) that should be obtained, be side chain on linker polymer, the linker have polymerizable functional group and Ester bond.
In the case that the functional group that raw polymer (P2) has is epoxy group, as the anti-of free-radical polymerised compound Answering property functional group preferably shows carboxyl and hydroxyl.Particularly preferably with the free-radical polymerised compound of carboxyl in them.? In this case, the raw polymer as obtained from the reacting of raw polymer (P2) and free-radical polymerised compound (P1), for, with the polymer of linker, the linker is with polymerizable functional group and ester bond (specifically ,-CH on side chain (OH)-CH2The divalent organic group that-OCO- is indicated).
In the case that the functional group that raw polymer (P2) has is hydroxyl, the reaction as free-radical polymerised compound Property functional group, preferable example go out isocyanate group, carboxyl and epoxy group.Particularly preferably there is oneself of isocyanate group in them By base polymerizable monomer.In this case, it is obtained by raw polymer (P2) with reacting for free-radical polymerised compound The raw polymer (P1) arrived, is the polymer on side chain with linker, and the linker has polymerizable functional group and ammonia Carbamate key.
In the case that the functional group that raw polymer (P2) has is isocyanate group, as free-radical polymerised compound Reactive functional groups, preferable example goes out hydroxyl and carboxyl.Particularly preferably with the free-radical polymerised list of hydroxyl in them Body.In this case, the polymerizable raw material as obtained from the reacting of raw polymer (P2) and free-radical polymerised compound Object (P1), is the polymer on side chain with linker, which has polymerizable functional group and urethane bond.
Workable raw polymer (P1) in preparation method as (2), such as can enumerate on side chain with methyl-prop LIR UC-102M or UC-203 (being KURARAY society system) of the polyisoprene of enoyl- and ester bond etc..
It is illustrated for the preparation method of above-mentioned (3) of copolymer (P).(methyl) propylene will be contained in above-mentioned (3) The side chain of unit other than the monomer component of acrylic monomer and the unit from alkadienes and/or alkene of raw polymer (P1) On in the method for polymerizable functional group bonding that has, by the way that alkadienes and/or alkene (are polymerize with polymerizable functional group Property double bond) unsaturated monomer copolymerization, or by alkadienes and/or alkene with containing with carboxyl or its anhydride group, epoxy group, The unsaturated monomer of the functional group of hydroxyl or isocyanate group is copolymerized, so with it is above explained with reactive functional groups from It is reacted by base polymerizable compound, available raw polymer (P1).Alternatively, by that will have from alkadienes and/or alkene The (co) polymer of the unit of hydrocarbon and the polymerization of unsaturated monomers with polymerizable functional group (polymeric double bond), or will have The (co) polymer of unit from alkadienes and/or alkene with have carboxyl or its anhydride group, epoxy group, hydroxyl or isocyanic acid The polymerization of unsaturated monomers of ester group, so it is anti-with the above explained free-radical polymerised compound with reactive functional groups It answers, also available raw polymer (P1).In the presence of raw polymer (P1) obtained in this way, by the way that (first will be contained Base) acrylic monomer polymerizing monomer components, obtain copolymer (P).Obtained copolymer (P) is polymer chain (B) and gathers Close the polymer of the unit bonding other than the unit from alkadienes and/or alkene of object chain (A).
By the (co) polymer of the unit with alkadienes and/or alkene or from them, and with polymerism function In the case where the polymerization of unsaturated monomers of group, as the unsaturated monomer with polymerizable functional group, multifunctional (first can be enumerated Base) acrylate, (methyl) acrylate containing vinyl ether group, (methyl) acrylate containing allyl etc. it is multifunctional (methyl) acrylic compounds, polyfunctional vinyl ether, multifunctional allylic compound, multifunctional aromatic vinyl Close object etc..
As multifunctional (methyl) acrylate, such as ethylene glycol two (methyl) acrylate, diethylene glycol two can be enumerated (methyl) acrylate, polyethylene glycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, bisphenol-A epoxy alkane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, the double acrylic acid of 2,2'- [oxo is bis- (methylene)], two Alkyl -2,2 '-[oxo is bis- (methylene)] double -2- acrylate etc..
As (methyl) acrylate containing vinyl ether group, such as (methyl) acrylic acid 2- ethyleneoxy second can be enumerated Ester, (methyl) acrylic acid 4- ethyleneoxy butyl ester, (methyl) acrylic acid 2- (vinyloxyethoxy) ethyl ester etc..
As (methyl) acrylate containing allyl, such as (methyl) allyl acrylate, α-allyloxy can be enumerated Methyl methacrylate, α-allyloxy octadecyl methacrylate, α-allyloxy methacrylic acid 2- decyl Arrcostab etc..
As polyfunctional vinyl ether, such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, poly- second can be enumerated Divinyl ether, hexylene glycol divinyl ether, bisphenol-A epoxy alkane divinyl ether, trimethylolpropane tris vinyl ethers Deng.
As multifunctional allylic compound, such as ethylene glycol diallyl ether, diethylene glycol diallyl can be enumerated Ether, polyethylene glycol diallyl ether, hexylene glycol diallyl ether, bisphenol-A epoxy alkane diallyl ether, trimethylolpropane tris alkene The multifunctional allyl ether of propyl ether, two trimethylolpropane tetraallyl ethers etc.；More officials of Triallyl isocyanurate etc. The isocyanuric acid ester of allyl can be contained；The multifunctional allyl ester of diallyl phthalate, diphenic acid diallyl etc.； Diallyl nadikimide compound etc.；Diallyl nadikimide compound etc..
As multifunctional aromatic ethenyl compound, such as divinylbenzene can be enumerated etc..
By the (co) polymer of the unit with alkadienes and/or alkene or from them, with containing with carboxyl or In the case where its anhydride group, epoxy group, hydroxyl or the polymerization of unsaturated monomers of isocyanate functional group, obtained polymer (hereinafter referred to as " raw polymer (P3) ") while having from the unit of alkadienes and/or alkene, also has and comes from diene Unit other than the unit of hydrocarbon and/or alkene is bonded with carboxyl or its anhydride group, epoxy on the side chain of other units The functional group of base, hydroxyl or isocyanate group.As raw polymer (P3), such as can to enumerate ethylene-(methyl) acrylic acid total Polymers, ethylene -2- ethoxy (methyl) acrylate copolymer, ethylene-glycidyl base (methyl) acrylate copolymer, second Alkene-polyethyleneglycol (methyl) acrylate copolymer, ethane-acetic acid ethyenyl ester-(methyl) acrylic copolymer, ethylene-(first Base) ethyl acrylate-maleic acid (acid anhydride) copolymer, ethane-acetic acid ethyenyl ester-maleic acid (acid anhydride) copolymer, ethane-acetic acid ethyenyl Ester -2- ethoxy (methyl) acrylate copolymer, ethane-acetic acid ethyenyl ester-glycidyl (meth) acrylate copolymerization The part of object, ethane-acetic acid ethyenyl ester-polyethyleneglycol (methyl) acrylate copolymer, vinyl-vinyl acetate copolymer It is saponified etc..In them, preferably ethylene-(methyl) acrylic copolymer, ethylene-(methyl) ethyl acrylate-maleic acid (acid anhydride) copolymer, ethane-acetic acid ethyenyl ester-glycidyl (meth) acrylate copolymer.
By making raw polymer (P3) and the above explained free-radical polymerised compound with reactive functional groups Reaction, obtains raw polymer (P1).The functional group that raw polymer (P3) has reacts with free-radical polymerised compound The details of property functional group, referring to above-mentioned (2) method in about their explanation.
In the method for above-mentioned (2) raw polymer (P2) and free-radical polymerised compound react or it is above-mentioned (3) Method in the reacting of raw polymer (P3) and free-radical polymerised compound, relative to raw polymer (P2) or original Expect 1 equivalent of the functional group in polymer (P3), the reactive functional groups of free-radical polymerised compound are preferably with 0.1-10 The mode of equivalent cooperates and is reacted.Thus, it is possible to improve the yield of finally obtained copolymer (P).
Above-mentioned reaction preferably carries out in a suitable organic solvent, as organic solvent, can enumerate toluene, dimethylbenzene, Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), butyl acetate, oxytol acetate etc..Reaction temperature is usually 20 DEG C -150 DEG C, preferably 50℃-120℃。
Raw polymer (P2) or raw polymer (P3) are preferably being catalyzed with reacting for free-radical polymerised compound It is carried out in the presence of agent.As catalyst, can be used in the esterification reaction acid or alkali compounds, such as sulfuric acid, to toluene sulphur Such as two fourth of lauric acid can be used in urethane reaction in acid, zinc chloride, pyridine, triethylamine, dimethyl benzylamine etc. Ji Xi etc..
When reaction, the generation of the homopolymer of vinyl monomer in order to prevent is further preferably reacted under oxygen or air atmosphere, And suitable polymerization inhibitor such as quinhydrones, hydroquinone monomethyl ether, phenthazine are added in reaction system.
In the method for above-mentioned (1)~(3), in the presence of raw polymer (P1) obtained as described above, pass through by (as needed can be further containing the monomer in circular structure with polymeric double bond) containing (methyl) acrylic monomer Monomer component is polymerize, available copolymer (P).Preferably, by the way that the monomer of (methyl) acrylic monomer will be contained Ingredient and raw polymer (P1) are graft-polymerized, and obtain copolymer (P).Each monomer component containing (methyl) acrylic monomer Dosage, the unit from (methyl) acrylate in finally obtained polymer chain (B) can be made with appropriate adjustment Content ratio is in expected range.From the viewpoint of the generation of gel compound in easy inhibition polymerization process, preferably by upper The method for stating (1) gathers the monomer component containing (methyl) acrylic monomer in the presence of raw polymer (P1) It closes.In addition, above-mentioned (2), (3) method in, by setting the control polymerization reaction such as shorter polymerization reaction time, can inhibit The generation of gel compound.
Mass polymerization, solution polymerization process, emulsion polymerization method, suspended polymerization etc. can be used in the polymerization of monomer component Well known polymerization, it is preferable to use solution polymerization process.When using solution polymerization process, small foreign matter can be inhibited to be mixed into copolymerization Object (P), it is easier to copolymer (P) be made to be suitable for optical material purposes etc..
As polymerized form, batchwise polymerization method, any one in continuous polymerization can be used for example.It is single when polymerization Body ingredient can be added together, can also be added by several times.
Polymer solvent can suitably be selected according to the composition of monomer component, can be used in common Raolical polymerizable The organic solvent used.Specifically, the aromatic hydrocarbon of toluene, dimethylbenzene, ethylbenzene etc. can be enumerated；Acetone, methyl ethyl ketone, first The ketone of base isobutyl ketone, cyclohexanone etc.；Tetrahydrofuran, dioxanes, glycol dimethyl ether, diethylene glycol dimethyl ether, methyl phenyl ethers anisole Deng ethers；The esters of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, 3- methoxybutyl acetic acid esters etc.；Methyl The dioxane of cellosolve, ethyl cellosolve, butyl cellosolve etc.；The alcohols of methanol, ethyl alcohol, isopropanol, n-butanol etc.；Second The nitrile of nitrile, propionitrile, butyronitrile, benzonitrile etc.；Chloroform；Dimethyl sulfoxide etc..These solvents can be used only a kind, also can be used together 2 Kind or more.
The polymerization reaction of raw polymer (P1) and monomer component, the preferably presence in polymerization catalyst (polymerization initiator) Lower progress.As polymerization catalyst, 2,2 '-azodiisobutyronitriles, 2,2 '-azo, two (2- amidine propanes) two can be used for example The azo compounds of hydrochloride, dimethyl -2,2 '-azo two (2 Methylpropionic acid ester), 4,4 '-azos two (4- cyanopentanoic acid) etc. Object；The persulfuric acid salt of potassium peroxydisulfate etc.；Isopropyl benzene hydroperoxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, mistake Aoxidize lauroyl, benzoyl peroxide, BPIC t butyl peroxy isopropyl carbonate, t-amyl peroxy -2 ethyl hexanoic acid ester, tertiary pentyl Peroctoate, t-amyl peroxy isononoate, t-amyl peroxy butylperoxyisopropyl carbonate, t-amyl peroxy 2- ethylhexyl carbonate The organic peroxide etc. of ester etc..They can be used only a kind, and also two or more kinds may be used.In addition, the method for above-mentioned (1) In, it is preferable to use taking the strong polymerization catalyst of hydrogen power by force, as such polymerization catalyst, it is preferable to use organic peroxide.It is poly- The dosage of catalyst is closed, such as relative to 100 mass parts of monomer component is preferably 0.01-1 mass parts.
About each plant demand of raw polymer (P1) and monomer component, relative to raw polymer (P1) and monomer component Total 100 mass parts, raw polymer (P1) is preferably 0.5 mass parts or more, more than more preferably 1 mass parts, further It is more than preferably 3 mass parts, it is additionally preferred to below the mass for 50, more preferably 30 below the mass, and further preferably 20 Below the mass.Relative to total 100 mass parts of raw polymer (P1) and monomer component, monomer component is preferably 50 mass Part or more, more than more preferably 70 mass parts, more than further preferably 80 mass parts, it is additionally preferred to below the mass for 99, More preferably 98 below the mass, and further preferably 97 below the mass.
The concentration of raw polymer (P1) in reaction solution, preferably 1 mass % or more, more preferably 3 mass % or more, Further preferably 5 mass % or more, it is additionally preferred to be 50 mass % hereinafter, more preferably 30 mass % are hereinafter, further excellent It is selected as 20 mass % or less.The concentration of monomer component in reaction solution, preferably 5 mass % or more, more preferably 10 mass % More than, it is additionally preferred to it is 80 mass % hereinafter, more preferably 70 mass % or less.Solvent strength in reaction solution, preferably 10 Quality % or more, more preferably 20 mass % or more, it is additionally preferred to be 97 mass % hereinafter, more preferably 95 mass % hereinafter, Further preferably 90 mass % are hereinafter, be still more preferably 80 mass % or less.In polymerization reaction, it can also be properly added Raw polymer (P1), monomer component, polymerization catalyst, reaction dissolvent etc..
Polymerization reaction preferably carries out under the atmosphere of the inert gas of nitrogen etc. or air-flow.In order to reduce residual monomers, make Azo compound and peroxide can be used together for polymerization initiator.Reaction temperature is preferably 50 DEG C -200 DEG C.Reaction time Carry out degree, the generation degree of gel compound of copolyreaction, one side appropriate adjustment, such as preferred progress 1 can be observed on one side - 20 hours hours.
By above-mentioned polymerization process, obtains the polymer chain containing the unit from (methyl) acrylic monomer and gather Close the copolymer of object chain (A) bonding.In polymerization process, as monomer component, (methyl) acrylic monomer is used and in ring In the case where monomer (for example, maleic anhydride or maleimide) in structure with polymeric double bond, there is (methyl) The polymer chain (B) of acrylic acid units and ring structure unit (maleic anhydride structure, maleimide structure) and polymer chain (A) The copolymer (P) of bonding.
On the other hand, the ring structure unit as polymer chain (B) is obtained with lactone ring structure, glutaric anhydride structure Or in the case where the copolymer (P) of glutarimide structure, ring structure formation process is carried out preferably after polymerization process.Ring knot It is configured in process, forms ring knot on the main chain of the polymer chain with (methyl) acrylic acid units formed in polymerization process Structure.Specifically, make adjacent (methyl) propylene of the polymer chain with (methyl) acrylic acid units formed in polymerization process Condensation reaction is carried out between the substituent group of acid unit, forms ring structure on the main chain of polymer chain.Condensation reaction includes esterification Reaction, acid anhydrides reaction, amidation process, imidization reaction etc..For example, can be by by adjacent (methyl) acrylic acid list 2 carboxylic acid group acid anhydrides of member form glutaric anhydride structure, can also form glutarimide structure by imidizate. In addition, the feelings of the group of a hydrogen atom containing protic with hydroxyl or amino etc. in adjacent (methyl) acrylic acid units Under condition, can by will should (methyl) acrylic acid units the hydrogen atom containing protic group and another (methyl) acrylic acid list The carboxylic acid group condensation of member, forms lactone ring structure.
In ring structure formation process, the condensation reaction of adjacent (methyl) acrylic acid units, preferably in catalyst (cyclisation Catalyst) in the presence of carry out.As cyclization catalyst, can be used selected from least one of acid, alkali and their salt. Acid, alkali and their salt can be organic matter, or inorganic matter, there is no particular limitation.Wherein, as cyclization Catalyst, it is preferable to use organic phosphorus compound.By using organic phosphorus compound as cyclization catalyst, can efficiently into Row condensation reaction, and the coloring for the copolymer (P) that can be reduced.
As the organic phosphine compound that can be used as cyclization catalyst and use, for example, alkyl (aryl) phosphonous acid can be enumerated And their monoesters or diester；Dialkyl group (aryl) phosphinic acids and their ester；Alkyl (aryl) phosphonic acids and they Monoesters or diester；Alkyl (aryl) ortho phosphorous acid and their ester；Monophosphite, diester or three esters；Methyl orthophosphoric acid, phosphoric acid Ethyl ester, phosphoric acid 2- ethylhexyl, octyl phosphate, isodecyl ester, lauryl phosphate, octadecyl phosphate, iso stearyl phosphorus Acid esters, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di(2-ethylhexyl)phosphate -2- ethylhexyl, phosphoric acid diisodecyl ester, di(2-ethylhexyl)phosphate laurel Ester, di(2-ethylhexyl)phosphate stearyl, di(2-ethylhexyl)phosphate iso stearyl ester, diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tricresyl phosphate are different Phosphate monoester, the diester of last of the ten Heavenly stems ester, tricresyl phosphate lauryl, tricresyl phosphate stearyl, tricresyl phosphate iso stearyl ester, triphenyl phosphate etc. Or three ester；Mono-, two- or three-alkyl (aryl) phosphine；Alkyl (aryl) halogen phosphine；Aoxidize mono-, two- or three-alkyl (aryl) phosphine； Tetraalkylphosphonium halide (aryl) Phosphonium etc..They can be used only a kind, and also two or more kinds may be used.In them, from catalyst activity Height, from the point of view of coloring is low, particularly preferably phosphate monoester or diester.The dosage of cyclization catalyst, for example, relative to polymerization process Obtained 00 mass parts of copolymer 1 are preferably 0.001-1 mass parts.
Reaction temperature in ring structure formation process, preferably 50 DEG C -300 DEG C.Reaction time can observe condensation on one side Carry out degree one side appropriate adjustment of reaction, such as preferred progress -6 hours 5 minutes.
By carrying out such as above-mentioned polymerization process or polymerization process and ring structure formation process, obtain containing copolymer (P) resin solution.The resin solution obtained in this way preferably removes foreign matter and being filtered with filter.Thus, copolymer (P) preparation method is filtered it is also preferable to include the resin solution for obtaining polymerization process or ring structure formation process Process (filter progress).By being filtered process, the foreign matter amount in copolymer (P) can be reduced.Therefore, by copolymer (P) The case where raw material as optical thin film etc., is easy to get concave-convex surface and defect is few, the transparency is high optical thin film.In addition, In the present invention, the yield of gel compound is suppressed to reduced levels in the polymerization process due to that can make copolymer (P), filtering The burden of filter is reduced in process, can continuously be filtered for a long time.Therefore, foreign matter amount can be obtained with high productivity few Copolymer (P).Filter progress followed by can continuously be implemented in polymerization process or ring structure formation process.
As filter used in filtering, known filter can be used, be not particularly limited, such as can To use leaf dish filter, candle filter, packaging disc filter, cylinder type filter etc..Wherein, preferably effectively filtering Area big leaf dish filter or candle filter.
The filtering accuracy (aperture) of filter, typically such as 15 μm or less.In addition, copolymer (P) is used for light In the case where the optical material for learning film etc., from the viewpoint of reducing its optical defect, filtering accuracy be preferably 10 μm with Under, more preferably 5 μm or less.There is no particular limitation for the lower limit of filtering accuracy, such as 0.2 μm or more.
In filter progress, it can directly filter polymerization process or what ring structure formation process obtained contains copolymer (P) resin solution can also be diluted with solvent or disperse to filter in a solvent.It, can be by it when copolymer (P) is solid It melts and is filtered with sintered filter etc., can also dissolve or disperse to filter in a solvent.Filtering can carry out under heating, In addition it can carry out under elevated pressure.
By resin solution be supplied to filter filtering when solution temperature, can be appropriate according to boiling point of polymer solvent etc. Setting, for example, preferably polymer solvent boiling point hereinafter, -10 DEG C of boiling point or less of more preferably polymer solvent.On the other hand, it supplies Be given to the resin solution of filter filtering temperature it is too low when, the viscosity of resin solution increases, and can increase for gear pump etc. Device load, be supplied to filter filtering resin solution temperature, preferably 50 DEG C or more, more preferably 80 DEG C with On.
The viscosity of the resin solution of filter filtering, at 85 DEG C, preferably 100Pas are supplied to hereinafter, more preferably 80Pas or less.Be supplied to filter filtering resin solution viscosity it is excessively high when, filter filter when crushing increase, mistake The processing capacity of filter filtering caused by filter unit is damaged, viscosity rises may be decreased.The pressure loss in filter filtering, Preferably 2.5MPa is hereinafter, more preferably in the range of 0.5MPa-2.0MPa, further preferably in the model of 0.5MPa-1.5MPa In enclosing.
(2. resin combination)
The present invention also provides contain the copolymer (P) with above explained polymer chain (A) and polymer chain (B) Resin combination.Resin combination of the invention not only has the excellent transparency, mechanical strength (example in well balanced mode Such as, impact strength etc.), heat resistance, and prepare when gel compound generation it is few.Hereinafter, resin combination of the invention is claimed For " resin combination (Q) ".
Resin combination (Q) can be used as resin component containing copolymer (P), can also contain other polymers as tree Rouge ingredient.In the case that resin combination (Q) contains other polymers, as other polymers, it is preferable to use (methyl) acrylic acid Quasi polymer, thus the homogenieity of resin combination (Q) improves, and is easy to improve the transparent and heat-resisting of resin combination (Q) Property.
(methyl) acrylic polymer can be to come from (methyl) propylene with what is illustrated in above-mentioned polymer chain (B) The polymer of the unit of acrylic monomer, it is preferable that come from (methyl) acrylate with what is illustrated in above-mentioned polymer chain (B) Unit.(methyl) acrylic polymer also can have the unsaturated from other of the middle explanation of above-mentioned polymer chain (B) The unit of monomer.From the viewpoint of intermiscibility of the raising with the copolymer (P) in resin combination (Q), (methyl) acrylic acid Quasi polymer more preferably has the unit from (methyl) acrylic monomer contained in the polymer chain (B) of copolymer (P).
(methyl) acrylic polymer is preferably the polymer with ring structure, has ring structure more preferably in main chain Polymer.Resin combination (Q) is by can be improved containing (methyl) acrylic polymer in main chain with ring structure The heat resistance of resin combination (Q).The ring structure of main chain as (methyl) acrylic polymer, can preferably enumerate lactonic ring Structure, cyclic imide structure (for example, maleimide structure, glutarimide structure etc.), cyclic acid anhydride structure (for example, Maleic anhydride structure, glutaric anhydride structure etc.) etc., the details of these ring structures is referring to the above-mentioned ring about polymer chain (B) The explanation of structure.Wherein, preferably there is the polymer chain (B) with copolymer (P) in the main chain of (methyl) acrylic polymer The identical ring structure of the ring structure having.
(methyl) acrylic acid that (methyl) acrylic polymer, the preferably polymer chain (B) with copolymer (P) have Unit, and the ring structure unit having with polymer chain (B).Resin combination (Q) contains such (methyl) acrylic acid It when quasi polymer, is improved with the intermiscibility of copolymer (P), is easy to improve the transparency and heat resistance of resin combination (Q), in addition The modulation of resin combination (Q) also becomes easy.
In the 100 mass % of solid component of resin combination (Q), the content ratio of copolymer (P), preferably 1 mass % More than, more preferably 2 mass % or more, further preferably 3 mass % or more are still more preferably 5 mass % or more, by This is easy the mechanical strength for improving resin combination (Q).The upper limit of the content ratio of copolymer (P) in resin combination (Q) There is no particular limitation, and resin combination (Q) can be only made of copolymer (P), in resin combination (Q), copolymer (P) Content ratio can be 90 mass % or less, or 70 mass % or less, 50 mass % or less, 40 mass % or less or 30 mass % or less.In the case that resin combination (Q) contains solvent, the solid content of resin combination (Q) refers to removing The amount of the resin combination (Q) of solvent.
In the 100 mass % of solid component of resin combination (Q), the content ratio of the polymer chain (A) of copolymer (P), Preferably 0.5 mass % or more, more preferably 1 mass % or more, further preferably 3 mass % or more, it is additionally preferred to be 50 Quality % hereinafter, more preferably 30 mass % hereinafter, further preferably 20 mass % or less.It is poly- in resin combination (Q) When the content ratio for closing object chain (A) is 0.5 mass % or more, it is easy to improve the mechanical strength of resin combination (Q).Resin combination When the content ratio of polymer chain (A) in object (Q) is 50 mass % or less, it is easy to improve the transparency of resin combination (Q) And heat resistance.The content ratio of polymer chain (A) can for example be used1H-NMR is acquired.
In the case that resin combination (Q) contains (methyl) acrylic polymer, the solid component of resin combination (Q) In 100 mass %, the content of (methyl) acrylic polymer, preferably 1 mass % or more, more preferably 20 mass % with On, further preferably 30 mass % or more, it is additionally preferred to be 99 mass % hereinafter, more preferably 95 mass % are hereinafter, into one Step is preferably 90 mass % or less.
In the 100 mass % of solid component of resin combination (Q), copolymer (P) and (methyl) acrylic polymer Total content ratio, preferably 50 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % with On, it is still more preferably 90 mass % or more.Copolymer (P) and (methyl) acrylic in resin combination (Q) There is no particular limitation for the upper limit of the content ratio of object, and resin combination (Q) can be substantially only by copolymer (P) and (methyl) Acrylic polymer is constituted, such as in the 100 mass % of solid component of resin combination (Q), copolymer (P) and (methyl) third Total content ratio of olefin(e) acid quasi polymer can be 99 mass % or more.
Resin combination (Q) can be containing the polymer other than (methyl) acrylic polymer, as such polymerization Object, such as the olefin polymer of polyethylene, polypropylene, ethylene-propylene polymer, poly- (4-methyl-1-pentene) etc. can be enumerated； The quasi polymer containing halogen of vinyl chloride, vinyl chloride resin etc.；Polystyrene, styrene-methylmethacrylate copolymer, benzene second The styrenic polymer of alkene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer etc.；Polymer poly terephthaldehyde The polyester of sour glycol ester, polybutylene terephthalate (PBT), polyethylene naphthalate etc.；Nylon 6, nylon66 fiber, nylon 610 equal polyamide；Polyacetals；Polycarbonate；Polyphenylene oxide；Polyphenylene sulfide；Polyether-ether-ketone；Polysulfones；Polyether sulfone；Polyether sulfone；It is poly- Amide imide；The rubber of polybutadiene rubber, the ABS resin of (methyl) acrylic rubber or ASA resin etc. is blended Matter polymer etc..
Resin combination (Q) can contain various additives within the scope of the effect of the invention.As addition Agent, such as the antioxidant of Hinered phenols, Phosphorus, sulphur class etc. can be enumerated；Resistance to light stabilizer, weathering stabilizers, heat stabilizer etc. Stabilizer；The supporting material of glass fibre, carbon fibre etc.；Ultraviolet absorbing agent；Near infrared ray absorption；Three (dibromos third Base) phosphate, triallyl phosphate, antimony oxide etc. fire retardant；Phase difference enhancer, phase difference depressant, phase difference are stablized The adjusting offset agent of agent etc.；Containing anionic, cationic, non-ionic surfactant antistatic agent；It is inorganic The colorant of pigment, organic pigment, dyestuff etc.；Organic filler and inorganic filler；Modifier；It organic filler and inorganic fills out Fill agent etc..The content ratio of each additive in resin combination (Q), preferably in 0-5 mass %, more preferably 0-2 mass %'s In range.
As ultraviolet absorbing agent, benzophenone compound, salicylic acid ester type compound, benzoates can be enumerated Object, triazole class compounds and compound in triazine class etc. are closed, well known ultraviolet absorbing agent can be used.As benzophenone Compound, can enumerate 2,4-DihydroxyBenzophenone, 4- n-octyloxy -2- dihydroxy benaophenonel, 2,2 '-dihydroxy -4, and 4 '-two Methoxy benzophenone etc..As salicylic acid ester type compound, can enumerate to tert-butylphenyl salicylate acid etc..As benzoic ether Class compound can enumerate 2,4- di-tert-butyl-phenyl -3 ', 5 '-di-t-butyls -4 '-hydroxybenzoate etc..As triazole type Object is closed, 2,2 '-di-2-ethylhexylphosphine oxides [4- (1,1,3,3- tetramethyl butyl) -6- (2H- benzotriazole -2- base) phenol], 2- can be enumerated (3,5- di-t-butyl -2- hydroxy phenyl) -5- chlorobenzotriazole, 2- (2H- benzotriazole -2- base)-paracresol, 2- (2H- benzo Triazole-2- base) bis- (1- methyl-1-phenethyl) phenol of-4,6-, 2 benzotriazole-2- base-4,6- DI-tert-butylphenol compounds, 2- [5- Chlorine (2H)-benzotriazole -2- base] -4- methyl-6-tert-butylphenol, 2- (2H- benzotriazole -2- base) -4,6- tert-butyl benzene Phenol, 2- (2H- benzotriazole -2- base) -4- (1,1,3,3- tetramethyl butyl) phenol etc..As compound in triazine class, can enumerate Mono- (the hydroxy phenyl) -1,3,5- triaizine compounds of 2- or bis- (the hydroxy phenyl) -1,3,5- triaizine compounds of 2,4-, 2,4,6- tri- (hydroxy phenyl) -1,3,5- triaizine compounds etc..As commercially available ultraviolet absorbing agent, such as can enumerate ultraviolet as triazines " TINUVIN (registered trademark) 1577 ", " TINUVIN (registered trademark) 460 ", " TINUVIN (registered trademark) of light absorbers 477 " (BASF Japan society systems), " ADK STAB (registered trademark) LA-F70 " (ADEKA society system) are inhaled as triazole type ultraviolet light Receive " ADK STAB (registered trademark) LA-31 " (the ADEKA society system) etc. of agent.Ultraviolet absorbing agent can be used only a kind, can also be with It is used in combination of two or more.
As antioxidant, the compound with radical-scavenging or peroxide decomposition function can be used, Well known antioxidant can be used.As antioxidant, such as can to enumerate hindered phenol anti-oxidants, hindered amines anti-oxidant Agent, phosphorus antioxidants, sulphur class antioxidant, benzotriazole antioxidant, benzophenone antioxidant, azanol class antioxygen Agent, salicylic acid esters antioxidant and triazines antioxidant etc..In these antioxidants, as can preferably enumerate by Hinder phenol antioxidant, hindered amines antioxidant, phosphorus antioxidants, sulphur class antioxidant.Hindered phenol can more preferably be enumerated Class antioxidant, hindered amines antioxidant, phosphorus antioxidants.Antioxidant can be used only a kind, also can be used together 2 kinds More than.
As hindered phenol anti-oxidants, 2,4- bis- [(lauryl is thio) methyl]-o-cresols, 1 can be enumerated, 3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl), 1,3,5- tri- (4- tert-butyl -3- hydroxyl -2,6- dimethyl benzyl) etc..
As hindered amines antioxidant, bis- (2,2,6,6- tetramethyl -4- piperidyl) sebacates, double can be used (N- methyl -2,2,6,6- tetramethyl -4- piperidyl) sebacate, N, bis- (the 2,2,6,6- tetramethyl -4- piperidyls) -1 of N ' -, 6- hexamethylene diamine, 2- methyl -2- (2,2,6,6- tetramethyl -4- piperidyl) amino-N- (2,2,6,6- tetramethyl -4- piperazine Piperidinyl) propionamide, four (2,2,6,6- tetramethyl -4- piperidyl) (1,2,3,4- butane tetracarboxylic acid esters, poly- [(6- (1,1,3,3- Tetramethyl butyl) imino group -1,3,5- triazine -2,4- diyl) ((2,2,6,6- tetramethyl -4- piperidyl) imino group) hexamethyl ((2,2,6,6- tetramethyl -4- piperidyl) imido)] etc..
As phosphorus antioxidants, three (isodecyl) phosphite esters, three (three decyls) phosphite esters, phenyl also can be used Iso-octyl phosphite ester, phenyl isodecyl phosphite, phenyl two (three decyls) phosphite ester, diphenyl iso-octyl phosphorous acid Ester, diphenyl isodecyl phosphite, three decyl phosphite ester of diphenyl, triphenyl phosphite, three (nonyl phenyl) phosphorous Acid esters, 4,4 ' diphenol alkyl phosphites, trisnonylphenyl phosphite, three (dinonylphenyl) phosphite esters, The compound etc. of other oligomerics and polymer-type with phosphite ester structure.
As sulphur class antioxidant, can enumerate 2,2- it is thio-bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) of divinyl Propionic ester], bis- [(octylsulfo) the methyl]-o-cresols of 2,4-, bis- [(lauryl is thio) methyl]-o-cresols of 2,4- etc..It can also To use the compound etc. of other oligomerics and polymer-type with sulfide based structural.
The weight average molecular weight of resin combination (Q), preferably 0.2 ten thousand or more, more preferably 0.5 ten thousand or more, it is further excellent 30,000 or more are selected as, is still more preferably 50,000 or more, particularly preferably 70,000 or more, it is additionally preferred to for 1,000,000 hereinafter, more excellent 500,000 are selected as hereinafter, further preferably 300,000 hereinafter, still more preferably for 200,000 or less.The weight of resin combination (Q) is equal Molecular weight is in such range, while the molding processibility of resin combination (Q) improves, is also easy to improve obtained molding The intensity of product.The weight average molecular weight of resin combination (Q) refers to and measures resin combination (Q) by gel permeation chromatography With polystyrene convert value, resin combination (Q) contain copolymer (P) and (methyl) acrylic polymer the case where Under, the weight average molecular weight of resin combination (Q) is the overall weight average molecular weight of these multiple polymers.
The weight average molecular weight of resin combination (Q), the preferably weight average molecular weight of the polymer chain (A) of copolymer (P) 1.1 times or more, more preferably 1.2 times or more, further preferably 1.3 times or more, it is additionally preferred to be 20 times hereinafter, more preferably 12 times hereinafter, further preferably 10 times hereinafter, still more preferably for 7 times hereinafter, particularly preferably 5 times or less.As a result, may be used Easily to assign each characteristic of the transparency, mechanical strength, heat resistance to resin combination (Q) in well balanced mode.
The refractive index of resin combination (Q) is preferably the value with the refractive index close of the polymer chain (A) of copolymer (P), Thus it is easy to ensure that the transparency of resin combination (Q).Specifically, the refractive index of resin combination (Q) and copolymer (P's) is poly- The specific refractivity for closing object chain (A) is preferably smaller than 0.1, more preferably 0.05 hereinafter, further preferably 0.02 or less.From same From the viewpoint of, the refractive index of resin combination (Q) is preferably the value with the refractive index close of copolymer (P), specifically, resin The refractive index of composition (Q) and the specific refractivity of copolymer (P) are preferably smaller than 0.1, more preferably 0.05 hereinafter, further excellent It is selected as 0.02 or less.
Total light transmittance when resin combination (Q) is made 160 μm of thickness of non-extension film is preferably 70% or more, more excellent It is selected as 80% or more, further preferably 90% or more.In addition, mist degree be preferably 5.0% hereinafter, more preferably 3.0% hereinafter, Further preferably 1.0% or less.About internal haze, the internal haze that every 100 μ m thick when non-extension film is made is preferred For 5.0% hereinafter, more preferably 3.0% hereinafter, further preferably 2.0% hereinafter, be still more preferably 1.0% or less.
Resin combination (Q) shows island structure when 160 μm of thickness of non-extension film is made, the island ruler in the structure It is very little preferably 500nm hereinafter, more preferably 400nm hereinafter, further preferably 350nm or less.As a result, by resin combination (Q) when forming film, it is easy to get the high film of the transparency.There is no particular limitation for the lower limit value of the island size of island structure, It such as can be 10nm or more, or 50nm or more.By the island structure for the non-extension film that resin combination (Q) is formed Observation pass through scanning electron microscope (STEM) and carry out, the method that specific measuring method is recorded referring to embodiment.
Resin combination (Q) preferably has glass transition temperature at 100 DEG C or more and less than 100 DEG C respectively.In addition, 100 DEG C or more of glass transition temperature is known as " glass transition temperature of high temperature side ", the vitrifying less than 100 DEG C is turned Temperature is known as " glass transition temperature of low temperature side ".The vitrifying that resin combination (Q) can have multiple high temperature sides turns Temperature, it is possible to have the glass transition temperature of multiple low temperature sides.There is the glass of high temperature side by resin combination (Q) Whens changing transition temperature, the heat resistance raising of resin combination (Q), and resin combination (Q) being shaped to film etc., even if Also do not soften under high temperature, molding processibility can be improved.There is the glass transition temperature of low temperature side by resin combination (Q) Degree, can be improved the mechanical strength and impact resistance of resin combination (Q).The vitrifying of the high temperature side of resin combination (Q) turns Temperature, preferably 113 DEG C or more, more preferably 116 DEG C or more, further preferably 120 DEG C or more, in addition from raising resin From the viewpoint of the processability of composition (Q), preferably smaller than 300 DEG C, more preferably less than 200 DEG C are further preferably no larger than 180 ℃.The glass transition temperature of the low temperature side of resin combination (Q), preferably -100 DEG C or more, more preferably -90 DEG C or more, Further preferably -80 DEG C or more, it is additionally preferred to less than 50 DEG C, more preferably less than 30 DEG C, be further preferably no larger than 10 DEG C.
Insoluble component of the resin combination (Q) in chloroform be preferably 10 mass % hereinafter, more preferably 8 mass % with Under, further preferably 5 mass % or less.The copolymer (P) contained in resin combination (Q) is handed over due to containing substantially no It is coupled structure, can also inhibits even if containing in a small amount of level, therefore the insoluble in chloroform of resin combination (Q) can be reduced The ratio of ingredient.Therefore, the foreign matter amount contained by resin combination (Q) is few, such as forms optical thin film by resin combination (Q) When, it is easy to get concave-convex surface and defect is few, the high film of the transparency.In addition, when removing foreign matter from resin combination, for different The burden that object removing filter applies is reduced, and preparation efficiency improves.
In contrast, for example, the disclosed elasticity with core-shell structure of Japanese Unexamined Patent Publication 2008-242421 bulletin is organic micro- In grain etc., since the organic fine particles are the graft copolymer with cross-linked structure, chloroform is not dissolved in.Therefore, there will be such friendship Be coupled structure copolymer be used as pursue high-quality optical thin film raw material when, can become film foreign matter and defect the reason of, The bad order of concave-convex surface, mist degree etc. occurs when film is extended, it is thus not preferred.In addition, from tree before film forming When removing foreign matter in oil/fat composition, the burden that organic fine particles apply foreign matter removing filter is high, will lead to productivity drop It is low.
Insoluble component of the resin combination in chloroform, is acquired by the method recorded in embodiment.Specifically, by resin Composition 1g is added in chloroform 20g, it is filtered with Teflon (registered trademark) the film filter in 0.5 μm of aperture, passes through survey The amount for determining the insoluble component of membrane filter trapping, acquires the ratio of insoluble component of the resin combination in chloroform.
The gas release that resin combination (Q) generates when heating 20 minutes at 290 DEG C is preferably 20/g hereinafter, more preferably For 10/g hereinafter, further preferably 5/g or less.Resin combination (Q) is carried out to formed body when hot briquetting as a result, The appearance of (such as film etc.) is good.The measurement of gas release is carried out using melt index apparatus specified in JIS K 7210, will be through The resin combination of drying process is filled in the machine barrel of melt index, is kept squeezing out after twenty minutes at 290 DEG C into strips, meter The generation number of existing bubble between the top graticule and lower part graticule of the item that number obtains, with of the bubble of every 1g resin combination Number is indicated.
Resin combination (Q) is based on the melt viscosity under 270 DEG C, 100 (/ seconds) of JIS K 7199 (1999) measurement, Preferably 50Pas or more, more preferably 100Pas or more, it is additionally preferred to be 5000Pas hereinafter, more preferably 1000Pas or less.The melt viscosity of resin combination (Q) is in such range, the molding processibility of resin combination (Q) It improves, and does not allow to be also easy to produce flake and die parting line etc. on formed body, the appearance of formed body is good.
Energy of rupture when resin combination (Q) is made 160 μm of thickness of non-extension film is preferably 20mJ or more, more preferably For 24mJ or more, further preferably 28mJ or more.When forming film by resin combination (Q) as a result, it is easy to get mechanical strong Spend high film.Energy of rupture is acquired by the method recorded in embodiment.
Trousers shape tearing strength when resin combination (Q) is made 40 μm of thickness of extension film is preferably 15mJ or more, more Preferably 18mJ or more, further preferably 22mJ or more.When forming film by resin combination (Q) as a result, it is easy to get and tears The high film of resistance to spalling.Trousers shape tearing strength is acquired by the method recorded in embodiment.
The folding strength of MIT folding strength test measurement when 40 μm of thickness of extension film is made in resin combination (Q) is tested Number is preferably 1000 times or more, more preferably 1200 times or more, further preferably 1350 times or more.As a result, by resin group When closing object (Q) formation film, it is easy to get the film for being difficult to rupture.Method of the MIT folding strength test by being recorded in embodiment It carries out.
There is no particular limitation for the preparation method of resin combination (Q), when polymerization generates copolymer (P), (methyl) propylene Acids polymers can also easily polymerize generation together.In the preparation method of above explained copolymer (P), copolymerization is generated While object (P), (methyl) acrylic polymer of the polymer chain (B) corresponding to copolymer (P) is also generated, at this moment, is led to It crosses and does not separate copolymer (P) and (methyl) acrylic polymer, it is available to contain copolymer (P) and (methyl) acrylic compounds The resin combination (Q) of polymer.In the preparation method of resin combination (Q) in this case, pass through copolymer (P) The polymerization process or polymerization process and ring structure formation process illustrated in preparation method, obtains copolymer (P) and main chain Upper (methyl) acrylic polymer with ring structure.
The preparation method of resin combination (Q) is not limited to above-mentioned method, copolymer (P) can also be separated, and and its Its mixed with polymers is as resin combination (Q).In addition, in the preparation method of above-mentioned copolymer (P), with copolymer (P1) Graft copolymerization after the completion of, can further add other monomers and carry out polymerization reactions to obtain resin combination (Q). Alternatively, the mixing of the copolymer (P) and (methyl) acrylic polymer obtained for the preparation method of above-mentioned copolymer (P) Other polymer (for example, other (methyl) acrylic polymers) can be further added as resin combination (Q) in object. In the case where other polymers are added and mix, mixing may be melted, in this case it is possible, for example, to use kneader With the general device of multiple screw extruder etc..
In the preparation method of resin combination (Q), can polymerization process or ring structure formation process followed by Carry out above explained filter progress.By being filtered process, the foreign matter amount in resin combination (Q) can be reduced, it can be with So that resin combination (Q) is suitable for pursuing the use of optical thin film of high-quality etc. on the way.The details of filter progress is referring to above-mentioned Copolymer (P) preparation method in filter progress explanation.
(processing and formings of 3. copolymers and resin combination)
Copolymer (P) and resin combination (Q), can be used with liquid, can also be used as solidfied material use.The feelings of the latter Under condition, by by copolymer (P) and resin combination (Q) heating melting, be shaped to arbitrary shape, formed body can be made. The shape of formed body can be suitably set depending on the application, such as can enumerate plate, sheet, granular, powdery, bulk, particles aggregate Body shape, spherical, ellipse spherical, lenticular, cubic, column, rodlike, cone-shaped, tubular, needle-shaped, fibrous, macaroni yarn Shape, Porous shape etc..The formed body of copolymer (P) and resin combination (Q), can be used ejection formation, extrusion molding, vacuum Molding, compression forming, blow molding etc., as shape in this case, such as preferably, particle diameter is 1 μm -1000 μm Powder, cylindric or spherical etc. the particle or their mixture that long axis is 1mm-10mm or so.
Copolymer (P) and resin combination (Q) can also be shaped to film.As the method for film forming, can be used Solution casting method (solution casting method), extrusion by melting, rolling process, method well known to compression forming methods etc..In them, preferably Solution casting method, extrusion by melting.
As the solvent that solution casting method uses, such as the chlorine system aliphatic hydrocarbon that chloroform, methylene chloride can be enumerated etc.；First Benzene, dimethylbenzene, benzene etc. it is aromatic hydrocarbon；The alcohols of methanol, ethyl alcohol, isopropanol, n-butanol, 2- butanol etc.；Methyl cellosolve, The dioxane of ethyl cellosolve, butyl cellosolve etc.；The ethers of diethyl ether, dioxanes, tetrahydrofuran etc.；Acetone, cyclohexanone Deng ketone: the esters of ethyl acetate, propyl acetate, butyl acetate etc.；Dimethylformamide；Dimethyl sulfoxide etc..They can To be used only a kind, also two or more kinds may be used.
As the device for carrying out solution casting method, such as drum-type casting machine, tape casting machine, spin coater can be enumerated Deng.
As extrusion by melting, T modulus method, plavini etc. can be enumerated.By film carry out melting extrusion molding when temperature (at Type temperature) be preferably 150 DEG C or more, more preferably 200 DEG C or more, it is additionally preferred to be 350 DEG C hereinafter, more preferably 300 DEG C with Under.
In T modulus method, it is wound on roller, is rolled up by the film for squeezing out the extruder for being equipped with T mould from front end The film being wound up on a roller.At this point, the temperature and speed batched by control, can apply extension on the extrusion direction of film (uniaxial extension).
It is preferable to use extruders for melting extrusion molding.Extruder has machine barrel, the screw rod being arranged in machine barrel, is preferably provided with Heating means.Extruder is according to the radical of screw rod, and there are the types of single axle extruding machine, biaxial extruder, multiple screw extruder etc., can To use any one extruder.Abundant plasticization and the good resin combination of kneaded state in order to obtain, extruder L/D value (L be extruder machine barrel length, D be machine barrel internal diameter) be preferably 10 or more, more preferably 15 or more, into one Step preferably 20 or more, it is additionally preferred to for 100 hereinafter, more preferably 80 hereinafter, further preferably 60 or less.L/D value is less than It, cannot be by resin combination fully plasticization, it may not be possible to obtain good kneaded state in the case where 10.L/D value is more than In the case where 100, excessively apply shearing fever to resin combination, the ingredient contained in resin combination is easy thermal decomposition.
The set temperature (heating temperature) of the machine barrel of extruder, preferably 200 DEG C or more, more preferably 250 DEG C or more, separately Outer preferably 350 DEG C hereinafter, more preferably 320 DEG C or less.When set temperature is less than 200 DEG C, the melt viscosity of resin combination Excessively high, the productivity of film may be decreased.In the case that set temperature is more than 350 DEG C, contain in resin combination at partial volume Easily thermal decomposition.
Extruder preferably has 1 or more Opening Ventilation portion.It, can be from Opening Ventilation by using such extruder Gas is decomposed in portion's sucking, to reduce the amount of the residual volatile ingredient of obtained film.It is decomposed to be sucked from Opening Ventilation portion Gas, for example, Opening Ventilation portion can be decompression state, pressure (absolute pressure of the degree of decompression as Opening Ventilation portion at this moment Power), preferably 1.3hPa or more, more preferably 13.3hPa or more, it is additionally preferred to be 931hPa hereinafter, more preferably 798hPa Below.In the case that the pressure in Opening Ventilation portion is higher than 931hPa, volatile ingredient or the polymerization by containing in resin combination The monomer component that the decomposition of object generates, is easy on the film remained in.On the other hand, the pressure in Opening Ventilation portion is kept It is industrial highly difficult lower than 1.3hPa.
When melting extrusion forms, the copolymer of molten condition (P) or resin combination (Q) are preferably used into polymer mistake Filter filtering, it is possible thereby to remove the foreign matter contained in copolymer (P) or resin combination (Q).As a result, by copolymer (P) or When resin combination (Q) forms optical thin film etc., optical defect in finally obtained optical thin film and in appearance can be reduced Defect amount.
The molding temperature of melting extrusion, such as preferably 200 DEG C or more, more preferably 250 DEG C or more, it is additionally preferred to be 350 DEG C hereinafter, more preferably 320 DEG C or less.When the molding temperature of melting extrusion is 200 DEG C or more, copolymer (P) and resin group The viscosity for closing object (Q) reduces, and can shorten the residence time in polymer filter.The molding temperature of melting extrusion is 350 DEG C or less when, such as film it is continuously shaped when, be difficult to be formed such as through-hole, flow pattern, flowing lines on film and lack It falls into, is easy to get the film of good appearance.
There is no particular limitation for the structure of polymer filter.For example, it is preferable to using more pieces of leaf dish types are equipped in shell The polymer filter of filter.The filter material of leaf dish type filter, can be used will be obtained from the sintering of metallic fiber nonwoven fabric Filter material, will be metal powder sintered obtained from filter material, by more pieces of metal meshes stacking filter material, by they combine mixed type filter material The filter material of any one type in.Wherein, it is preferable to use by filter material obtained from the sintering of metallic fiber nonwoven fabric.
There is no particular limitation for the filtering accuracy (aperture) of polymer filter.In view of as the foreign matter for removing object Size, filtering accuracy be usually 15 μm hereinafter, preferably 10 μm hereinafter, more preferably 5 μm or less.The lower limit of filtering accuracy does not have It is special to limit, it is contemplated that extend the residence time of copolymer (P) or resin combination (Q) in polymer filter, copolymerization The productivity of object (P) or resin combination (Q) heat deterioration or film reduces, and preferably 1 μm or more.
There is no particular limitation for the shape of polymer filter.As the type of polymer filter, such as tool can be enumerated Have a multiple resin communication ports, the interior flow pattern of flow path in center-pole with resin, section on multiple vertex or face with leaf dish The inner circumferential face contact of formula filter, center-pole outside have outer flow pattern of flow path of resin etc..Wherein, due to the stop place of resin Point is less, it is preferable to use the polymer filter of outer flow pattern.
The residence time of copolymer (P) or resin combination (Q) in polymer filter, preferably 20 minutes with Under, more preferably 10 minutes hereinafter, further preferably 5 minutes or less.In melt filteration, the entrance pressure of polymer filter The outlet pressure of power and the filter, such as respectively 3MPa or more 15MPa or less and 0.3MPa or more 10MPa.It melted The pressure loss (inlet pressure of polymer filter and the pressure difference of outlet pressure) in filter, preferably 1MPa or more 15MPa Below.The pressure loss is in 1MPa situation below, and copolymer (P) and resin combination (Q) are easy to deviate and pass through polymer mistake The flow path of filter.The reason of quality for the film that the deviation of flow path is reduces.In the case that the pressure loss is more than 15MPa, Polymer filter is easy breakage.
When copolymer (P) or resin combination (Q) are carried out melt filteration, preferably by extruder and polymer mistake Gear pump is set between filter, stabilizes the pressure in polymer filter.By the melt filteration of polymer filter, remove Other than in melting extrusion molding, it can implement on arbitrary opportunity.
By extrusion by melting by film forming in the case where, can also extend and extension film is made.It, can be with by extending Further increase the mechanical strength of film.As the extension method for obtaining extension film, known prolong can be applicable in Stretching method.Such as the uniaxial extension that unsupported width uniaxial extension, fixed width uniaxial extension can be enumerated etc.；Gradually twin shaft extend, The twin shaft of twin shaft extension simultaneously etc. extends；It is formed and when film extends in its a piece of or two sides then shrink film The layered product is carried out heating and extends the convergent force that processing assigns film extending direction and vertical direction, distinguished by layered product In the extension etc. for the birefringent film that the molecular group that extending direction and thickness direction are orientated mixes.From the resistance to of raising film , it is preferable to use twin shaft extends from the viewpoint of the mechanical strength of folding endurance etc..In turn, from raising relative to arbitrary vertical in film surface , it is preferable to use twin shaft extends simultaneously from the viewpoint of the mechanical strength of the straight folding resistance in two directions etc..As appointing in face Two vertical directions of meaning, such as side vertical with slow axis in direction and film surface parallel with slow axis in film surface can be enumerated To.In addition, the extension condition of extension ratio, elongating temperature, extension speed etc., suitable according to desired mechanical strength and phase difference value When setting, there is no particular limitation.
As extension apparatus, such as roll-type elongator, expanding type elongator can be enumerated, as small test extension apparatus Cupping machine, uniaxial extension machine, gradually twin shaft elongator, simultaneously twin shaft elongator etc., can be used in these devices Any one.
As elongating temperature, preferably near the maximum glass transition temperature of copolymer (P) or resin combination (Q) It carries out.And specifically, it is preferable in the range of+50 DEG C of temperature of -30 DEG C~maximum glass transition of maximum glass transition temperature into Row, more preferably carries out in the range of+45 DEG C of temperature of -20 DEG C~maximum glass transition of maximum glass transition temperature, into one Step preferably carries out in the range of+40 DEG C of temperature of -10 DEG C~maximum glass transition of maximum glass transition temperature.Than highest glass When -30 DEG C of glass transition temperature is lower, it may not be possible to obtain sufficient extension ratio.Than+50 DEG C of maximum glass transition temperature When higher, cause the flowing (flow) of resin and be difficult to steadily be extended.
The extension ratio defined with area ratio, in the range of preferably 1.1-30 times, more preferably 1.2-20 times of range It is interior, in the range of further preferably 1.3-10 times.Extension in the case where extending to some direction, relative to a direction Multiplying power, in the range of preferably 1.05-10 times, in the range of more preferably 1.1-7 times, further preferably 1.2-5 times of model In enclosing.When extension ratio being set in such range, it is easier to obtain mechanical strength raising of film etc. along with extension Effect.
As extension speed (direction), preferably 10-20, in the range of 000%/minute, more preferably 100-10, In the range of 000%/minute.When lower than 10%/minute, sufficient extension ratio needs to spend the time in order to obtain, there is preparation The trend of increased costs.Higher than 20, when 000%/minute, the rupture etc. of extension film may cause.
In the case that extension film is suitable for optical thin film, in order to which the optical characteristics and machinery of stable optical film are special Property, after preferably extending over, implement heat treatment (annealing) as needed.
(4. optical thin film)
The film formed by copolymer (P) or resin combination (Q) can be suitable as optically thin since the transparency is good Film.The optical thin film obtained in this way, mechanical strength and heat resistance are good.Optical thin film can be extension film, or Non- extension film.As optical thin film, for example, can enumerate optics protective film (specifically, various CDs (VD, CD, DVD, MD, LD etc.) substrate protective film), be polarized used in the polarizer that has of the image display device of liquid crystal display etc. Device protective film, compensation film for angular field of view, optical diffusion film, reflectance coating, antireflection film, antiglare film, brightness enhancement film, touch screen are conductive Film, phase difference film etc..
The thickness of optical thin film, from the viewpoint of improving optically thin film strength, preferably 5 μm or more, more preferably 15 μm or more, further preferably 20 μm or more.On the other hand, from the viewpoint of the slimming of optical thin film, optical thin film Thickness be preferably 350 μm hereinafter, more preferably 200 μm hereinafter, further preferably 150 μm or less.The thickness of optical thin film The digimatic micrometer that three Feng She can be used for example is measured.
Optical thin film preferably has high transparency, such as total light transmittance is preferably 70% or more, and more preferably 80% or more, Further preferably 90% or more.
Optical thin film, from improve the transparency from the viewpoint of, mist degree be preferably 5.0% hereinafter, more preferably 3.0% with Under, further preferably 1.0% or less.In addition internal haze be preferably 5.0% hereinafter, more preferably 3.0% hereinafter, further Preferably 2.0% hereinafter, be still more preferably 1.0% or less.
Preferably, optical thin film relative to phase difference Re in the face of the light of wavelength 589nm be 0nm or more 1000nm hereinafter, The phase difference Rth of thickness direction relative to the light is the above 1000nm or less of -1000nm.It is highly preferred that Re is 0nm or more 100nm is hereinafter, Rth is the above 100nm or less of -100nm；It is further preferred that Re be 0nm or more 50nm hereinafter, Rth be- 30nm or more 30nm or less；It is particularly preferred that Re is 0nm or more 10nm hereinafter, Rth is the above 10nm or less of -10nm.It shows The optical thin film of the phase difference Rth of phase difference Re and thickness direction in such face has good viewing angle characteristic and contrast Characteristic, can be adapted for include liquid crystal display image display device.In addition, phase difference Re Re=(nx-ny) × d in face The phase difference Rth of definition, thickness direction is defined with Rth=d × { (nx+ny)/2-nz }, and nx indicates the slow-axis direction in film surface The refractive index in (the maximum direction of refractive index in film surface), ny indicate the refractive index in film surface with nx vertical direction, and nz indicates thin The refractive index of film thickness direction, d indicate the thickness (nm) of film.
Optical thin film, can be to be only made of the film that copolymer (P) or resin combination (Q) are formed, can also be Other optical materials composition is laminated on the film.By being laminated other optical materials, optical thin film optics can be further assigned Characteristic.As other optical materials, such as polarizer, polycarbonate system extension oriented film, cyclic polyolefin system can be enumerated and prolonged Stretch oriented film etc..
On the surface of optical thin film, as needed, various functional coatings can be set.As functional coating, such as Can enumerate antistatic layer, adhesive layer, following layer, easy following layer, anti-dazzle (free from glare) layer, photocatalyst layer etc. stain-proofing layer, Anti-reflection layer, hard conating, ultraviolet screener layer, heat ray shielding layer, electromagnetic wave shielding, gas-barrier layer etc..In addition, in light The surface for learning film, can be set the optical adjustment layer of the transmitance or reflectivity for appropriate adjustment incident ray.
Optical thin film of the invention is particularly preferably suitable for polarizer protective film.Polarizer protective film is in addition to containing copolymerization Other than object (P), it is not particularly limited.It, can be in the polarizer in the case that optical thin film is suitable for polarizer protective film On one side or optical thin film (polarizer protective film) is arranged in two sides, to constitute polarizer.Optical thin film (polarizer protective film), It is preferred that directly or using other interlayers ground connection being fixed on polaroid with solid or sticker.
There is no particular limitation for the type of the polarizer, such as obtained from can enumerating polyvinyl alcohol film being dyed and extended The polarizer；The polyene polarizer of the polyvinyl chloride handled through the polyvinyl alcohol of dehydration or dechlorinatedization hydrogen etc.；Using more The reflective polarizer of layer laminate or cholesteryl liquid crystal；The polarizer etc. being made of film crystalline film.As polarizer One example of structure, can enumerate: carry out after the dichroic substance of polyvinyl alcohol iodine or dichroic dye etc. is dyed single Axis extends to obtain the polarizer, and in the one side of the polarizer or the structure of two sides setting polarizer protective film (optical thin film).
By forming transparency conducting layer on surface, optical thin film can also be used as transparent conductive film use.As composition The material of transparency conducting layer can be used any materials used in the previous field as conductive material, can specifically enumerate: have Machine conductive compound；Organic conductive polymer；Indium oxide, tin oxide, zinc oxide, indium-tin-oxide (ITO), antimony-tin oxygen The metal oxide of compound (ATO), zinc-aluminum oxide, indium-zinc oxide (IZO) etc.；The metal of gold, silver, copper, palladium, aluminium etc..
It is aobvious can be preferably applied to image to optical thin film (for example, polarizer protective film, transparent conductive film) of the invention Showing device.As image display device, such as liquid crystal display device can be enumerated etc..Such as in the case where liquid crystal display device, figure As display unit may be constructed are as follows: the component with liquid crystal cells, polarizer, backlight etc., and there is optical thin film of the invention. As the image display device other than liquid crystal display device, for example, electroluminescent (EL) display panel can be enumerated, plasma is shown Panel (PDP), Field Emission Display (FED), QLED, miniature LED etc..
This application claims preferential based on Japanese patent application filed on January 13rd, 2017 the 2017-004468th The interests of power.The full content of the specification of Japanese patent application filed on January 13rd, 2017 the 2017-004468th, draws Enter into the present invention as reference.
Embodiment
Hereinafter, carrying out more specific description to the present invention by embodiment and comparative example, the present invention is not by following implementations The limitation of example and comparative example.In addition, below unless otherwise instructed, " part " expression " mass parts ", " % " expression " quality % ".
(1) analysis method
(1-1) weight average molecular weight (Mw) and number-average molecular weight (Mn)
Weight average molecular weight and number-average molecular weight use gel permeation chromatography (GPC), are acquired by polystyrene conversion. It measures the device used and determination condition is as follows.
The system of measurement: Tosoh society system, GPC system HLC-8220
Measure lateral column structure
Guard column: Tosoh society system, TSKguardcolumn SuperHZ-L
Splitter: Tosoh society system, TSKgel SuperHZM-M 2 series connection
Referring to lateral column structure
Reference column: Tosoh system, TSKgel SuperH-RC
Developing solvent: chloroform (and Wako Pure Chemical Industries system, superfine)
Solvent flux: 0.6mL/ minutes
Standard sample: TSK standard polystyren (Tosoh society system, PS- oligomer kit)
(1-2) glass transition temperature (Tg)
Glass transition temperature is acquired according to JIS K 7121 (2012).Specifically, (of science using differential scanning calorimeter System, Thermo plus EVO DSC-8230), under nitrogen atmosphere, the sample of about 10mg is warming up to 300 DEG C from room temperature and (is risen 20 DEG C/min of warm speed) and DSC curve is obtained, it is evaluated by the DSC curve by starting point method.Use Alpha-alumina as Reference.Discontented 40 DEG C of glass transition temperature uses differential scanning calorimeter (Netch society system, DSC-3500), in nitrogen atmosphere Under enclosing, sample is warming up to 60 DEG C (10 DEG C/min of heating rates) from -100 DEG C and obtains DSC curve, is passed through by the DSC curve Point method is evaluated.Use empty container as reference.
(1-3) monomer reaction rate
Monomer reaction rate (conversion ratio) uses gas chromatograph (society, Shimadzu Seisakusho Ltd. system, GC-2014), is polymerize by measurement Residual monomers amount in reaction solution and acquire.
(filtration test) is evaluated in (1-4) gelation
The gelation evaluation of resin combination is carried out by filter filtration test.Filter (GL is installed using front end Science society system, chromatodisk 13N, 0.45 μm of aperture) plastic injector filtering resin combination 0.1 mass % chloroform it is molten Liquid is evaluated as zero when can filter 2mL full dose, midway plugged filter, and solution is evaluated as when cannot filter 2mL ×.
(1-5) chloroform insoluble component
Resin combination 1g is added in chloroform 20g, by its with the membrane filter in 0.5 μm of aperture (ADVANTEC society system, T050A047A it) filters, and filtered membrane filter is dry.According to the mass M of the membrane filter before filtering0(g), it filters The mass M of the membrane filter after drying afterwards1(g), the chloroform insoluble component of resin combination is acquired as the following formula: chloroform not melt into Divide (quality %)=(M1-M0)/1×100。
(1-6) energy of rupture (falling ball impact test)
Energy of rupture acquires as follows.Firstly, resin combination is film-made by hot pressing, 160 μm of thickness of film is made and (does not prolong Stretch film).Next, implementing 10 tests for highly falling the ball of quality 0.0054kg from certain on the thin film, find out thin The average value of height (destruction height) when film is destroyed.Specifically, several stages are set height to, are successively made from low clearance When ball is fallen, the height of film breaks is found out, is repeated 10 times the height for acquiring 10 film breaks, finds out its average value work For destruction height.Whether film is destroyed, and after to film falling sphere, deformation whether is observed on the visual confirmation film and is sentenced It is disconnected.In the case where observing deformation, it is believed that film is destroyed.It acquires as the following formula energy of rupture (E): energy of rupture E (mJ)=ball matter Measure (kg) × destruction height average value (mm) × 9.8 (m/s2)。
(1-7) total light transmittance
By the way that resin combination hot pressing to be film-made, 160 μm of thickness of film (non-extension film) is obtained, haze meter is used (electricity color industry society, Japan system, NDH-5000) measurement total light transmittance.
(1-8) internal haze
Resin combination is hot-forming at 250 DEG C, the film (non-extension film) of about 160 μm of thickness of production.In stone Ying Chizhong fills it up with 1,2,3,4-tetrahydro-naphthalene (naphthane), by production it is thin film dipped wherein, use haze meter (Japan's electricity color work Industry society system, NDH-5000) measurement mist degree, the internal haze of every 100 μ m thick is calculated according to the following formula: the inside of every 100 μ m thick Measured value (%) × (thickness (μm) of 100 μm/film) for mist degree (%)=obtain.In addition, measurement is carried out using 3 pieces of films, The internal haze of every 100 μ m thick is calculated from its average value.
(1-9) dispersity (passes through the observation of the island structure size of STEM)
For by by resin combination at 250 DEG C it is hot-forming and make 160 μm of thickness of film (do not extend thin Film), by scanning electron microscope (High-Technologies society, Hitachi system, FE-SEM S-4800), observe the phase of film Separate the dispersity (island structure) formed.Determination condition are as follows: acceleration voltage 20kV, 5 μ A of emission current or 10 μ A, W.D. =8mm.Island size is calculated by measuring the maximum length of any 10 island portions as its average value.
(1-10) MIT folding strength tests (folding strength)
Resin combination is hot-forming at 250 DEG C, obtain 160 μm of thickness of non-extension film.Do not prolong what is obtained The size that film is cut into 96mm × 96mm is stretched, (Toyo Seiki makes society, institute system, X-6S) is extended by using gradually twin shaft, is being set With 240mm/ minutes extension speeds according to longitudinal direction (direction MD) and lateral (direction TD) at a temperature of Tg+24 DEG C of oil/fat composition Sequence respectively by extension ratio be 2 times in a manner of carry out gradually twin shaft extend, and by cooling, obtain 40 μm of thickness of extension Film.The size that obtained extension film is cut into 90mm × 15mm uses MIT folding strength testing machine as test film (TESTER industry society system, BE-201) applies load 200g, according to JIS P under 23 DEG C of temperature, the atmosphere of relative humidity 50% 8115 (2001) measure MIT folding strength test number (TN).
(1-11) trousers shape tearing strength (tearing strength)
According to JIS K 7128-1 (1998), trousers shape tearing strength is found out.It specifically, will be according to the note of above-mentioned (1-10) item The size that obtained extension film is cut into 120mm × 30mm is carried, it is small that 1 is stood under 23 DEG C of temperature, the atmosphere of relative humidity 50% When more than after be used as test film, using Autograph (society, Shimadzu Seisakusho Ltd. system, AGS-X) with 200mm/ minutes test speeds Tested, calculate remove tearing start 20mm and tearing terminate before 5mm other than 35mm tear edge average value, will The average value of 5 pieces of samples is as measurement result.
(1-12) phase difference
For the extension film obtained according to the record of above-mentioned (1-10) item, using full-automatic birefringence meter, (prince is measured Machine society system, KOBRA-WR), under conditions of 40 ° of incidence angle, measure relative to phase difference Re and thickness in the face of wavelength 590nm Spend the phase difference Rth in direction.Refractive index with slow-axis direction of the film in face is nx, with fast axis direction of the film in face Refractive index is ny, and the refractive index with the thickness direction of film is nz, with film with a thickness of d, is acquired in face respectively by following formula The phase difference Rth of phase difference Re and thickness direction.
Phase difference Re=(nx-ny) × d in face
Thickness direction phase difference Rth=[(nx+ny)/2-nz] × d
(2) preparation of resin combination
(2-1) embodiment 1: the modulation of resin combination (A-1)
In the reactor for having agitating device, temperature sensor, cooling tube, nitrogen ingress pipe, polyisoprene is added Maleic anhydride adduct and 3 parts of the esterification products (KURARAY society system, UC-102M) of 2-Hydroxyethyl methacrylate, methyl-prop 26 parts of e pioic acid methyl ester (MMA), 1 part of 2- (methylol) methyl acrylate (MHMA), as 50 parts of toluene of polymer solvent, exist on one side Wherein by nitrogen, it is warming up to 105 DEG C on one side.Then, t-amyl peroxy isononoate (the ARKEMA Ji as initiator is added Rich society's system, LUPEROX (registered trademark) 570) 0.09 part, polymerisation in solution in 30 minutes is carried out at 105-110 DEG C.Here, conduct Cyclization catalyst is added .01 parts of octadecyl phosphoesterase 30, reacts 10 minutes.It is obtained as a result, containing (methyl) third containing lactonic ring Olefin(e) acid quasi polymer and the polymer chain are grafted on the resin combination of the graft copolymer on polyisoprene chain.By gathering The reactivity that the reactivity for closing the MMA that the residual monomers amount in reaction solution calculates is 16%, MHMA is 10%.It is calculated by reactivity (methyl) the acrylic polymer chain being bonded with polyisoprene chain, the ratio of components with (methyl) acrylic polymer (quality criteria) is MMA:MHMA=97.7:2.3, and the content ratio of the unit from (methyl) acrylate is 96.2 matter % is measured, the content ratio of ring structure unit is 3.5 mass %.It, can be preferably when taking out a part of reaction solution and being filtered experiment It is filtered.
Next, 50 parts of addition methyl ethyl ketone (MEK) is diluted in obtained reaction solution, it is used into aperture 10 μm PTFE (polytetrafluoroethylene (PTFE)) filter processed be filtered after, stir in a large amount of methanol, be slowly added on one side on one side.It takes The white solid precipitated herein out is obtained by about 1 hour removing solvent dry at 2.6kPa, 80 DEG C containing containing lactonic ring (methyl) acrylic polymer and the polymer chain be grafted on the resin group of the graft copolymer on polyisoprene chain It closes object (A-1).The weight average molecular weight of resin combination (A-1) is 13.8 ten thousand, and number-average molecular weight is 3.8 ten thousand, chloroform insoluble component It is 2%.
(2-2) embodiment 2: the modulation of resin combination (A-2)
In the reactor for having agitating device, temperature sensor, cooling tube, nitrogen ingress pipe, polyisoprene is added Maleic anhydride adduct and 3 parts of the esterification products (KURARAY society system, UC-102M) of 2-Hydroxyethyl methacrylate, methyl-prop 23 parts of e pioic acid methyl ester (MMA), 3 parts of phenyl maleimide (PMI), as 50 parts of toluene of polymer solvent, on one side lead to wherein Nitrogen is crossed, is warming up to 105 DEG C on one side.Then, t-amyl peroxy isononoate (the ARKEMA Ji Fushe as initiator is added System, LUPEROX (registered trademark) 570) 0.09 part, it is carried out polymerisation in solution 30 minutes at 105-110 DEG C.Contained as a result, (methyl) acrylic polymer of the ring containing maleimide and the polymer chain are grafted on the grafting on polyisoprene chain The resin combination of copolymer.The reactivity of the MMA calculated by the residual monomers amount in polymerization liquid is the anti-of 14%, PMI Should rate be 21%.(methyl) acrylic polymer chain being bonded with polyisoprene chain calculated by reactivity, with (methyl) The ratio of components (quality criteria) of acrylic polymer is MMA:PMI=83.6:16.4, comes from the unit of (methyl) acrylate Content ratio be 83.6 mass %, the content ratio of ring structure unit is 16.4 mass %.A part of reaction solution is taken out to carry out When filtration experiment, can preferably it be filtered.
Next, 50 parts of addition methyl ethyl ketone (MEK) is diluted in obtained reaction solution, it is used into aperture 10 μm PTFE filter be filtered after, stir in a large amount of methanol, be slowly added on one side on one side.What taking-up precipitated herein White solid obtains the (first containing the ring containing maleimide by about 1 hour removing solvent dry at 2.6kPa, 80 DEG C Base) acrylic polymer and the polymer chain be grafted on the resin combination of the graft copolymer on polyisoprene chain (A-2).The weight average molecular weight of resin combination (A-2) is 11.1 ten thousand, and number-average molecular weight is 3.1 ten thousand, and chloroform insoluble component is 3%.
(2-3) comparative example 1: the modulation of resin combination (A-3)
In the reactor for having agitating device, temperature sensor, cooling tube, nitrogen ingress pipe, polyisoprene is added Maleic anhydride adduct and 2-Hydroxyethyl methacrylate 3 parts of carboxylate (KURARAY society system, UC-102M), metering system Sour 27 parts of methyl esters (MMA), as 50 parts of toluene of polymer solvent, on one side wherein by nitrogen, be warming up to 105 DEG C on one side.So Afterwards, the t-amyl peroxy isononoate (ARKEMA Ji Fu society system, LUPEROX (registered trademark) 570) as initiator is added It 0.09 part, is carried out polymerisation in solution 30 minutes at 105-110 DEG C.It is obtained as a result, containing methylmethacrylate polymer (PMMA) and the polymer chain is grafted on the resin combination of the graft copolymer on polyisoprene chain.By polymerization reaction The reactivity for the MMA that residual monomers amount in liquid calculates is 16%.
Next, after 50 parts of addition methyl ethyl ketone (MEK) is diluted in obtained reaction solution, in a large amount of first It stirs in alcohol, is slowly added on one side on one side.The white solid precipitated herein is taken out, it is small by drying about 1 at 2.6kPa, 80 DEG C When remove solvent, obtain being grafted on polyisoprene containing methylmethacrylate polymer (PMMA) and the polymer chain The resin combination (A-3) of graft copolymer on chain.The weight average molecular weight of resin combination (A-3) is 12.4 ten thousand, and number is divided equally Son amount is 3.1 ten thousand.
(2-4) comparative example 2: the synthesis of resin combination (B-1)
In the reactor for having agitating device, temperature sensor, cooling tube, nitrogen ingress pipe, methacrylic acid is added 48 parts of methyl esters (MMA), 2 parts of 2- (methylol) methyl acrylate (MHMA), as 50 parts of toluene of polymer solvent, on one side wherein By nitrogen, it is warming up to 105 DEG C on one side.Then, t-amyl peroxy isononoate (the ARKEMA Ji Fushe as initiator is added System, LUPEROX (registered trademark) 570) 0.2 part, it is carried out polymerisation in solution 180 minutes at 105-110 DEG C.Here, conduct is added .01 parts of the octadecyl phosphoesterase 30 of cyclization catalyst after reaction 1 hour, heats 1 hour for 240 DEG C in autoclave.By This, obtains the resin combination containing (methyl) acrylic polymer containing lactonic ring.It is single by the remaining in polymerization liquid The reactivity that the reactivity for the MMA that the scale of construction calculates is 82%, MHMA is 88%.(methyl) containing lactonic ring calculated by reactivity The ratio of components (quality criteria) of acrylic polymer is MMA:MHMA=95.7:4.3, comes from the unit of (methyl) acrylate Content ratio be 93.1 mass %, the content ratio of ring structure unit is 6.4 mass %.
Next, after 50 parts of addition methyl ethyl ketone (MEK) is diluted in obtained reaction solution, in a large amount of first It stirs in alcohol, is slowly added on one side on one side.The white solid precipitated herein is taken out, by small in 2.6kPa, 200 DEG C of dryings about 1 When remove solvent, obtain the resin combination (B-1) containing (methyl) acrylic polymer containing lactonic ring.Resin combination (B-1) weight average molecular weight is 13.8 ten thousand, and number-average molecular weight is 5.7 ten thousand.
(2-5) comparative example 3: the modulation of resin combination (B-2)
In the reactor for having agitating device, temperature sensor, cooling tube, nitrogen ingress pipe, methacrylic acid is added 47 parts of methyl esters (MMA), 3 parts of PMI, as 50 parts of toluene of polymer solvent, on one side wherein by nitrogen, be warming up to 105 on one side ℃.Then, t-amyl peroxy isononoate (ARKEMA Ji Fu society system, the LUPEROX (registered trademark) as initiator is added 570) it 0.2 part, is carried out polymerisation in solution 180 minutes at 105-110 DEG C.(the first containing the ring containing maleimide is obtained as a result, Base) acrylic polymer resin combination.It is by the reactivity of MMA that the residual monomers amount in polymerization liquid calculates The reactivity of 85%, PMI are 82%.By the group of (methyl) acrylic polymer of the ring containing maleimide of reactivity calculating At being MMA:PMI=94.2:5.8 than (quality criteria), the content ratio of the unit from (methyl) acrylate is 94.2 matter % is measured, the content ratio of ring structure unit is 5.8 mass %.
Next, after 50 parts of addition methyl ethyl ketone (MEK) is diluted in obtained reaction solution, in a large amount of first It stirs in alcohol, is slowly added on one side on one side.The white solid precipitated herein is taken out, by small in 2.6kPa, 200 DEG C of dryings about 1 When remove solvent, obtain the resin combination (B-2) of (methyl) acrylic polymer containing the ring containing maleimide.Resin The weight average molecular weight of composition (B-2) is 12.9 ten thousand, and number-average molecular weight is 5.9 ten thousand.
(2-6) embodiment 3: the modulation of resin combination (C-1)
9 parts of the resin combination (B-1) that 1 part of the resin combination (A-1) that embodiment 1 obtains is obtained with comparative example 2 is molten Solution, by about 1 hour removing solvent dry at 2.6kPa, 150 DEG C, obtains resin combination in 40 parts of MEK and after mixing (C-1).The weight average molecular weight of resin combination (C-1) is 13.0 ten thousand, and number-average molecular weight is 5.9 ten thousand.
(2-7) embodiment 4: the modulation of resin combination (C-2)
It is 9 parts of resin combination (B-2) that 1 part of resin combination (A-2) that embodiment 2 obtains, comparative example 3 are obtained, purple 0.01 part of ultraviolet absorbers (ADEKA society system, LA-31), antioxidant (BASF society system, Irganox (registered trademark) 1010) 0.001 part, 0.001 part of antioxidant (ADEKA society system, PEP-36), after dissolving and mix in 40 parts of MEK, by 2.6kPa, dry about 1 hour removing solvent at 150 DEG C, obtain resin combination (C-2).Resin combination (C-2's) divides equally again Son amount is 13.2 ten thousand, and number-average molecular weight is 5.1 ten thousand.
(2-8) comparative example 4: the modulation of resin combination (A-4)
In embodiment 1, in addition to using the maleic anhydride adduct and 2-Hydroxyethyl methacrylate of polyisoprene 3 parts of esterification products, 26.7 parts of MMA, other than 0.3 part of MMA, polymerization reaction and cyclization have been carried out similarly to Example 1. The reactivity that the reactivity of the MMA calculated by the residual monomers amount in polymerization liquid is 18%, MHMA is 12%.By reactivity (methyl) the acrylic polymer chain being bonded with polyisoprene chain calculated, the composition with (methyl) acrylic polymer It is MMA:MHMA=99.3:0.7 than (quality criteria), the content ratio of the unit from (methyl) acrylate is 98.9 matter % is measured, the content ratio of ring structure unit is 1.0 mass %.It, can be preferably when taking out a part of reaction solution and being filtered experiment It is filtered.Then, similarly to Example 1, by by the filtering of obtained reaction solution, reprecipitation, drying, obtaining containing containing interior (methyl) acrylic polymer and the polymer chain of ester ring are grafted on the tree of the graft copolymer on polyisoprene chain Oil/fat composition (A-4).The weight average molecular weight of resin combination (A-4) is 12.2 ten thousand, and number-average molecular weight is 3.1 ten thousand, and chloroform is insoluble Ingredient is 2%.
(2-9) comparative example 5: the modulation of resin combination (B-3)
In comparative example 2, other than using 49 parts of MMA, 1 part of MHMA, it has been carried out similarly and has polymerize instead with comparative example 2 Should and cyclization.The reactivity of the MMA calculated by the residual monomers amount in polymerization liquid is that the reactivity of 81%, MHMA is 89%.The ratio of components (quality criteria) of (methyl) acrylic polymer containing lactonic ring calculated by reactivity is MMA:MHMA =97.8:2.2, from (methyl) acrylate unit content ratio be 96.5 mass %, ring structure unit containing than Example is 3.2 mass %.Then, in the same manner as comparative example 2, by being contained the filtering of obtained reaction solution, reprecipitation, drying There is the resin combination (B-3) of (methyl) acrylic polymer containing lactonic ring.The weight average molecular weight of resin combination (B-3) It is 14.5 ten thousand, number-average molecular weight is 6.3 ten thousand.
(2-10) comparative example 6: the modulation of resin combination (C-3)
9 parts of the resin combination (B-3) that 1 part of the resin combination (A-4) that comparative example 4 obtains is obtained with comparative example 5 is molten Solution, by about 1 hour removing solvent dry at 2.6kPa, 150 DEG C, obtains resin combination in 40 parts of MEK and after mixing (C-3).The weight average molecular weight of resin combination (C-3) is 14.4 ten thousand, and number-average molecular weight is 6.0 ten thousand.
(2-11) comparative example 7: the modulation of resin combination (A-5)
In embodiment 1, in addition to using the maleic anhydride adduct and 2-Hydroxyethyl methacrylate of polyisoprene 3 parts of esterification products, 13 parts of MMA, 13 parts of MHMA, as other than .03 parts of octadecyl phosphoesterase 30 of cyclization catalyst, with reality It applies example 1 and has been carried out similarly polymerization reaction and cyclization.By the reaction for the MMA that the residual monomers amount in polymerization liquid calculates The reactivity that rate is 19%, MHMA is 13%.(methyl) acrylic polymer being bonded with polyisoprene calculated by reactivity Object chain is closed, the ratio of components (quality criteria) with (methyl) acrylic polymer is MMA:MHMA=59.4:40.6, comes from (first Base) content ratio of unit of acrylate is 27.4 mass %, the content ratio of ring structure unit is 67.1 mass %.It takes out When a part of reaction solution is filtered experiment, the boosting of filter is observed.Then, similarly to Example 1, by that will obtain Reaction solution filtering, reprecipitation, drying, obtain containing (methyl) acrylic polymer and the polymer containing lactonic ring Chain is grafted on the resin combination (A-5) of the graft copolymer on polyisoprene.The weight average molecular weight of resin combination (A-5) It is 18.1 ten thousand, number-average molecular weight is 3.2 ten thousand, and chloroform insoluble component is 11%.
(2-12) comparative example 8: the modulation of resin combination (B-4)
In comparative example 2, other than using 25 parts of MMA, 25 parts of MHMA, it has been carried out similarly and has polymerize with comparative example 2 Reaction and cyclization.The reactivity that the reactivity of the MMA calculated by the residual monomers amount in polymerization liquid is 87%, MHMA It is 85%.The ratio of components (quality criteria) of (methyl) acrylic polymer containing lactonic ring calculated by reactivity is MMA: The content ratio of MHMA=50.6:49.4, the unit from (methyl) acrylate are 9.2 mass %, and ring structure unit contains Proportional is 83.9 mass %.Then, in the same manner as comparative example 2, by obtaining the filtering of obtained reaction solution, reprecipitation, drying To the resin combination (B-4) for containing (methyl) acrylic polymer containing lactonic ring.Resin combination (B-4's) divides equally again Son amount is 18.9 ten thousand, and number-average molecular weight is 5.2 ten thousand.
(2-13) comparative example 9: the modulation of resin combination (C-4)
1 part of resin combination (A-5), 9 parts of the resin combination (B-4) obtained with comparative example 8 that comparative example 7 obtains is existed After dissolving and mix in 40 parts of MEK, by about 1 hour removing solvent dry at 2.6kPa, 150 DEG C, resin combination is obtained (C-4).The weight average molecular weight of resin combination (C-4) is 17.8 ten thousand, and number-average molecular weight is 5.0 ten thousand.
(2-14) embodiment 5: the modulation of resin combination (D-1)
In the reactor for having agitating device, temperature sensor, cooling tube, nitrogen ingress pipe, SEBS three block is added Copolymer (Kraton society system, A1536, olefinic double bond amount 0.10mmol/g, 39 mass % of styrene units content, refractive index 1.519) 5 parts, 73 parts of methyl methacrylate (MMA), 18 parts of phenyl maleimide (PMI), n-dodecyl mercaptan (nDM) 0.05 part, as 100 parts of toluene of polymer solvent, on one side wherein by nitrogen, be warming up to 105 DEG C on one side.Then, it is added and makees For the BPIC t butyl peroxy isopropyl carbonate (chemical drug Akzo society system, Kayakarubon (registered trademark) Bic75) of initiator 0.009 part, and by 5 parts of styrene (St) and with 0.018 part of BPIC t butyl peroxy isopropyl carbonate of 1 part of dilution with toluene, Existed while with certain speed dropwise addition with 3 hours and carries out polymerisation in solution, and then aging 4 hours at 105-110 DEG C.As a result, To containing polymerizeing (methyl) acrylic polymer and the polymerization of the ring containing maleimide formed by MMA, PMI and St Object chain is bonded in the resin combination of the graft copolymer on SEBS triblock polymer chain.It is single by the remaining in polymerization liquid The reactivity that the reactivity that the reactivity for the MMA that the scale of construction calculates is 95%, PMI is 98%, St is 100%.It is calculated by reactivity (methyl) the acrylic polymer chain being bonded with SEBS triblock polymer chain, the group with (methyl) acrylic polymer It is MMA:PMI:St=75.9:18.9:5.2, the content ratio of the unit from (methyl) acrylate at than (quality criteria) For 75.9 mass %, the content ratio of ring structure unit is 18.9 mass %.When taking out a part of reaction solution and being filtered experiment, It can preferably be filtered.
Then the polymerization liquid that will be obtained, with blow vent number after the processing speed importing for the 600g/h that converted with resin for 1 In the exhaust screw biaxial extruder (aperture: 15mm, L/D:45) that a, preceding blow vent number is 2, carried out in the extruder Devolatilization obtains (methyl) acrylic polymer containing the ring containing maleimide and polymer chain bonding by squeezing out The transparent grain of the resin combination (D-1) of graft copolymer on SEBS triblock polymer chain.In addition, biaxial extruder Operating condition be 260 DEG C of barrel temperature, revolving speed 300rpm, degree of decompression 13.3-400hPa (10-300mmHg).Resin combination (D-1) weight average molecular weight is 15.0 ten thousand, and number-average molecular weight is 6.0 ten thousand, and the glass transition temperature of high temperature side is 138 DEG C, low The glass transition temperature of warm side is -68 DEG C, and chloroform insoluble component is 0.3%, refractive index 1.517.Resin combination (D-1) Extension film face in the phase difference Rth of phase difference Re and thickness direction be respectively 0.9nm and 2.9nm.
(2-15) embodiment 6: the modulation of resin combination (D-2)
In embodiment 5, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor 10 parts of (Kraton society system, A1536), 69 parts of MMA, other than 17 parts of PMI, polymerization reaction has been carried out similarly to Example 5.By It is the reactivity of 99%, St that the reactivity for the MMA that residual monomers amount in polymerization liquid calculates, which is the reactivity of 96%, PMI, It is 100%.The acrylic polymer chain being bonded with SEBS triblock copolymer chain calculated by reactivity, with (methyl) propylene The ratio of components (quality criteria) of acids polymers is MMA:PMI:St=75.2:19.1:5.7, from (methyl) acrylate The content ratio of unit is 75.2 mass %, and the content ratio of ring structure unit is 19.1 mass %.Take out a part of reaction solution When being filtered experiment, can preferably it be filtered.By obtained polymerization liquid similarly to Example 6 in extruder into Row devolatilization obtains the particle of transparent resin combination (D-2).The weight average molecular weight of resin combination (D-2) is 14.8 ten thousand, number Average molecular weight is 5.9 ten thousand, and the glass transition temperature of high temperature side is 138 DEG C, and the glass transition temperature of low temperature side is -68 DEG C, Chloroform insoluble component is 0.3%, refractive index 1.517.The island ruler of the island structure of the non-extension film of resin combination (D-2) Very little is 200nm, and the phase difference Rth of phase difference Re and thickness direction is respectively 0.2nm and 3.5nm in the face of extension film.
(2-16) embodiment 7: the modulation of resin combination (D-3)
In embodiment 5, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor 15 parts of (Kraton society system, A1536), 65 parts of MMA, 16 parts of PMI use 4 parts as the monomer component St by the way that addition is added dropwise In addition, polymerization reaction has been carried out similarly to Example 5.By the reaction for the MMA that the residual monomers amount in polymerization liquid calculates The reactivity that the reactivity that rate is 96%, PMI is 99%, St is 100%.By reactivity calculate with SEBS triblock polymer (methyl) acrylic polymer chain of chain bonding, the ratio of components (quality criteria) with (methyl) acrylic polymer is MMA: PMI:St=75.9:19.3:4.9, the content ratio of the unit from (methyl) acrylate are 75.9 mass %, ring structure list The content ratio of member is 19.3 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it be filtered.Will To polymerization liquid devolatilization is carried out in extruder similarly to Example 5, obtain of transparent resin combination (D-3) Grain.The weight average molecular weight of resin combination (D-3) is 14.0 ten thousand, and number-average molecular weight is 5.3 ten thousand, the glass transition temperature of high temperature side Degree is 137 DEG C, and the glass transition temperature of low temperature side is -68 DEG C, and chloroform insoluble component is 0.3%, refractive index 1.517.Tree The island of the island structure of the non-extension film of oil/fat composition (D-3) is having a size of 200nm, phase difference Re and thick in the face of extension film The phase difference Rth for spending direction is respectively 0.8nm and 4.5nm.
(2-17) embodiment 8: the modulation of resin combination (D-4)
In embodiment 5, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor 20 parts of (Kraton society system, A1536), 61 parts of MMA, 15 parts of PMI, 4 parts are used as the monomer component St by the way that addition is added dropwise In addition, polymerization reaction has been carried out similarly to Example 5.By the reaction for the MMA that the residual monomers amount in polymerization liquid calculates The reactivity that the reactivity that rate is 97%, PMI is 99%, St is 100%.By reactivity calculate with SEBS triblock polymer (methyl) acrylic polymer chain of chain bonding, the ratio of components (quality criteria) with (methyl) acrylic polymer is MMA: PMI:St=76.1:18.8:5.1, the content ratio of the unit from (methyl) acrylate are 76.1 mass %, ring structure list The content ratio of member is 18.8 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it be filtered.Will To polymerization liquid devolatilization is carried out in extruder similarly to Example 5, obtain of transparent resin combination (D-4) Grain.The weight average molecular weight of resin combination (D-4) is 14.5 ten thousand, and number-average molecular weight is 6.0 ten thousand, the glass transition temperature of high temperature side Degree is 136 DEG C, and the glass transition temperature of low temperature side is -68 DEG C, and chloroform insoluble component is 0.4%, refractive index 1.517.Tree The island of the island structure of the non-extension film of oil/fat composition (D-4) is having a size of 250nm, phase difference Re and thick in the face of extension film The phase difference Rth for spending direction is respectively 0.5nm and 6.2nm.
(2-18) embodiment 9: the modulation of resin combination (D-5)
In embodiment 5, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor (Aldrich society system, product number 200557, olefinic double bond amount 0.10mmol/g, 26 mass % of styrene units content, folding Penetrate rate 1.513) 10 parts, 72 parts of MMA, 16 parts of PMI, it is used other than 2 parts as the monomer component St by the way that addition is added dropwise, with reality It applies example 5 and has been carried out similarly polymerization reaction.The reactivity of the MMA calculated by the residual monomers amount in polymerization liquid is 96%, The reactivity that the reactivity of PMI is 99%, St is 100%.It is bonded by what reactivity calculated with SEBS triblock polymer chain (methyl) acrylic polymer chain, the ratio of components (quality criteria) with (methyl) acrylic polymer are MMA:PMI:St= The content ratio of 79.4:18.3:2.3, the unit from (methyl) acrylate are 79.4 mass %, and ring structure unit contains Ratio is 18.3 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it be filtered.The polymerization that will be obtained Reaction solution carries out devolatilization in extruder similarly to Example 5, obtains the particle of transparent resin combination (D-5).Resin The weight average molecular weight of composition (D-5) is 17.2 ten thousand, and number-average molecular weight is 7.1 ten thousand, and glass transition temperature is 138 DEG C, chloroform Insoluble component is 0.4%, refractive index 1.515.The island of the island structure of the non-extension film of resin combination (D-5) having a size of 250nm, the phase difference Rth of phase difference Re and thickness direction is respectively 0.5nm and 4.9nm in the face of extension film.
(2-19) embodiment 10: the modulation of resin combination (D-6)
In embodiment 5, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor Object (society, Asahi Chemical Industry system, Tuftec (registered trademark) H1041, olefinic double bond amount 0.44mmol/g, 30 matter of styrene units content Measure %, refractive index 1.515) 10 parts, 70 parts of MMA, 16 parts of PMI, as the monomer component St by the way that addition is added dropwise use 4 parts with Outside, polymerization reaction has been carried out similarly to Example 5.By the reactivity for the MMA that the residual monomers amount in polymerization liquid calculates The reactivity that reactivity for 97%, PMI is 99%, St is 100%.By reactivity calculate with SEBS triblock polymer chain (methyl) acrylic polymer chain of bonding, the ratio of components (quality criteria) with (methyl) acrylic polymer is MMA: PMI:St=77.4:18.1:4.6, the content ratio of the unit from (methyl) acrylate are 77.4 mass %, ring structure list The content ratio of member is 18.1 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it be filtered.Will To polymerization liquid devolatilization is carried out in extruder similarly to Example 5, obtain of transparent resin combination (D-6) Grain.The weight average molecular weight of resin combination (D-6) is 13.5 ten thousand, and number-average molecular weight is 5.6 ten thousand, glass transition temperature 138 DEG C, chloroform insoluble component is 0.5%, refractive index 1.516.The island structure of the non-extension film of resin combination (D-6) Island is having a size of 300nm, and the phase difference Rth of phase difference Re and thickness direction is respectively 0.3nm and 2.3nm in the face of extension film.
(2-20) embodiment 11: the modulation of resin combination (D-7)
In embodiment 5, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor (society, Asahi Chemical Industry system, Tuftec (registered trademark) P1083, olefinic double bond amount 2.40mmol/g, 20 matter of styrene units content Measure %, refractive index 1.500) 10 parts, 83 parts of MMA, 6 parts of PMI, as the monomer component St by the way that addition is added dropwise use 1 part with Outside, polymerization reaction has been carried out similarly to Example 5.By the reactivity for the MMA that the residual monomers amount in polymerization liquid calculates The reactivity that reactivity for 96%, PMI is 99%, St is 100%.By reactivity calculate with SEBS triblock polymer chain (methyl) acrylic polymer chain of bonding, the ratio of components (quality criteria) with (methyl) acrylic polymer is MMA: PMI:St=92.6:6.3:1.1, the content ratio of the unit from (methyl) acrylate are 92.6 mass %, ring structure list The content ratio of member is 6.3 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it be filtered.Will To polymerization liquid devolatilization is carried out in extruder similarly to Example 5, obtain of transparent resin combination (D-7) Grain.The weight average molecular weight of resin combination (D-7) is 16.3 ten thousand, and number-average molecular weight is 6.2 ten thousand, glass transition temperature 123 DEG C, chloroform insoluble component is 0.9%, refractive index 1.500.Phase difference Re in the face of the extension film of resin combination (D-7) Phase difference Rth with thickness direction is respectively 0.3nm and 4.5nm.
(2-21) embodiment 12: the modulation of resin combination (D-8)
In embodiment 5, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor (society, Asahi Chemical Industry system, Tuftec (registered trademark) H1517, olefinic double bond amount 0.11mmol/g, 43 matter of styrene units content Measure %, refractive index 1.525) 10 parts, 63 parts of MMA, 24 parts of PMI, as the monomer component St by the way that addition is added dropwise use 3 parts with Outside, polymerization reaction has been carried out similarly to Example 5.By the reactivity for the MMA that the residual monomers amount in polymerization liquid calculates The reactivity that reactivity for 95%, PMI is 98%, St is 100%.By reactivity calculate with SEBS triblock polymer chain (methyl) acrylic polymer chain of bonding, the ratio of components (quality criteria) with (methyl) acrylic polymer is MMA: PMI:St=69.3:27.2:3.5, the content ratio of the unit from (methyl) acrylate are 69.3 mass %, ring structure list The content ratio of member is 27.2 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it be filtered.Will To polymerization liquid devolatilization is carried out in extruder similarly to Example 5, obtain of transparent resin combination (D-8) Grain.The weight average molecular weight of resin combination (D-8) is 16.6 ten thousand, and number-average molecular weight is 6.3 ten thousand, glass transition temperature 151 DEG C, chloroform insoluble component is 0.5%, refractive index 1.525.Phase difference Re in the face of the extension film of resin combination (D-8) Phase difference Rth with thickness direction is respectively 0.5nm and 5.9nm.
(2-22) comparative example 10: the modulation of resin combination (D-9)
In embodiment 5, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor (JSR society system, Dynaron (registered trademark) 9901P, olefinic double bond amount 0.06mmol/g, 50 matter of styrene units content Measure %, refractive index 1.530) 10 parts, 30 parts of MMA, 55 parts of PMI, as the monomer component St by the way that addition is added dropwise use 5 parts with Outside, polymerization reaction has been carried out similarly to Example 5.By the reactivity for the MMA that the residual monomers amount in polymerization liquid calculates The reactivity that reactivity for 98%, PMI is 98%, St is 100%.By reactivity calculate with SEBS triblock polymer chain (methyl) acrylic polymer chain of bonding, the ratio of components (quality criteria) with (methyl) acrylic polymer is MMA: PMI:St=33.3:61.0:5.7, the content ratio of the unit from (methyl) acrylate are 33.3 mass %, ring structure list The content ratio of member is 61.0 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it be filtered.Will To polymerization liquid devolatilization is carried out in extruder similarly to Example 5, obtain of transparent resin combination (D-9) Grain.The weight average molecular weight of resin combination (D-9) is 14.9 ten thousand, and number-average molecular weight is 5.9 ten thousand, glass transition temperature 201 DEG C, chloroform insoluble component is 2.1%, refractive index 1.560.In addition, attempting prolonging for the non-extension film of resin combination (D-9) It stretches, since intensity deficiency cannot extend.
(2-23) comparative example 11: the modulation of resin combination (D-10)
In embodiment 5, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor (society, Asahi Chemical Industry system, H1052, olefinic double bond amount 0.27mmol/g, 20 mass % of styrene units content, refractive index 1.500) 10 parts, 88.5 parts of MMA, 1.5 parts of PMI, it is same with embodiment 5 other than as the monomer component St by the way that addition is added dropwise Sample polymerization reaction is carried out.The reactivity of the MMA calculated by the residual monomers amount in polymerization liquid is the anti-of 98%, PMI Should rate be 98%.(methyl) the acrylic polymer chain being bonded with SEBS triblock polymer chain calculated by reactivity, with The ratio of components (quality criteria) of (methyl) acrylic polymer is MMA:PMI=98.3:1.7, comes from (methyl) acrylate The content ratio of unit be 98.3 mass %, the content ratio of ring structure unit is 1.7 mass %.Take out a part of reaction solution When being filtered experiment, can preferably it be filtered.By obtained polymerization liquid similarly to Example 5 in extruder into Row devolatilization obtains the particle of transparent resin combination (D-10).The weight average molecular weight of resin combination (D-10) is 14.5 ten thousand, Number-average molecular weight is 6.0 ten thousand, and glass transition temperature is 112 DEG C, and chloroform insoluble component is 0.4%, refractive index 1.500.
(2-24) embodiment 13: the modulation of resin combination (D-11)
In the reactor for having agitating device, temperature sensor, cooling tube, nitrogen ingress pipe, SEBS three block is added Copolymer (society, Asahi Chemical Industry system, H1052, olefinic double bond amount 0.27mmol/g, 20 mass % of styrene units content, refractive index 1.500) 10 parts, 75 parts of methyl methacrylate (MMA), 13.5 parts of 2- (methylol) methyl acrylate (MHMA), n-dodecane 0.05 part of base mercaptan (nDM), as 100 parts of toluene of polymer solvent, on one side wherein by nitrogen, be warming up to 105 DEG C on one side. Then, BPIC t butyl peroxy isopropyl carbonate (chemical drug Akzo society system, the Kayakarubon (registrar as initiator is added Mark) Bic75) 0.009 part, and by 2 parts of styrene (St) and with 0.015 part of tert-butyl peroxy isopropyl of 1 part of dilution with toluene Base carbonic ester was existed while with certain speed dropwise addition with 2 hours and carries out polymerisation in solution at 105-110 DEG C, and then aging 4 is small When..07 parts of octadecyl phosphoesterase 30 as cyclization catalyst are added herein, 2 hours rings are carried out under 90-110 DEG C of reflux Change reaction.Obtain as a result, containing polymerize by MMA, MHMA and St (methyl) acrylic polymer containing lactonic ring formed, with And the resin combination of graft copolymer that the polymer chain is bonded with SEBS triblock polymer chain.By in polymerization liquid The reactivity that the reactivity that the reactivity for the MMA that residual monomers amount calculates is 94%, MHMA is 94%, St is 99%.By reacting (methyl) acrylic polymer chain being bonded with SEBS triblock copolymer chain that rate calculates, with (methyl) acrylic The ratio of components (quality criteria) of object is MMA:MHMA:St=82.6:14.9:2.5, and the unit from (methyl) acrylate contains Proportional is 72.9 mass %, and the content ratio of ring structure unit is 22.8 mass %, the unit from styrene containing than Example is 2.4 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it be filtered.
Then obtained polymerization liquid is added in autoclave after carrying out heat treatment in 1 hour at 240 DEG C, with The exhaust screw twin shaft that blow vent number is 1, preceding blow vent number is 2 after being imported with the processing speed of resin conversion 600g/h In extruder (aperture: 15mm, L/D:45), devolatilization is carried out in the extruder, by squeezing out, is obtained containing containing lactonic ring The resin for the graft copolymer that (methyl) acrylic polymer and the polymer chain are bonded with SEBS triblock polymer chain The transparent grain of composition (D-11).In addition, the operating condition of biaxial extruder is 260 DEG C of barrel temperature, revolving speed 300rpm subtracts Pressure degree 13.3-400hPa (10-300mmHg).The weight average molecular weight of resin combination (D-11) is 15.5 ten thousand, and number-average molecular weight is 5.9 ten thousand, the glass transition temperature of high temperature side is 127 DEG C, and the glass transition temperature of low temperature side is -54 DEG C, chloroform not melt into It is divided into 0.4%, refractive index 1.500.The island of the island structure of the non-extension film of resin combination (D-11) having a size of 250nm, the phase difference Rth of phase difference Re and thickness direction is respectively 0.3nm and 4.9nm in the face of extension film.
(2-25) embodiment 14: the modulation of resin combination (D-12)
In embodiment 13, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor Object (KURARAY society system, HYBRAR (registered trademark) 7125, olefinic double bond amount 0.44mmol/g, 20 matter of styrene units content Measure %) 10 parts, 75 parts of MMA, other than 13.5 parts of MHMA, carried out polymerization reaction and cyclization similarly to Example 13. It is the reaction of 94%, St that the reactivity of the MMA calculated by the residual monomers amount in polymerization liquid, which is the reactivity of 94%, MHMA, Rate is 100%.(methyl) the acrylic polymer chain being bonded with SEBS triblock polymer chain calculated by reactivity, with The ratio of components (quality criteria) of (methyl) acrylic polymer is MMA:MHMA:St=82.7:14.8:2.5, is come from (methyl) The content ratio of the unit of acrylate is 73.0 mass %, and the content ratio of ring structure unit is 22.7 mass %, comes from benzene The content ratio of the unit of ethylene is 2.4 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it carry out Filter.Similarly to Example 13 by obtained polymerization liquid, after autoclave processing, devolatilization is carried out in extruder, Obtain the particle of transparent resin combination (D-12).The weight average molecular weight of resin combination (D-12) is 16.2 ten thousand, and number is divided equally Son amount is 6.1 ten thousand, and glass transition temperature is 127 DEG C, and chloroform insoluble component is 0.4%, refractive index 1.500.Resin combination The island of the island structure of the non-extension film of object (D-12) is having a size of 250nm, phase difference Re and thickness side in the face of extension film To phase difference Rth be respectively 0.2nm and 4.5nm.
(2-26) embodiment 15: the modulation of resin combination (D-13)
In embodiment 13, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor Object (society, Asahi Chemical Industry system, Tuftec (registered trademark) P1083, olefinic double bond amount 2.01mmol/g, 20 matter of styrene units content Measure %) 6 parts, SEBS triblock copolymer 2 (society, Asahi Chemical Industry system, Tuftec (registered trademark) H1052, olefinic double bond amount 0.27mmol/g, 20 mass % of styrene units content, refractive index 1.500) 4 parts, MMA75 parts, MHMA13.5 parts, as passing through The monomer component St of addition is added dropwise using other than 4 parts, has carried out polymerization reaction and cyclization similarly to Example 13.By gathering Close reaction solution in residual monomers amount calculate MMA reactivity be 94%, MHMA reactivity be 94%, St reactivity be 100%.(methyl) acrylic polymer chain being bonded with SEBS triblock polymer chain calculated by reactivity, with (methyl) The ratio of components (quality criteria) of acrylic polymer is MMA:MHMA:St=82.6:14.9:2.5, comes from (methyl) acrylic acid The content ratio of the unit of ester is 72.6 mass %, and the content ratio of ring structure unit is 23.0 mass %, from styrene The content ratio of unit is 2.4 mass %.When taking out a part of reaction solution and being filtered experiment, can preferably it be filtered.It will Obtained polymerization liquid similarly to Example 13, after autoclave processing, devolatilization is carried out in extruder, is obtained The particle of bright resin combination (D-13).The weight average molecular weight of resin combination (D-13) is 15.1 ten thousand, and number-average molecular weight is 5.7 ten thousand, the glass transition temperature of high temperature side is 127 DEG C, and the glass transition temperature of low temperature side is -61 DEG C, chloroform not melt into It is divided into 0.4%, refractive index 1.500.The island of the island structure of the non-extension film of resin combination (D-13) having a size of 150nm, the phase difference Rth of phase difference Re and thickness direction is respectively 0.3nm and 3.5nm in the face of extension film.
(2-27) comparative example 12: the modulation of resin combination (D-14)
In embodiment 13, in addition to using SEBS triblock copolymer as the monomer component being initially added in reactor Object (society, Asahi Chemical Industry system, Tuftec (registered trademark) H1041, olefinic double bond amount 0.45mmol/g, 30 matter of styrene units content Measure %) 10 parts, MMA40 part, MHMA45 part, it is used other than 5 parts as the monomer component St added by dropwise addition, with embodiment 13 It has been carried out similarly polymerization reaction.The reactivity of the MMA calculated by the residual monomers amount in polymerization liquid is 94%, MHMA's The reactivity that reactivity is 90%, St is 100%.(methyl) being bonded with SEBS triblock polymer chain calculated by reactivity Acrylic polymer chain, the ratio of components (quality criteria) with (methyl) acrylic polymer is MMA:MHMA:St=45.2: The content ratio of 48.7:6.0, the unit from (methyl) acrylate are 3.7 mass %, and the content ratio of ring structure unit is 82.6 mass %, the content ratio of the unit from styrene are 6.9 mass %.It takes out a part of reaction solution and is filtered test When, observe that filter boosts.The glass transition temperature of obtained resin combination (D-14) is 158 DEG C, chloroform not melt into It is divided into 10.4%.
[table 1]
[table 2]
[table 3]
Each embodiment, the result of comparative example are incorporated in table 1- table 3.The comparison of ring structure is imported not in grafted chain The resin combination A-3 of example 1, glass transition temperature is low, and heat resistance is low.In addition, even if having imported ring structure, without containing grafting The resin combination B-1 of the comparative example 2 of copolymer, the resin combination B-2 of comparative example 3, comparative example 5 resin combination B-3, The resin combination B-4 of comparative example 8, impact strength (energy of rupture) is low, bad mechanical strength.The resin combination A-4 of comparative example 4, The resin combination C-3 of comparative example 6, the resin combination A-5 of comparative example 7, comparative example 9 resin combination C-4, comparative example 10 Resin combination D-9, the resin combination D-10 of comparative example 11, comparative example 12 resin combination D-14, grafted chain tool Circular structure unit, since the content ratio of (methyl) acrylic ester unit in grafted chain is less than 45 mass % to more than 98 Quality %, glass transition temperature is low and poor heat resistance, and impact strength (energy of rupture) is low, bad mechanical strength, or produces when preparation Raw gel compound, contains more foreign matter.On the other hand, each resin combination of embodiment 1-15, not only with well balanced side Formula has the excellent transparency, mechanical strength, heat resistance, and the generation of gel compound is few.
Industrial utilizability
According to the present invention, due to the available transparency, mechanical strength, the copolymer of excellent heat resistance and resin combination Object can be prepared excellent polarizer protective film, polarizer, image and show by the way that they are used in optical thin film etc. Device etc..

Claims (16)

1. a kind of copolymer, which contains: with the unit from alkadienes and/or alkene polymer chain (A) and Polymer chain (B) with the unit with ring structure on unit and main chain from (methyl) acrylic monomer, feature It is,
In the polymer chain (B), the content ratio of the unit from (methyl) acrylate is 45 mass % or more 98 mass % or less.
2. copolymer according to claim 1, wherein polymer chain (B) is the polymer being grafted on polymer chain (A) Chain.
3. copolymer according to claim 1 or 2, wherein the ring structure is lactone ring structure and/or maleimide Structure.
4. copolymer described in any one of -3 according to claim 1, wherein described to come from the polymer chain (B) Total content ratio of the unit with ring structure is 90 mass % on the unit and the main chain of (methyl) acrylic monomer More than.
5. a kind of resin combination, which is characterized in that the resin combination contains to be total to described in any one of claim 1-4 Polymers and (methyl) acrylic polymer.
6. resin combination according to claim 5, wherein (methyl) acrylic polymer has described come from The unit of (methyl) acrylic monomer.
7. resin combination according to claim 5 or 6, wherein (methyl) acrylic polymer has described With the unit of ring structure on main chain.
8. the resin combination according to any one of claim 5-7, wherein the resin combination is respectively 100 DEG C or more and less than 100 DEG C have glass transition temperature.
9. the resin combination according to any one of claim 5-8, wherein the resin combination is in chloroform Insoluble component is 10 mass % or less.
10. a kind of optical thin film, which contains copolymer described in any one of claim 1-4 or right is wanted Seek resin combination described in any one of 5-9.
11. a kind of polarizer, which includes optical thin film described in any one of claim 10.
12. a kind of image display device, which includes optical thin film described in any one of claim 10.
13. a kind of preparation method of copolymer is the preparation method of copolymer described in any one of claim 1-4, It is characterized in that, the preparation method includes following process,
In the presence of polymer (P1) with the unit from alkadienes and/or alkene, (methyl) acrylic compounds will be contained The process that the monomer component of monomer in monomer and ring structure with polymeric double bond is polymerize.
14. a kind of preparation method of copolymer is the preparation method of copolymer described in any one of claim 1-4, It is characterized in that, the preparation method includes following process,
In the presence of polymer (P1) with the unit from alkadienes and/or alkene, (methyl) acrylic compounds will be contained The process that the monomer component of monomer is polymerize, and
What is formed in the polymerization process has on the main chain of the polymer chain of the unit from (methyl) acrylic monomer The process for forming ring structure.
15. the preparation method of copolymer according to claim 13, wherein the preparation method further include: by the polymerization The process that the resin solution that process obtains is filtered.
16. the preparation method of copolymer according to claim 14, wherein the preparation method further include: by the ring knot It is configured to the process that the resin solution that process obtains is filtered.
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