CN102262250A - Optical film - Google Patents
Optical film Download PDFInfo
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- CN102262250A CN102262250A CN2011101398934A CN201110139893A CN102262250A CN 102262250 A CN102262250 A CN 102262250A CN 2011101398934 A CN2011101398934 A CN 2011101398934A CN 201110139893 A CN201110139893 A CN 201110139893A CN 102262250 A CN102262250 A CN 102262250A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- Crystallography & Structural Chemistry (AREA)
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polarising Elements (AREA)
- Graft Or Block Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides an optical film, which is polymerized by polymerized components in a compound. The compound comprises at least one of polymers composed of monomers expressed in a formula (1) and monomers expressed in a polymerized formula (1) and resin having aromatic nucleus or aromatic heterocyclic rings and containing 11 to 100 mole %. (R1 represents hydrogen atom or methyl, R2 represents 1 valence bridge ring type hydrocarbyl which can have substitutional groups and 5 to 15 carbon atoms, a CH2 contained in the bridge ring type hydrocarbyl can be substituted by NR3, O, CO or S, R3 represents alkyl having 1 to 3 hydrogen atoms or 1 to 3 carbon atoms, and n1 represents an integer from 1 to 3.
Description
Technical field
The present invention relates to blooming.
Background technology
Image display devices such as liquid crystal indicator use blooming.As such blooming, in TOHKEMY 2010-116528 communique, disclose and used the blooming that contains the composition of resin and N-vinylcarbazole and form, described resin has the structural unit from urethane acrylate, described urethane acrylate obtains by making polyhexamethylene carbonic ester glycol, 1,4 cyclohexane dimethanol, isophorone diisocyanate and the reaction of acrylic acid 2-hydroxy methacrylate.
Summary of the invention
The present invention provides the invention of following scheme.
＜1〉a kind of blooming obtains by making the polymerism composition polymerization that contains in the composition, and described composition contains:
In the polymkeric substance that is selected from the monomer shown in the formula (1) and obtains by the monomer shown in the gathering (1) at least a kind and
The resin that in the entire infrastructure unit, contains the structural unit of 11～100 moles of % with aromatic rings or heteroaromatic;
(in the formula, R
1Expression hydrogen atom or methyl, R
2Expression can have the endocyclic alkyl that substituent carbon number is 5～15 1 valency, contain in this endocyclic alkyl-CH
2-can be by-NR
3-,-O-,-CO-or-S-replaces; R
3Expression hydrogen atom or carbon number are 1～3 alkyl; n
1The integer of expression 0～3);
＜2〉according to＜1〉described blooming, wherein, resin is at least a kind that is selected from polycarbonate and the polyethersulfone;
＜3〉according to＜1〉or＜2〉described blooming, wherein, R
1Be methyl;
＜4〉according to＜1 〉～＜3 in each described blooming, wherein, composition also contains Photoepolymerizationinitiater initiater;
＜5〉a kind of polarizer adopts＜1 〉～＜4 in each described blooming make;
＜6〉a kind of composition, wherein contain:
In the polymkeric substance that is selected from the monomer shown in the formula (1) and obtains by the monomer shown in the gathering (1) at least a kind and
The resin that in the entire infrastructure unit, contains the structural unit of 11～100 moles of % with aromatic rings or heteroaromatic;
(in the formula, R
1Expression hydrogen atom or methyl, R
2Expression can have the endocyclic alkyl that substituent carbon number is 5～15 1 valency, contain in this endocyclic alkyl-CH
2-can be by-NR
3-,-O-,-CO-or-S-replaces; R
3Expression hydrogen atom or carbon number are 1～3 alkyl; n
1The integer of expression 0～3);
＜7〉according to＜6〉described composition, wherein, also contain Photoepolymerizationinitiater initiater;
＜8〉according to＜6〉or＜7〉described composition, wherein, also contain solvent;
＜9〉a kind of polymkeric substance is with＜6 〉～＜8 in the polymerism composition polymerization that contains in each described composition and obtaining;
＜10〉a kind of manufacture method of blooming is characterized in that, will＜8〉described composition curtain coating to the even surface after, heat up in a steamer and desolvate and obtain.
Embodiment
In the present invention, " blooming " is meant and can makes light transmissive film, be the film with optical function.Optical function is meant refraction, birefringence, antireflection, field angle expansion, light diffusion, brightness raising etc.
Blooming of the present invention obtains by the polymerism composition that contains in the polymerization composition of the present invention.
Composition of the present invention is the composition that contains following compositions:
In the polymkeric substance (being designated hereinafter simply as " polymkeric substance (1) ") that is selected from the monomer shown in the formula (1) (being designated hereinafter simply as " monomer (1) ") and obtains at least a kind by the monomer shown in the gathering (1) and
The resin (being designated hereinafter simply as " resin (2) ") that in the entire infrastructure unit, contains the structural unit of 11～100 moles of % with aromatic rings or heteroaromatic;
In the formula (1), R
1Expression hydrogen atom or methyl are preferably methyl.
R
2Expression can have the endocyclic alkyl that substituent carbon number is 5～15 1 valency.As there not being the endocyclic alkyl that replaces, can enumerate the group shown in the following formula.
Contain in this endocyclic alkyl-CH
2-can be by-NR
3-,-O-,-CO-or-S-replaces; R
3Expression hydrogen atom or carbon number are 1～3 alkyl.As carbon number is 1～3 alkyl, can enumerate methyl, ethyl and propyl group.As contain in this endocyclic alkyl-CH
2-quilt-NR
3-,-O-,-CO-or-group that S-replaces, can enumerate oxa-adamantyl, oxo adamantyl, N-methyl azepine norborny and 5-oxa--4-oxo three ring [5.2.1.0
3,7] nonyl.
As the substituting group that this endocyclic alkyl can have, (OH), carbon number is 1～3 alkoxy, amino, nitro, carboxyl (COOH), sulfo group (SO can to enumerate carbon number and be 1～3 alkyl, hydroxyl
3H), chloro (chlorine atom), bromo (bromine atoms) and iodo (iodine atom).As carbon number is 1～3 alkyl, can enumerate methyl, ethyl and propyl group.As carbon number is 1～3 alkoxy, can enumerate methoxyl, ethoxy and propoxyl group.As the endocyclic alkyl that is replaced by these substituting groups, can enumerate hydroxyadamantane base, methoxyl adamantyl, nitro norborny, carboxyl three ring decyls and chloro two ring decyls.
R
2Be preferably following radicals.
In the formula (1), n
1The integer of expression 0～3 is preferably 0 or 1.
As preferred monomer (1), can enumerate the compound shown in the formula (1-1)～(1-6).Monomer (1) is under the situation of these compounds, and the photoelastic coefficient of the blooming that obtains is littler.
Polymkeric substance (1) can be a polymerization single polymerization monomer (1) and the polymkeric substance that obtains also can be the multipolymer of monomer (1) and monomer (1) monomer in addition only.As monomer (1) monomer in addition, can enumerate the monomer shown in the formula described later (A).
Polymkeric substance (1) for example can carry out polymerization by known radical polymerization with the monomer that imports the structural unit that constitutes polymkeric substance (1) and obtain.As known radical polymerization, can enumerate solution polymerization process, suspension polymerization, emulsion polymerization and mass polymerization, consider the preferred solution polymerization from the easiness of the molecular-weight adjusting of polymkeric substance (1) and the aspect of film forming.Consider that from the aspect of the transparency of the blooming that obtains polymkeric substance (1) is preferably atactic polymers.Polymkeric substance (1) can be commercially available polymkeric substance.
As the polymerization initiator that uses in the radical polymerization; can enumerate 2; 2 '-azoisobutyronitrile; 2; 2 '-azo two (2-methylbutyronitrile); 1; 1 '-azo two (cyclohexane-1-nitrile); 2; 2 '-azo two (2; the 4-methyl pentane nitrile); 2; 2 '-azo two (2; 4-dimethyl-4-methoxyl valeronitrile); dimethyl-2; 2 '-azo two (2 Methylpropionic acid ester); 2; 2 '-azo two azo-compounds such as (2-hydroxymethyl propionitrile); lauryl peroxide; tert butyl hydroperoxide; benzoyl peroxide; tert butyl peroxy benzoate; cumene hydroperoxide; diisopropyl peroxydicarbonate; the dipropyl peroxy dicarbonate; tert-butyl hydroperoxide neodecanoic acid ester; t-butylperoxy pivarate; (3; 5; 5-trimethyl acetyl base) organic peroxide such as superoxide, and potassium persulfate; ammonium persulfate; inorganic peroxides such as hydrogen peroxide.In addition, can also enumerate and with the redox series initiators of thermal polymerization and reductive agent as polymerization initiator.
As the solvent that uses in the solution polymerization process, as long as do not hinder polymerization just unqualified.As solvent, can enumerate aromatic hydrocarbon solvents such as toluene, dimethylbenzene, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, and ketone solvent such as acetone, methyl ethyl ketone, methylisobutylketone, cyclopentanone, cyclohexanone.
In solution polymerization process, the total amount of introducing the monomer of the structural unit that constitutes polymkeric substance (1) is preferably in reaction solution more than the 10 quality %, and more preferably 15～50 quality % are preferably 20～40 quality % especially.The total amount of the monomer of the structural unit of introducing formation polymkeric substance (1) is when above-mentioned scope, and polymerization is controlled, the viscosity excellence of resulting resin solution.
Polymkeric substance (1) is under the situation of multipolymer of monomer (1) and monomer (1) monomer in addition, with respect to the total of the entire infrastructure unit of polymkeric substance (1), is preferably more than the 40 quality % from the structural unit of monomer (1), more preferably more than the 50 quality %.
Temperature of reaction in the solution polymerization process is preferably 15 ℃～120 ℃, more preferably 30 ℃～110 ℃, is preferably 40 ℃～100 ℃ especially.Polymerization temperature is in above-mentioned scope the time, and polymerization control is excellent.
The number-average molecular weight of polymkeric substance (1) is preferably 1,000～1, and 000,000, more preferably 2,000～800,000, be preferably 3,000～500,000 especially.The number-average molecular weight of polymkeric substance (1) is in above-mentioned scope the time, viscosity, film forming, toughness and the excellent heat resistance of polymkeric substance (1).
With respect at least a kind and the total amount of resin (2) being selected from monomer (1) and the polymkeric substance (1), at least a kind the content that is selected from monomer (1) and the polymkeric substance (1) in the composition of the present invention is preferably 5 quality %～70 quality %, more preferably 7 quality %～65 quality % are preferably 10 quality %～60 quality % especially.In the time of in above-mentioned scope, the photoelastic coefficient of the blooming that obtains becomes littler.
Composition of the present invention preferably contains monomer (1).
The resin that contains in the composition of the present invention (2) contains the structural unit with aromatic rings or heteroaromatic of 11～100 moles of % in the entire infrastructure unit.The content of structural unit with aromatic rings or heteroaromatic is when this scope, and the photoelastic coefficient of the blooming that obtains diminishes.The content of the structural unit with aromatic rings or heteroaromatic in the resin (2) is preferably 50～100 moles of % in the entire infrastructure unit, more preferably 80～100 moles of %.In the time of in above-mentioned scope, the photoelastic coefficient of the blooming that obtains becomes littler.
As above-mentioned aromatic rings, can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, aphthacene ring, 1,2-benzo phenanthrene ring, 9,10-benzo phenanthrene ring, pyrene ring, pentacene ring, Pi ring, benzopyrene ring, perylene ring and coronene ring, preferred phenyl ring and naphthalene nucleus.As heteroaromatic, can enumerate furan nucleus, pyrrole ring, thiphene ring, phospha luxuriant (ホ ス ホ one Le) ring, imidazole ring, purine ring, pyrazoles ring, indazole ring,
Azoles ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring etc. contain at least a heteroatoms that is selected from oxygen atom, nitrogen-atoms, sulphur atom and the phosphorus atoms ring as the ring structure atom.Structural unit with aromatic rings or heteroaromatic also can be the structural unit with ring that aromatic rings and the mutual condensation of heteroaromatic form.As such condensed ring, can enumerate coumarone ring, isobenzofuran ring, indole ring, iso-indoles ring, benzothiophene ring, the luxuriant ring of benzo phospha, benzimidazole ring, benzo
Azoles ring, benzisoxa
Azoles ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, carbazole ring, acridine ring, quinazoline ring and cinnolines ring.
As resin (2), can enumerate the resin that obtains by addition polymerization, the resin that obtains by polycondensation and the resin that obtains by ring-opening polymerization.
The resin (2) that obtains by addition polymerization can obtain by making the monomer with polymerism unsaturated double-bond carry out addition polymerization.As addition polymerization, can enumerate free radical polymerization, cationic polymerization and anionic catalytic polymerization.In from the entire infrastructure unit that constitutes monomer resin (2), that have the polymerism unsaturated double-bond obtain by addition polymerization, be 11～100 moles of % from the ratio of the structural unit of monomer with aromatic rings or heteroaromatic and polymerism unsaturated double-bond.
As monomer, can enumerate styrene, methyl styrene, chlorostyrene, vinyl benzoic acid, vinylphenol, vinyl naphthalene, vinyl anthracene, phenyl acrylate, phenyl methacrylate, acrylic acid naphthalene ester, methacrylic acid naphthalene ester, benzyl acrylate, benzyl methacrylate and N-phenylmaleimide with aromatic rings and polymerism unsaturated double-bond.
As monomer, can enumerate vinyl indoles, vinyl imidazole, vinylpyridine, vinylcarbazole and vinyl phthalimide with heteroaromatic and polymerism unsaturated double-bond.
The resin (2) that obtains by addition polymerization can be to have the polymerism unsaturated double-bond and do not have the monomer of aromatic rings or heteroaromatic and have the polymerism unsaturated double-bond and have aromatic rings or the multipolymer of the monomer of heteroaromatic.As having the polymerism unsaturated double-bond and not having the monomer of aromatic rings or heteroaromatic, can enumerate the monomer that does not have aromatic rings or heteroaromatic in the monomer (A) shown in the formula described later (A).
As the resin that obtains by addition polymerization (2), can enumerate polystyrene, polymethylstyrene, polychlorostyrene, the polyvinyl benzoic acid, polyvinyl pyrrolidone, the polyvinyl indoles, polyvinylphenol, polyvinylnaphthaleneand, the polyvinyl anthracene, polyvinyl imidazol, polyvinylpyridine, Polyvinyl carbazole, the polyvinyl phthalimide, the polyacrylic acid phenyl ester, the polymethyl acid phenenyl ester, polyacrylic acid naphthalene ester, polymethylacrylic acid naphthalene ester, the polypropylene acid benzyl ester, polybenzyl methacrylate, styrene-maleic anhydride copolymer, Styrene-Butadiene and styrene-acrylonitrile copolymer.
As the resin that obtains by polycondensation (2), can enumerate polycarbonate, polyester (for example polyethylene terephthalate, polybutylene terephthalate etc.), polyethersulfone, polyurethane, urethane acrylate, polyureas, polyurethane-urea, polyurethane-urea acrylate, polyimide, polyamide, phenolics and melamine resin.
Consider resin (2) optimization polycarbonate or polyethersulfone from the film strength, processability and the thermotolerance aspect that obtain.
Polycarbonate obtains by the polycondensation in 1: 1 of diatomic alcohol compounds photoreactive gas.With mutual bonding, 1 from diatomic alcohol compounds (have the structure of 2 hydroxyls (compound OH)) and 1 from the structure of phosgene during together as 1 structural unit, resin (2) contains the structural unit with aromatic rings or heteroaromatic of 11～100 moles of % in the entire infrastructure unit of resin (2).In polycarbonate, the structural unit with aromatic rings or heteroaromatic is the structural unit that contains from the structure of the diatomic alcohol compounds with aromatic rings or heteroaromatic.
As diatomic alcohol compounds with aromatic rings or heteroaromatic, can enumerate catechol, resorcinol, p-dihydroxy-benzene, methyl hydroquinone, the phenyl p-dihydroxy-benzene, 1, the 2-dihydroxy naphthlene, 1, the 3-dihydroxy naphthlene, 1, the 4-dihydroxy naphthlene, 1, the 5-dihydroxy naphthlene, 1, the 6-dihydroxy naphthlene, 1, the 7-dihydroxy naphthlene, 2, the 3-dihydroxy naphthlene, 2, the 6-dihydroxy naphthlene, 2, the 7-dihydroxy naphthlene, 2,2 '-biphenol, 4,4 '-biphenol, 2,2-pair-(4-hydroxy phenyl) propane, 1,1-pair-(4-hydroxy phenyl) methane, 4,4 '-ethylidene bis-phenol, 4,4 '-dihydroxy benaophenonel, 2,2 '-dihydroxy benaophenonel, 2,4 dihydroxyl benzophenone, 2,4 '-dihydroxy benaophenonel, 2,2 '-dihydroxydiphenyl ether, 4,4 '-dihydroxydiphenyl ether, 3,3 '-dihydroxy diphenylamine, 4,4 '-dihydroxy-diphenyl sulfone, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl) sulfone, two (4-hydroxy phenyl) thioether, two (4-hydroxy-3-methyl phenyl) thioether, 4,4 '-dihydroxy tetraphenylmethane, 1,1 '-two-(4-hydroxy phenyl) cyclohexane, 1,1 '-two-(4-hydroxy phenyl)-3,3 ', the 5-trimethyl-cyclohexane, 9,9 '-two (4-hydroxy phenyl) fluorenes, 9,9 '-two (4-hydroxy-3-methyl phenyl) fluorenes and 9,9 '-two (3-amino-4-hydroxy phenyl) fluorenes.
As polycarbonate, can enumerate 2, the condensed polymer and 1 of 2-pair-(4-hydroxy phenyl) propane and phosgene, the condensed polymer of 1-pair-(4-hydroxy phenyl) methane and phosgene.
Polyethersulfone is to have the binary organic group to pass through-SO
2-and-resin of the main chain of the mutual bonding of O-, compound that for example can be by having the halogen atom 2 or more and having-SO
2-and 2 above hydroxyls (polycondensation of compound OH), have the compound of the hydroxyl 2 or more and have-SO
2-and the polycondensation of the compound of 2 above halogen atoms and obtaining.Will be from the structure of above-mentioned compound with the halogen atom more than 2 with from the structure of compound during respectively as 1 structural unit with the hydroxyl more than 2, in the entire infrastructure unit in resin, contain the structural unit of 11～100 moles of % with aromatic rings or heteroaromatic.
As having aromatic rings or heteroaromatic and having the compound of the hydroxyl more than 2, can enumerate above-mentioned diatomic alcohol compounds with aromatic rings or heteroaromatic.As having aromatic rings or heteroaromatic and having-SO
2-(compound OH) can be enumerated 4,4 ' dihydroxy-diphenyl sulfone and two (4-hydroxyl-3,5-3,5-dimethylphenyl) sulfones with 2 above hydroxyls.
As having aromatic rings or heteroaromatic, and compound with the halogen atom more than 2, can enumerate 2,2 '-two (4-fluoro phenyl) propane, 2,2 '-two-(4-chlorophenyl) propane, 2,2 '-two-(4-bromo phenyl) propane, 2,2 '-two-(4-iodine substituted phenyl) methane, 1,1 '-two (4-fluoro phenyl) methane, 1,1 '-two-(4-chlorophenyl) methane, 1,1 '-two-(4-bromo phenyl) methane, 1,1 '-two-(4-iodine substituted phenyl) methane, 4,4 '-two fluoro benzophenone, 4,4 '-benzophenone of dichloro, 4,4 '-two bromo benzophenone, 4,4 '-two iodo benzophenone, 2,2 '-two fluoro benzophenone, 2,2 '-benzophenone of dichloro, 2,2 '-two bromo benzophenone, 2,2 '-two iodo benzophenone, 2,4-two fluoro benzophenone, 2, the 4-benzophenone of dichloro, 2,4-two bromo benzophenone, 2,4-two iodo benzophenone, 2,4 '-two fluoro benzophenone, 2,4 '-benzophenone of dichloro, 2,4 '-two bromo benzophenone, 2,4 '-two iodo benzophenone, 2,2 '-two fluoro diphenyl ethers, 2,2 '-dichloro-diphenyl ether, 2,2 '-two bromo diphenyl ethers, 2,2 '-two iodo diphenyl ethers, 4,4 '-two fluoro diphenyl ethers, 4,4 '-dichloro-diphenyl ether, 4,4 '-two bromo diphenyl ethers, 4,4 '-two iodo diphenyl ethers, 3,3 '-two fluoro diphenylamine, 3,3 '-dichloro-diphenylamine, 3,3 '-two bromo diphenylamine, 3,3 '-two iodo diphenylamine, two (4-fluoro phenyl) thioether, two (4-chlorophenyl) thioether, two (4-bromo phenyl) thioether, two (4-iodine substituted phenyl) thioether, two (4-fluoro-3-aminomethyl phenyl) thioether, two (4-chloro-3-aminomethyl phenyl) thioether, two (4-bromo-3-aminomethyl phenyl) thioether and two (4-iodo-3-aminomethyl phenyl) thioether.
As having aromatic rings or heteroaromatic and having-SO
2-and the compound of 2 above halogen atoms, can enumerate 4,4 '-two fluoro diphenyl sulfones, 4,4 '-dichloro-diphenyl sulfone, 4,4 '-two bromo diphenyl sulfones, 4,4 '-two iodo diphenyl sulfones, two (4-fluoro-3, the 5-3,5-dimethylphenyl) sulfone, two (4-chloro-3, the 5-3,5-dimethylphenyl) sulfone, two (4-bromo-3,5-3,5-dimethylphenyl) sulfone and two (4-iodo-3,5-3,5-dimethylphenyl) sulfone.
As polyethersulfone, can enumerate in the presence of sal tartari, make the reaction of dichloro diphenylsulfone and bisphenol S and the resin that obtains; In the presence of potassium hydroxide, make 4 of 50 moles of %, 4 of 4 '-dihydroxy benaophenonel, 30 moles of %, 4 of 4 '-dichloro benzophenone and 20 moles of %, 4 '-dichloro diphenylsulfone reaction and the resin that obtains; And the resin of No. 1678805 record of Jap.P..
From the viscosity of resin (2), the viewpoint of toughness, processability and the optical characteristics of the dissolubility of solvent, the blooming that obtains is considered that the number-average molecular weight of resin (2) is preferably 1,000～1,000,000.The weight-average molecular weight of resin (2) is preferably 1,000～3,000,000.
With respect to being selected from monomer (1) and the polymkeric substance (1) at least a kind total amount with resin (2), the content of resin (2) is preferably 30 quality %～95 quality %, and more preferably 35 quality %～93 quality % are preferably 40 quality %～90 quality % especially.In the time of in above-mentioned scope, the photoelastic coefficient of the blooming that obtains is littler.
Composition of the present invention preferably contains Photoepolymerizationinitiater initiater (3).Photoepolymerizationinitiater initiater is the compound that produces living radical, acid by illumination.Wherein, more preferably produce the polymerization initiator of living radical by illumination.
As Photoepolymerizationinitiater initiater, can enumerate benzoin compound, benzophenone cpd, aceotphenone compound, acyl group phosphine oxide compound, triaizine compounds, iodine
Salt and sulfonium salt.
As the benzoin compound, can enumerate benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether and benzoin isobutyl ether.
As benzophenone cpd, can enumerate benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone and 2,4, the 6-tri-methyl benzophenone.
As aceotphenone compound, can enumerate diethoxy acetophenone, 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1,2-diphenyl-2,2-dimethoxy-ethane-1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer of propane-1-ketone.
As the acyl group phosphine oxide compound, can enumerate 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide and two (2,4,6-trimethylbenzene formyl) phenyl phosphine oxide.As triaizine compounds, can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1,3 of 4-, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl of 4-]-1,3,5-triazines and 2, two (the trichloromethyl)-6-[2-(3 of 4-, the 4-Dimethoxyphenyl) vinyl]-1,3,5-triazines.
As Photoepolymerizationinitiater initiater (3), also can use Irgacure907, Irgacure184, Irgacure651, Irgacure819, Irgacure250, Irgacure369, Irgacure OXE01, Irgacure OXE02 (above) all by BASF JAPAN (strain) system, Seikuol BZ, Seikuol Z, Seikuol BEE (above) all by Seiko chemistry (strain) system, KAYACURE BP100, KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS (above) all by Japanese chemical drug (strain) system, UVI-6992 (DOW corporate system), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1414, Adeka Optomer N-1606, Adeka Optomer N-1717, Adeka Optomer N-1919 (above) all by (strain) ADEKA system, TAZ-A, TAZ-PP (above) and TAZ-104 commercially available Photoepolymerizationinitiater initiaters such as (Sanwa Chemical corporate systems) by Nihon SiberHegner corporate system.
With respect to being selected from monomer (1) and the polymkeric substance (1) at least a kind total amount with resin (2), the content of Photoepolymerizationinitiater initiater (3) is generally 0.1 quality %-10 quality %, is preferably 0.5 quality %～5 quality %.In the time of in above-mentioned scope, the transmissivity of gained blooming uprises.And then, because the degree of polymerization of monomer (1) etc. uprises, so the photoelastic coefficient of the blooming that can reduce to obtain.
Composition of the present invention can also contain photosensitizer.In order to promote to produce free radical, acid, and carry out the polymerization of monomer (1) etc., be used in combination with Photoepolymerizationinitiater initiater with high sensitivity from Photoepolymerizationinitiater initiater (3).As photosensitizer, (for example can enumerate xanthone compounds such as xanthone, thioxanthones, 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone etc.), anthracene, have substituent anthracene compounds such as alkyl ether (for example, dibutoxy anthracene etc.), phenothiazine and rubrene.
With respect to being selected from monomer (1) and the polymkeric substance (1) at least a kind total amount with resin (2), the use amount of photosensitizer is generally 0.1 quality %～30 quality %, is preferably 0.5 quality %～10 quality %.In the time of in above-mentioned scope, can make monomer polymerizations such as (1), can access the blooming of high-transmission rate with high sensitivity.
Composition of the present invention can also contain the compound shown in the formula (A) (below, abbreviate monomer (A) as).
In the formula (A), R
3Be hydrogen atom or methyl, be preferably hydrogen atom.
In the formula (A), R
4Be that can to have ester ring type alkyl that substituent carbon number is 6～20 1 valency, can have substituent carbon number be that the aryl radical of 6～20 1 valency maybe can have the heterocyclic group that substituent carbon number is 4～20 1 valency.
Be the ester ring type alkyl of 6～20 1 valency as carbon number, can enumerate cyclohexyl, suberyl, ring octyl group, decahydro naphthyl, three ring decyls, isobornyl, norborny and adamantyl.
Be the aryl radical of 6～20 1 valency as carbon number, can enumerate the group shown in phenyl, naphthyl, anthryl and the following formula.
Be the heterocyclic group of 4～20 1 valency as carbon number, can enumerate pyrrole radicals, furyl, thienyl, pyrazinyl, pyrazolyl, imidazole radicals, pyridine radicals, piperidyl, piperazinyl, tetrahydrofuran base, indyl, thiazolyl and carbazyl.
In addition, these groups condensation mutually.R
4Be preferably carbon number and be the aryl radical of 6～20 1 valency or carbon number and be the heterocyclic group of 4～20 1 valency.
Above-mentioned ester ring type alkyl, aryl radical and heterocyclic group can have substituting group respectively, as substituting group, can enumerate hydroxyl (OH); Carbon numbers such as methyl, ethyl, isopropyl, the tert-butyl group, octyl group are 1～12 alkyl; Carbon number such as methoxyl, ethoxy is 1～12 alkoxy; Carbon numbers such as phenyl, naphthyl, phenyl are 6～12 aryl; Carbon numbers such as benzyl are 7～12 aralkyl; Glycidoxy; Carbon numbers such as acetyl group are 2～4 acyl group; Carbon numbers such as acetoxyl group are 1～12 acyloxy; Amino; Methylamino, ethylamino, dimethylamino etc. are the amino that 1～12 alkyl replaces by 1 or 2 carbon numbers; Fluorine-based (fluorine atom), chloro (chlorine atom), bromo halo groups (halogen atom) such as (bromine atoms); Oxo group (=O); And carboxyl (CO
2H).
As R
4Monomer (A) for aryl radical, can enumerate styrene, o-methyl styrene, between methyl styrene, p-methylstyrene, 2, the 4-dimethyl styrene, adjacent ethyl styrene, to ethyl styrene, trimethylbenzene ethene, propylstyrene, t-butyl styrene, cyclohexyl benzene ethene, dodecyl styrene, hydroxy styrenes, tert-butoxy styrene, vinyl benzoic acid, vinyl acetate base benzyl ester, chloro styrene, to chlorostyrene, aminobenzene ethene, 4-ethenylphenyl benzene, 2-ethyl-4-benzyl styrene, 4-(phenyl butyl) styrene, 4-hydroxyl-4 '-vinyl biphenyl, vinyl naphthalene and vinyl anthracene.
As R
4Be the monomer (A) of heterocyclic group, can enumerate N-vinyl pyrrolidone, N-vinylcarbazole, N-vinylpyridine, N-vinyl phthalimide and N-vinyl indoles etc.
As monomer (A), optimization styrene, N-vinylcarbazole, vinyl naphthalene and vinyl anthracene, more preferably styrene and N-vinylcarbazole.During for these monomers, the blooming that obtains can carry out consistent more polarized light conversion in broadband.
With respect to the amount of having removed solvent and Photoepolymerizationinitiater initiater from composition of the present invention, the content of monomer (A) is generally 0～40 quality %, is preferably 10～30 quality %, is preferably 15～20 quality especially.If in above-mentioned scope, the blooming that then obtains can carry out consistent more polarized light conversion in broadband.
Monomer (A) can use separately, also can be also with multiple.
Composition of the present invention can contain the compound shown in the formula (B) (being designated hereinafter simply as monomer (B)).
In the formula (B), R
5For hydrogen atom or methyl, be preferably methyl.
In the formula (B), R
6For-OR
7Or NR
7R
8, R
7For hydrogen atom or carbon number are 1～6 alkyl, R
8Be that carbon number is 1～6 alkyl.The hydrogen atom that contains in this alkyl can be by hydroxyl (OH) or carboxyl (CO
2H) replace, contain in this alkyl-CH
2-can by-O-,-CO-,-S-or NH-replace.
As carbon number is 1～6 alkyl, can enumerate methyl, ethyl and hexyl.
As the object lesson of monomer (B), can enumerate acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, sec-butyl acrylate, the secondary butyl ester of methacrylic acid, tert-butyl acrylate, the metering system tert-butyl acrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-(dimethylamino) ethyl ester, methacrylic acid 2-(dimethylamino) ethyl ester, glycerine one acrylate and glycerine monomethyl acrylate.
As monomer (B), preferable methyl acrylic acid 2-hydroxy methacrylate, methacrylic acid 2-(dimethylamino) ethyl ester and glycerine monomethyl acrylate.If be these monomers, then can improve the degree of polymerization, and the transmissivity of the blooming that obtains and flatness height.
With respect to the amount of having removed solvent and Photoepolymerizationinitiater initiater from composition of the present invention, the content of monomer (B) is generally 0～50 quality %, is preferably 3～30 quality %, is preferably 5～25 quality % especially.If in above-mentioned scope, then can carry out copolymerization and improve the degree of polymerization, and can obtain the blooming of high-transmission rate with monomer (1) etc.
Monomer (B) can use separately, also can be also with multiple.
Composition of the present invention preferably contains solvent.As solvent, can enumerate tetrahydrofuran, oxinane, 1,4-two
Alkane, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethyl carbitol, the diglycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, the propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, the diethylene glycol monoethyl ether acetic acid esters, the diethylene glycol monobutyl ether acetic acid esters, methoxy butyl acetate, acetate methoxyl pentyl ester, methyl phenyl ethers anisole, phenetol, ether solvents such as methylbenzene methyl ether;
Benzene,toluene,xylene, industry
Deng aromatic hydrocarbon solvent;
Ketone solvents such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone;
Alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol and glycerine;
Ethyl acetate, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, ester solvents such as gamma-butyrolacton;
N, amide solvents such as dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone;
And dimethyl sulfoxide (DMSO).
Composition of the present invention contains under the situation of solvent, and with respect to composition of the present invention, the content of solvent is generally 30～95 quality %, is preferably 40～90 quality %, is preferably 50～80 quality % especially.If in above-mentioned scope, then dissolved monomer, initiating agent equably, and then the coating homogeneity excellence of composition.
Solvent can use separately, also can be also with multiple.
Composition of the present invention can contain polymerization inhibitor, levelling agent and plastifier as required.
As polymerization inhibitor, can enumerate catechol, pyrogallol classes, 2 such as hydroquinone type, butyl-catechol such as p-dihydroxy-benzene, 2,6,6-tetramethyl-free radical scavenger, benzenethiol class, beta-naphthylamine class and betanaphthol classes such as 1-piperidyl oxygen base free radical.
With respect at least a kind and the total amount of resin (2) being selected from monomer (1) and the polymkeric substance (1), the content of polymerization inhibitor is preferably 0.1 quality %～30 quality %, more preferably 0.5 quality %～10 quality %.In the time of in above-mentioned scope, can access high-transmission rate and stable blooming.
As levelling agent, can enumerate organically-modified silicone oil is that levelling agent, polyacrylate are that levelling agent and perfluoroalkyl are levelling agent.Specifically can enumerate DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (above) entirely by Toray Dow Corning (strain) system, KP321, KP323, KP324, KP326, KP340, KP341 (above) all by SHIN-ETSU HANTOTAI's chemical industry (strain) system, TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (above) all by MOMENTIVE PERFORMANCE MATERIALS JAPAN LLC system, Fluorinert (trade name) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (above) all by Sumitomo 3M (strain) system, Megaface (trade name) R-08, Megaface R-30, Megaface R-90, Megaface F-410, Megaface F-411, Megaface F-443, Megaface F-445, Megaface F-470, Megaface F-477, Megaface F-479, Megaface F-482, Megaface F-483 (above) by DIC (strain) system, EFTOP (trade name) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (above) all by Mitsubishi Materials Electronic Chemicals (strain) system, Surfron (trade name) S-381, Surfron S-382, Surfron S-383, Surfron S-393, Surfron SC-101, Surfron SC-105, KH-40, SA-100 (above) all by AGC Agc Seimi Chemical Co., Ltd. system, trade name E1830, trade name E5844 (Daikin Fine Chemical Kenkyusho, K.K. system).
Levelling agent can use separately, also can be also with multiple.
By using levelling agent, can be so that the film that arrives be more level and smooth.And then during film forming, can control the flowability of composition of the present invention, perhaps regulate the cross-linking density of blooming of the present invention.
With respect to the amount of removing from composition of the present invention after desolvating, the content of levelling agent is generally 0.0001 quality %～2 quality %, is preferably 0.0005 quality %～1 quality %.If in above-mentioned scope, then can obtain high-transmission rate and level and smooth blooming.
As plastifier, can enumerate phosphate, carboxylate and ethyl glycolate.As phosphate, can enumerate Triphenyl phosphate (TPP), tricresyl phosphate (TCP), phosphate toluene diphenyl ester, octyl diphenyl phosphate, phosphoric acid xenyl diphenyl ester, trioctyl phosphate and tributyl phosphate etc.
As carbonic ester; can enumerate repefral (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP), di (2-ethylhexyl) phthalate phthalic esters such as (DEHP); citrates such as O-CitroflexA-2 (OACTE), O-citroflex A-4 (OACTB), acetyl triethyl citrate, acetyl tributyl citrate, butyl oleate, methyl ricinoleate, dibutyl sebacate and various trimellitate.
As ethyl glycolate, can enumerate glycerol triacetate; glycerin tributyrate; butyl phthalyl butyl glycolate; ethyl phthalyl ethyl glycollate; methyl phthalyl ethyl glycollate; the trimethylolpropane tris benzoic ether; pentaerythrite four benzoic ethers; one two (trimethylolpropane) tetracetate that contracts; one two (trimethylolpropanes), four propionic esters that contract; pentaerythrite tetra-acetate; sorbitol hexaacetate; D-sorbite six propionic esters; D-sorbite triacetate tripropionate; inositol pentaacetate and sorbitan four butyric esters.
As plastifier, can further enumerate (two) pentaerythritol esters of Japanese kokai publication hei 11-124445 communique record, the glyceride type of Japanese kokai publication hei 11-246704 communique record, the double glyceride class of TOHKEMY 2000-63560 communique record, the citric acid ester type of Japanese kokai publication hei 11-92574 communique record, the substituted-phenyl phosphoric acid ester of Japanese kokai publication hei 11-90946 communique record etc.
Wherein, as plastifier; preferably phosphoric acid triphenyl ester; tricresyl phosphate; phosphate toluene diphenyl ester; tributyl phosphate; repefral; diethyl phthalate; dibutyl phthalate; dioctyl phthalate; di (2-ethylhexyl) phthalate; glycerol triacetate; ethyl phthalyl ethyl glycollate; the trimethylolpropane tris benzoic ether; pentaerythrite four benzoic ethers; one two (trimethylolpropane) tetracetate that contracts; pentaerythrite tetra-acetate; sorbitol hexaacetate; D-sorbite six propionic esters and D-sorbite triacetate tripropionate, more preferably Triphenyl phosphate; diethyl phthalate; ethyl phthalyl ethyl glycollate; the trimethylolpropane tris benzoic ether; pentaerythrite four benzoic ethers; one two (trimethylolpropane) tetracetate that contracts; sorbitol hexaacetate; D-sorbite six propionic esters and D-sorbite triacetate tripropionate.
With respect to the amount of removing from composition of the present invention after desolvating, the content of plastifier is preferably 0.1～30 quality %.Plastifier can use separately, also can be also with multiple.
Blooming of the present invention is the blooming that obtains by the polymerism composition polymerization that will contain in the composition of the present invention.This blooming has preferably further carried out the film that stretches.Can carry out polymerization and stretching respectively, also can carry out simultaneously.In addition, carry out respectively can stretching after the polymerization under the situation of polymerization and stretching, carry out polymerization after also can stretching.The polymerization of polymerization preferred light.More preferably, make the polymerism composition that contains in the said composition carry out photopolymerization, stretch and obtain blooming composition film forming of the present invention.
As the method that makes composition film forming of the present invention, can enumerate with composition curtain coating of the present invention to even surface and heat up in a steamer the solvent cast method of desolvating, be membranaceous extrusion by melting etc. with melt extruding machine etc. with composition extrusion molding of the present invention.The solvent cast method is because film forming and preferred easily.
As the method for the polymerism composition polymerization that will contain in the composition of the present invention, can enumerate method to the composition irradiating ultraviolet light of the present invention of film forming etc.As the generation source of ultraviolet light, can enumerate fluorescence chemical lamp, black lamp, low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, sunray, electrodeless lamp etc.The exposure intensity of ultraviolet light can be carried out with certain intensity all the time, also can change intensity in photopolymerisable process.
As the method that will stretch, can enumerate the pulling method that utilizes stenter, utilize pulling method that stretches between roller etc. by the film that composition of the present invention obtains.Stretching can be uniaxial tension, in biaxial stretch-formed any, also can be vertically stretch, in the horizontal stretching any.
As the method for uniaxial tension, can enumerate utilize stretch between roller to uniaxial tension method longitudinally, used stenter to horizontal uniaxial tension method etc.; As biaxial stretch-formed method, can enumerate the track width of the tenter clip gap that strengthens clamping film side, according to the expansion of guide rail, also biaxial stretch-formed when laterally stretching in longitudinal stretching; After utilizing the longitudinal stretching that stretches between roller, with its both ends of tenter clip gap clamping, with stenter to the biaxial stretch-formed method one by one of horizontal stretching etc.
Consider preferred horizontal uniaxial tension and biaxial stretch-formed, preferred especially horizontal uniaxial tension from the viewpoint of throughput rate.
By horizontal uniaxial tension, biaxial stretch-formed, can obtain having the blooming of optics biaxiality.Here, the optics biaxiality is meant that the refractive index with the vertical both direction in the face is made as n respectively
x, n
y(n wherein
x＞n
y), the refractive index of thickness direction is made as n
zThe time, n
x≠ n
y≠ n
zCharacter.
Blooming with optics biaxiality also can carry out the polarized light conversion of unanimity to the thickness direction of blooming.
If the photoelastic coefficient of blooming is little, then show the good optical characteristic, and then when being applicable to display device, tonal variation is few, can carry out excellent black demonstration (?represent).Specifically, photoelastic coefficient is preferably 50 * 10
-12Pa
-1Below.
Blooming of the present invention is because photoelastic coefficient is little, so can be used as λ/2 plates and λ/4 plate equiphase difference plates, field angle raising film etc.In addition, when blooming is λ/4 plates, can and make broadband circular polarizing disk, in addition, during for λ/2 plates, itself and straight line polaroid can be made up and make broadband polarized light rotating element itself and the combination of straight line polaroid.They can be used for the anti-reflection filter of various liquid crystal indicators, cathode ray tube (CRT), touch panel, electroluminescence (EL) lamp etc. and liquid crystal projector etc.
Embodiment
Below, further describe the present invention according to embodiment, but the invention is not restricted to these embodiment." % " in the example and " part ", quality % and mass parts are just represented in short of special record respectively.
(synthesis example 1)
In the reactive tank that possesses stirring machine, thermometer and reflux condenser, add 20.64 parts of polyhexamethylene carbonic ester glycol (mean molecular weight 860), 1,113.41 parts of 5.19 parts of 4-cyclohexanedimethanols, 0.11 part of dibutyl tin laurate and propylene glycol methyl ether acetates, under stream of nitrogen gas stirs, splash into 14.67 parts of isophorone diisocyanate.After splashing into end, under stream of nitrogen gas, in 90 ℃ of reactions 5 hours.Then, add 1.60 parts of acrylic acid 2-hydroxy methacrylates in the reaction mixture that obtains, in 50 ℃ of reactions 1 hour, having obtained containing number-average molecular weight was 4.0 * 10
4The urethane acrylate solution of urethane acrylate.This urethane acrylate does not contain the structural unit with aromatic rings or heteroaromatic.
Number-average molecular weight is to use gel permeation chromatography (GPC) (eastern Cao (strain) system, the polystyrene conversion value of HLC-8220) analyzing under the following analysis condition.
[preparation of compositions]
(embodiment 1～6)
Mix following compositions, prepared composition 1～6.
Monomer (1): 10 parts of the compounds of table 1 record
Resin (2): 138 parts of solution (A)
Photoepolymerizationinitiater initiater (3): 0.4 part of phenyl (1-hydroxy-cyclohexyl) ketone (Irgacure 184:BASFJAPAN (strain) system)
Solvent: 20 parts of chloroforms
Levelling agent: Megaface F-477 (DIC (strain) system)
Solution (A): the poly bisphenol carbonic ester (content of the structural unit in the entire infrastructure unit: (Sigma-Aldrich Japan (strain) system 100 moles of %) with aromatic rings or heteroaromatic, weight-average molecular weight=64,000, Tg=150 ℃) chloroformic solution (solid component content: 15%)
(embodiment 7～12)
Mix following compositions, prepared composition 7～12.
Monomer (1): 10 parts of the compounds of table 1 record
Resin (2): 80 parts of-solution (B)
0.4 part of Photoepolymerizationinitiater initiater (3): Irgacure 184 (BASFJAPAN (strain) system)
Solvent: N, 20 parts of dinethylformamide/cyclohexanone/2-butanone mixed solvent (mixing ratio is counted 20: 80: 25 with volume ratio)
Levelling agent: Megaface F-477 (DIC (strain) system)
Solution (B): the polyethersulfone compound (content of the structural unit in the entire infrastructure unit: (trade name: Sumika Excel PES 4800P 100 moles of %) with aromatic rings or heteroaromatic, Sumitomo Chemical (strain) system) N, dinethylformamide/cyclohexanone/2-butanone mixed solvent (mixing ratio is counted 20: 80: 25 with volume ratio) solution (solid component content: 25%)
Table 1
[making of blooming]
With applicator (gap width: 500 μ m), composition 1～12 is coated on the mold release film (thickness 188 μ m) of polyethylene terephthalate system, then in closed container, at room temperature placed 5 minutes, then following dry 10 minutes at 40 ℃, and then after under 80 ℃ dry 15 minutes, carry out 600mJ/cm with high-pressure sodium lamp
2The illumination of (365nm benchmark).After the illumination, peel off, obtained blooming from mold release film.
(comparative example 1)
With 7 parts of 66.7 parts of urethane acrylate solution, the N-vinylcarbazole of making in the synthesis example 1, (Irgacure 184 for Photoepolymerizationinitiater initiater (3), Ciba Specialty Chemicals (strain) system) 0.4 part, propylene glycol methyl ether acetate mix preparation solution for 20.0 parts.(gap width: 700 μ m), on the mold release film of polyethylene terephthalate system, then 80 ℃ of dryings 15 minutes, (high-pressure sodium lamp: every 1Pass is 650mJ/cm to carry out the UV irradiation with this solution coat with applicator
2: 365nm), and then serviceability temperature regulates the AutoGraph drawing machine and stretches 3.0 times, obtains blooming.
[mensuration of photoelastic coefficient]
Cut out the sheet of 150mm * 600mm size from the blooming that obtains, use automatic birefringence meter (KOBRA-WR, prince's instrumentation machine (strain) system), at room temperature, phase difference value (Re) in the face when scope that is determined at 0N～50N respectively changes 5 tension force is obtained photoelastic coefficient by the slope of the near linear of making according to following formula.The results are shown in table 2.
Re/d＝C·σ
Wherein, d represents the thickness of blooming, and σ represents tension force, and C represents photoelastic coefficient.
[table 2]
| Photoelastic coefficient/Pa -1 | |
| Embodiment 1 | 17×10 -12 |
| Embodiment 2 | 19×10 -12 |
| Embodiment 3 | 42×10 -12 |
| Embodiment 4 | 12×10 -12 |
| Embodiment 5 | 18×10 -12 |
| Embodiment 6 | 20×10 -12 |
| Embodiment 7 | 35×10 -12 |
| Embodiment 8 | 40×10 -12 |
| Embodiment 9 | 47×10 -12 |
| Embodiment 10 | 33×10 -12 |
| Embodiment 11 | 35×10 -12 |
| Embodiment 12 | 38×10 -12 |
| Comparative example 1 | 110×10 -12 |
The photoelastic coefficient of blooming of having confirmed embodiment is little.
Utilize possibility on the industry
Blooming of the present invention so it is few to possess the display device tonal variation of blooming of the present invention, can carry out excellent black demonstration because photoelastic coefficient is little.
Claims (10)
1. a blooming obtains by making the polymerism composition polymerization that contains in the composition, and described composition contains:
In the polymkeric substance that is selected from the monomer shown in the formula (1) and obtains by the monomer shown in the gathering (1) at least a kind and
The resin that in the entire infrastructure unit, contains the structural unit of 11～100 moles of % with aromatic rings or heteroaromatic;
In the formula, R
1Expression hydrogen atom or methyl, R
2Expression can have the endocyclic alkyl that substituent carbon number is 5～15 1 valency, contain in this endocyclic alkyl-CH
2-can be by-NR
3-,-O-,-CO-or-S-replaces; R
3Expression hydrogen atom or carbon number are 1～3 alkyl; n
1The integer of expression 0～3.
2. blooming according to claim 1, wherein, resin is at least a kind that is selected from polycarbonate and the polyethersulfone.
3. blooming according to claim 1, wherein, R
1Be methyl.
4. blooming according to claim 1, wherein, composition also contains Photoepolymerizationinitiater initiater.
5. polarizer adopts in the claim 1～4 each described blooming to make.
6. composition, contain:
In the polymkeric substance that is selected from the monomer shown in the formula (1) and obtains by the monomer shown in the gathering (1) at least a kind and
The resin that in the entire infrastructure unit, contains the structural unit of 11～100 moles of % with aromatic rings or heteroaromatic;
In the formula, R
1Expression hydrogen atom or methyl, R
2Expression can have the endocyclic alkyl that substituent carbon number is 5～15 1 valency, contain in this endocyclic alkyl-CH
2-can be by-NR
3,-O-,-CO-or-S-replaces; R
3Expression hydrogen atom or carbon number are 1～3 alkyl; n
1The integer of expression 0～3.
7. composition according to claim 6 wherein, also contains Photoepolymerizationinitiater initiater.
8. according to claim 6 or 7 described compositions, wherein, also contain solvent.
9. a polymkeric substance obtains by the polymerism composition that contains in the described composition of polymerization claim 6.
10. the manufacture method of a blooming after the described composition curtain coating of claim 8 is to the even surface, is heated up in a steamer and is desolvated and obtain.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-122505 | 2010-05-28 | ||
| JP2010122505 | 2010-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102262250A true CN102262250A (en) | 2011-11-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101398934A Pending CN102262250A (en) | 2010-05-28 | 2011-05-24 | Optical film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2012008547A (en) |
| KR (1) | KR20110131112A (en) |
| CN (1) | CN102262250A (en) |
| TW (1) | TW201209093A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110199210A (en) * | 2017-01-20 | 2019-09-03 | 住友化学株式会社 | The manufacturing method of optical film and optical film |
| CN111971589A (en) * | 2018-03-30 | 2020-11-20 | 三井化学株式会社 | Optical lens |
| CN112566949A (en) * | 2018-08-09 | 2021-03-26 | 住友化学株式会社 | Resin and adhesive composition |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013089091A1 (en) * | 2011-12-16 | 2013-06-20 | リンテック株式会社 | Curable resin composition, curable resin molded body, cured resin molded body, method for producing each of same, and laminate body |
| US9102833B2 (en) | 2011-12-16 | 2015-08-11 | Lintec Corporation | Curable resin composition, curable resin molded body, cured resin molded body, method for producing each of same, and laminate body |
| WO2013191516A1 (en) * | 2012-06-22 | 2013-12-27 | 코오롱인더스트리 주식회사 | Photopolymerisable composition, and optical sheet comprising resin curing layer formed therefrom |
| JP5891972B2 (en) * | 2012-06-29 | 2016-03-23 | 東亞合成株式会社 | Optical film or sheet, polarizer protective film, and polarizing plate |
| JP6212420B2 (en) * | 2014-03-25 | 2017-10-11 | 富士フイルム株式会社 | Composition, Underfill Laminate, Laminate, Semiconductor Device Manufacturing Method, and Semiconductor Device |
| WO2021117836A1 (en) * | 2019-12-13 | 2021-06-17 | キヤノン株式会社 | Photocurable material composition, and cured product of photocurable material composition and method for manufacturing same |
-
2011
- 2011-05-19 JP JP2011112165A patent/JP2012008547A/en not_active Withdrawn
- 2011-05-23 TW TW100118012A patent/TW201209093A/en unknown
- 2011-05-24 KR KR1020110049168A patent/KR20110131112A/en not_active Application Discontinuation
- 2011-05-24 CN CN2011101398934A patent/CN102262250A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110199210A (en) * | 2017-01-20 | 2019-09-03 | 住友化学株式会社 | The manufacturing method of optical film and optical film |
| CN111971589A (en) * | 2018-03-30 | 2020-11-20 | 三井化学株式会社 | Optical lens |
| CN112566949A (en) * | 2018-08-09 | 2021-03-26 | 住友化学株式会社 | Resin and adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110131112A (en) | 2011-12-06 |
| TW201209093A (en) | 2012-03-01 |
| JP2012008547A (en) | 2012-01-12 |
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Application publication date: 20111130 |