CN101809057B - Polyester composition for production of thermally cured film - Google Patents
Polyester composition for production of thermally cured film Download PDFInfo
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- CN101809057B CN101809057B CN2008801097562A CN200880109756A CN101809057B CN 101809057 B CN101809057 B CN 101809057B CN 2008801097562 A CN2008801097562 A CN 2008801097562A CN 200880109756 A CN200880109756 A CN 200880109756A CN 101809057 B CN101809057 B CN 101809057B
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
To provide a material which can be formed into a cured film having high solvent resistance, liquid crystal-aligning properties, heat resistance, high transparency and high planarization, and which can be dissolved in a glycol-type solvent and a lactic acid ester-type solvent (which are solvents applicable in the production line for a planarized film of a color filter) in the formation of a cured film from the material. Disclosed is a polyester composition for the production of a thermally cured film, which comprises the following components (A) and (B): (A) a polyester having a constituent unit represented by the formula (1); and (B) an epoxy compound having two or more epoxy groups. (1) wherein A and B independently represent an organic group containing a ring structure.
Description
Technical field
The present invention relates to the formation of thermofixation film and form the cured film that obtains with polymer blend with polymer blend with by this thermofixation film.More specifically, the present invention relates to have high transparent, smooth voltinism, and the thermofixation film with liquid crystal aligning ability, high solvent resistance forms with polymer blend and this cured film, and the purposes of this cured film.This thermofixation film forms the colour filter overcoating agent that is particularly suitable for having concurrently the liquid crystal aligning function in the liquid-crystal display with polymer blend.
Background technology
Usually, in optics such as liquid crystal display device, organic EL (electroluminescent) element, solid-state imaging element, element surface is provided with protective membrane to prevent in manufacturing processed, being exposed to solvent or heat.This protective membrane not only adhesivity height, the solvent resistance with the substrate of being protected is high, but also requires performances such as the transparency, thermotolerance.
Under the situation of the protective membrane that such protective membrane is used as the colour filter that uses in color liquid crystal display arrangement or the solid-state imaging element; Usually require to have the colour filter that makes this basal substrate or the performance of black matrix resin planarization, promptly as the performance of planarization film.Particularly when making the color liquid crystal display device of STN mode or TFT mode, need to control the bonding precision between filter substrate and the relative substrate very tightly, must make the unit interval between substrate even.In addition, in order to keep optical transmission rate, need high transparent as these planarization films of this protective membrane through colour filter.
On the other hand, studied in recent years through in the unit of liquid-crystal display, importing the phase differential material and realized cost degradation, lightweight, be employed on such phase differential material the coating of liquid crystalline monomer usually and make its orientation, material of photocuring then.In order to make this phase differential material orientation, lower membrane need be the material that after friction treatment, has orientation.Therefore, after forming liquid crystal orientation film on the outer covering layer of colour filter, form phase differential material (with reference to Fig. 2 (a)).If can form the film (with reference to Fig. 2 (b)) of the outer covering layer of holding a concurrent post this liquid crystal orientation film and colour filter, then can obtain cost degradation, technology is counted greater advantages such as minimizing, therefore need such material badly.
Usually, the outer covering layer of this colour filter adopts the high vinyl resin of the transparency.In these vinyl resins,, extensively adopt glycolic solvents or esters solvents such as ethyl lactate, n-Butyl lactate such as propylene glycol monomethyl ether or propylene glycol monomethyl ether from the viewpoint of security, operability.Such vinyl resin is given thermotolerance or solvent resistance (patent documentation 1,2) through thermofixation or photocuring.Yet,, can not show sufficient orientation even such planarization film is carried out friction treatment though Thermocurable in the past or light solidified vinyl resin demonstrate the suitable transparency or smooth voltinism.
On the other hand, liquid crystal orientation film adopts the material of being processed by solvent soluble polyimide or polyamic acid usually.Reported through when afterwards toasting, making the complete imidization of these materials give solvent resistance, shown sufficient orientation (patent documentation 3) through friction treatment.Yet, under situation, have problems such as the smooth voltinism and the transparency reduce significantly as the planarization film of colour filter.In addition, polyimide or polyamic acid dissolve in N-Methyl pyrrolidone or gamma-butyrolactone equal solvent, but the solvability in glycolic solvents or esters solvent is lower, thereby are difficult to be applicable to the planarization film production line.
Patent documentation 1: the spy opens the 2000-103937 communique
Patent documentation 2: the spy opens the 2000-119472 communique
Patent documentation 3: the spy opens the 2005-037920 communique
Summary of the invention
The present invention is based on the above-mentioned fact and propose; Problem to be solved provides and forms the back in cured film and show high solvent resistance, liquid crystal aligning property, thermotolerance, high transparent and high smooth voltinism, and cured film when forming applicable to the production line of the planarization film of colour filter, be dissolvable in water the material of glycolic solvents or lactic acid ester solvent.
The present inventor furthers investigate in order to solve above-mentioned problem, thereby accomplishes the present invention.
That is,, relate to the thermofixation film formation that contains following compositions (A) and composition (B) and use polymer blend as the 1st viewpoint.
Composition (A): comprise the polyester of the represented structural unit of following formula (1),
Composition (B): epoxy compounds with 2 above epoxy group(ing).
(in the formula, A is selected from least a in the represented group of following formula (A-1)-Shi (A-15), and B is selected from least a in the represented group of following formula (B-1)-Shi (B-5).)
As the 2nd viewpoint, relate to forming and use polymer blend according to the thermofixation film put down in writing in the 1st viewpoint, in the above-mentioned formula (1), A is selected from least a in the represented group of following formula (A-1)-Shi (A-8).
As the 3rd viewpoint; Relate to and form according to the thermofixation film put down in writing in the 1st viewpoint or the 2nd viewpoint that use polymer blend, composition (A) be through making the tetracarboxylic acid composition and the (ii) represented diol compound of following formula that comprise the represented tetracarboxylic dianhydride of following formula (i) react the polyester that obtains.
(in the formula, A is identical with the definition in the above-mentioned formula (1) with B.)
As the 4th viewpoint, relate to according to the thermofixation film formation of each record in the 1st viewpoint-the 3rd viewpoint and use polymer blend, the weight-average molecular weight of composition (A) polyester is 1 with polystyrene conversion, 000-30,000.
As the 5th viewpoint, relate to according to the thermofixation film formation of putting down in writing in the 1st viewpoint-the 4th viewpoint and use polymer blend, it also contains bismaleimide compound as composition (C).
As the 6th viewpoint, relate to according to the thermofixation film formation of each record in the 1st viewpoint-the 5th viewpoint and use polymer blend, contain the composition (B) of 3-50 mass parts based on 100 mass parts compositions (A).
As the 7th viewpoint, relate to according to the thermofixation film formation of putting down in writing in the 5th viewpoint or the 6th viewpoint and use polymer blend, contain the composition (C) of 0.5-50 mass parts based on 100 mass parts compositions (A).
As the 8th viewpoint, relate to and adopt in the 1st viewpoint-the 7th viewpoint thermofixation film of putting down in writing in each to form the cured film that obtains with polymer blend.
As the 9th viewpoint, relate to and adopt in the 1st viewpoint-the 7th viewpoint thermofixation film of putting down in writing in each to form the liquid crystal orientation film that obtains with polymer blend.
Thermofixation film formation of the present invention can form with polymer blend has high smooth voltinism, high transparent, high solvent resistance, high heat resistance; But also have the cured film of liquid crystal aligning ability, therefore can be as the formation material of liquid crystal orientation film or planarization film.Particularly can once form in the past the outer covering layer of independent liquid crystal orientation film that forms and colour filter and as " planarization film " of both characteristics, simplification and the minimizing of technology number through ME can realize cost degradation etc.
In addition, thermofixation film of the present invention forms and dissolves in glycolic solvents and lactic acid ester solvent with polymer blend, so can be suitable for mainly using the production line of the planarization film of these solvents.
Embodiment
As previously mentioned, in the cured film of crylic acid resin that in the past proposes and polyimide resin class, also the cured film of all properties such as liquid crystal orientation film or the desired smooth voltinism of planarization film, the transparency, orientation can be fully satisfied in discovery.
In addition, once propose to use up to now polyester as the oriented material of liquid crystal display device (with reference to the spy open flat 5-158055 communique, the spy opens the 2002-229039 communique), but these all do not have Thermocurable, the poor solvent resistance of the film of formation.
The invention is characterized in the raising of adopting polyester to realize above-mentioned performance with Thermocurable, the present invention be contain the epoxy compounds with 2 above epoxy group(ing) of the polyester of composition (A) and composition (B), the formation of thermofixation film uses polymer blend.And said thermofixation film forms with polymer blend except containing composition (A), the composition (B), can also containing bismaleimide compound as composition (C).
Hereinafter will specify each composition.
< composition (A) >
Composition (A) is the polyester that comprises the represented structural unit of following formula (1).
In above-mentioned formula, A is selected from least a in the represented group of following formula (A-1)-Shi (A-15), and B is selected from least a in the represented group of following formula (B-1)-Shi (B-5).
In the represented group of above-mentioned formula (A-1)-Shi (A-15), from improving stable on heating viewpoint, preferred formula (the A-1)-represented group of Shi (A-8), the group of especially preferably from formula (A-1)-(A-2), selecting.
In addition, in the represented group of above-mentioned formula (B-1)-Shi (B-5), the group of especially preferably from (B-1)-(B-4), selecting.
The polyester of composition (A) is preferably the polyester that comprises the represented modular construction of formula (1), and at this moment, A and B can be a kind of independently of one another, also can be multiple.
In this case, each is the performance except other, and in order to attempt to improve thermotolerance, at least 60 moles of % of the A of formula (1) are preferably above-mentioned formula (A-1)-represented group of Shi (A-8).
The weight-average molecular weight of the polyester of composition (A) is 1,000-30, and 000, be preferably 1,500-10,000.Under the situation of weight-average molecular weight less than above-mentioned scope of the polyester of composition (A), orientation and solvent resistance reduce sometimes, if surpass above-mentioned scope then smooth voltinism reduces sometimes.
< method of manufacture of composition (A) >
In the present invention, through making (ii) represented diol compound (diol component) reaction of represented tetracarboxylic dianhydride of following formula (i) (sour composition) and following formula obtain composition (A) polyester.
In the above-mentioned formula, A is identical with the definition in the above-mentioned formula (1) with B.
In the present invention, sour composition and diol component can be a kind of compound independently of one another, also can be multiple compounds.
In addition, in the present invention, can realize improving other each performance and thermotolerance through adopting the polyester that uses aliphatic tetracarboxylic dianhydride to obtain.Therefore, preferably, for the polyester of composition of the present invention (A), at least 60 moles of % are aliphatic tetracarboxylic dianhydride in the employed sour composition, and particularly, the A that is preferably in the formula (i) is the tetracarboxylic dianhydride of the represented group of above-mentioned formula (A-1)-Shi (A-8).
In the polyester of mentioned component (A); Expectation tetracarboxylic dianhydride's the total amount (total amount of sour composition) and the proportioning of the total amount (total amount of diol component) of diol compound, i.e. < total mole number of diol compound >/< total mole number of tetracarboxylic dianhydride's compound>is 0.5-1.5.With common polycondensation likewise, this mol ratio is more near 1, the polymerization degree of the polyester of generation is bigger, molecular weight is big more.
Reduce for fear of stability in storage, preferably protect the end of the polyester of composition (A) with dicarboxylic anhydride or alcohol.From the orientation aspect, more preferably protect with acid anhydrides.
The end of above-mentioned polyester changes along with the variation of the proportioning of sour composition and diol component.For example, under the situation that makes the reaction of excess acid composition, the terminal acid anhydrides that forms easily.
In addition, adopting the excess diol composition to carry out under the polymeric situation, the terminal hydroxyl that forms easily.In this case, make the reaction of this terminal hydroxyl and carboxylic acid anhydride, can use acid anhydrides closed end hydroxyl.Instance as such carboxylic acid anhydride; Can enumerate Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, maleic anhydride, naphthalic anhydride, hydrogenation Tetra hydro Phthalic anhydride, methyl-5-norbornylene-2; 3-dicarboxylic anhydride, itaconic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, two ring [2.2.2] octenes-2,3-dicarboxylic anhydride etc.
In the manufacturing of the polyester of mentioned component (A), the temperature of reaction of sour composition and diol component can be selected the arbitrary temp in 50-200 ℃, preferred 80-170 ℃.For example, be that 100 ℃-140 ℃, reaction times are can obtain polyester under 2-48 hour in temperature of reaction.
In addition, can select the arbitrary temp in 50-200 ℃, preferred 80-170 ℃ with the temperature of reaction under the situation of acid anhydrides protection terminal hydroxyl.
The reaction of above-mentioned sour composition and diol component is carried out in solvent usually.As operable solvent this moment, hydroxyl or amino etc. do not get final product with the solvent of the functional group of anhydride reaction, not special restriction.Can enumerate for example N; Dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, N-vinyl pyrrolidone, N-methyl caprolactam, DMSO 99.8MIN., tetramethyl-urea, METHYL SULFONYL METHANE., hexamethyl sulfoxide, meta-cresol, gamma-butyrolactone, pimelinketone, ketopentamethylene, butanone, MIBK, 2-heptanone, propylene glycol monomethyl ether, Ucar 35 propyl ether acetic ester, 3-methoxypropionic acid methyl esters, 2-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 2-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 2-ethoxyl ethyl propionate etc.
These solvents can use separately also can mix use, but from security, to the suitability aspect of the overcoating agent production line of colour filter, more preferably propylene glycol monomethyl ether.
In addition, even if the solvent of dissolved polyester not also can use with above-mentioned solvent in the scope that the polyester that generates through polyreaction is not separated out.
Also can adopt catalyzer when in addition, above-mentioned sour composition (formula (i)) is with diol component (formula (ii)) reaction.
The concrete example of the catalyzer that adopts during as polyester; Can enumerate quaternary ammonium salts such as benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl tripropyl ammonium chloride, benzyl tripropyl brometo de amonio, tetramethyl ammonium chloride, tetraethylammonium bromide, 4-propyl ammonium chloride, 4-propyl bromide, quaternary alkylphosphonium salts such as tetraphenyl phosphonium chloride, 4-phenyl phosphonium bromide, benzyl base triphenyl phosphonium chloride, benzyl three phenyl phosphonium bromides, ethyl triphenyl phosphonium chloride, ethyl triphenyl phosphonium bromide.
The solution that comprises the polyester of the composition (A) that obtains thus can intactly be used for the thermofixation film and form the preparation with polymer blend.In addition, can from poor solvents such as water, methyl alcohol, ethanol, ether, hexane, precipitate and isolate polyester and recovery use.
< composition (B) >
As the epoxy compounds with 2 above epoxy group(ing) of composition of the present invention (B), for example, for example can enumerate three (2; The 3-epoxypropyl) isocyanuric acid ester, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxy ethyl) hexanaphthene, glycerine triglycidyl group ether, Diethylene Glycol diglycidyl ether, 2; 6-diglycidyl phenylglycidyl ether, 1,1,3-three is [to (2; The 3-glycidoxy) phenyl] propane, 1; 2-cyclohexane dicarboxylic acid diglycidyl ester, 4,4 '-methylene-bis (N, N-diglycidylaniline), 3; 4-epoxycyclohexyl methyl-3,4-epoxy cyclohexane manthanoate, trimethylolethane trimethacrylate glycidyl ether and bisphenol-A-diglycidyl ether and tetramethylolmethane poly epihydric alcohol base ether etc.
In addition, from obtaining easy aspect, can adopt the commercial compound.Below enumerate out concrete example (trade(brand)name), but be not limited to these: the epoxy resin of YH-434, YH434L (Dongdu changes into (strain) system) etc. with amino; The epoxy resin with cyclohexene oxide structure of エ Port リ one De GT-401, same GT-403, same GT-301, same GT-302, セ ロ キ サ イ De 2021, セ ロ キ サ イ De 3000 (ダ イ セ Le chemical industry (strain) system) etc.; The bisphenol A type epoxy resin of エ ピ コ one ト 1001, together 1002, together 1003, together 1004, together 1007, together 1009, together 1010, together 828 (above is that oiling シ ェ Le エ Port キ シ (strain) (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) at present) makes) etc.; The bisphenol f type epoxy resin of エ ピ コ one ト 807 (oiling シ ェ Le エ Port キ シ (strain) (existing ジ ャ パ Application エ Port キ シ レ ジ Application (strain)) system) etc.; エ ピ コ one ト 152, with 154 (above be oiling シ ェ Le エ Port キ シ (strain) (existing ジ ャ パ Application エ Port キ シ レ ジ Application (strain)) system), EPPN201, with the phenol phenolic resin type epoxy resin of 202 (above is that Japanese chemical drug (strain) is made) etc.; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (more than; Japan's chemical drug (strain) is made), the cresol novolac resin type epoxy resin of エ ピ コ one ト 180S75 (oiling シ ェ Le エ Port キ シ (strain) (existing ジ ャ パ Application エ Port キ シ レ ジ Application (strain)) system) etc.; デ Na コ one Le EX-252 (Na ガ セ ケ system テ Star Network ス (strain) system); CY175, CY177, CY179, ア ラ Le ダ イ ト CY-182, same CY-192, same CY-184 (more than; CIBA-GEIGY A.G system); エ ピ Network ロ Application 200, with 400 (more than, big Japanese イ Application キ chemical industry (strain) system), エ ピ コ one ト 871, with 872 (more than; Oiling シ ェ Le エ Port キ シ (strain) (existing ジ ャ パ Application エ Port キ シ レ ジ Application (strain)) system), the alicyclic epoxy resin of ED-5661, ED-5662 (above is セ ラ ニ one ズ コ one テ ィ Application グ (strain) system) etc.; The aliphatic poly glycidyl ether of デ Na コ one Le EX-611, same EX-612, same EX-614, same EX-622, same EX-411, same EX-512, same EX-522, same EX-421, same EX-313, same EX-314, same EX-321 (Na ガ セ ケ system テ Star Network ス (strain) system) etc. etc.
In addition, as compound, can use polymkeric substance with epoxy group(ing) with at least two epoxy group(ing).As such polymkeric substance, just can use not special restriction so long as have the polymkeric substance of epoxy group(ing).
Above-mentioned polymkeric substance with epoxy group(ing) can for example have the addition polymerization property monomer of epoxy group(ing) through employing to carry out addition polymerization and makes.Can enumerate the for example multipolymer of poly epihydric alcohol base propenoate, methyl propenoic acid glycidyl base ester and Jia Jibingxisuanyizhi, the polycondensation polymer of the addition polymerization polymkeric substance of the multipolymer of methyl propenoic acid glycidyl base ester and vinylbenzene and 2-hydroxyethyl methacrylate etc. or epoxy-Novolak resin etc.
Perhaps, above-mentioned polymkeric substance with epoxy group(ing) can react through the compound that makes macromolecular compound with hydroxyl and Epicholorohydrin, glycidyl tosylate etc. have epoxy group(ing) and make.
As the weight-average molecular weight of such polymkeric substance, be for example 300-200,000.
These epoxy compoundss with 2 above epoxy group(ing) can use separately or combination use more than 2 kinds.
It is the 3-50 mass parts that thermofixation film of the present invention forms the polyester that content with the epoxy compounds with 2 above epoxy group(ing) of the composition in the polymer blend (B) is preferably based on 100 mass parts compositions (A); More preferably the 5-40 mass parts is preferably the 10-30 mass parts especially.Under the too small situation of this ratio, the solvent resistance or the thermotolerance that are formed the cured film that obtains with polymer blend by the thermofixation film reduce sometimes, and on the contrary, under excessive situation, solvent resistance reduces sometimes, stability in storage reduces sometimes.
< composition (C) >
As the composition among the present invention (C), can comprise the bismaleimide compound shown in the following formula (2).
Composition (C) bismaleimide compound can improve smooth voltinism.
In the formula, R
1Be to be selected from fatty group, to comprise the fatty group of ring type structure and the organic group of aromatic series base, or the organic group that forms by a plurality of moiety combinations that are selected from these organic groups.R
1Can comprise keys such as ester bond, ehter bond, amido linkage, amino-formate bond.
As such bismaleimide compound, can enumerate for example N, N '-3,3-ditan bismaleimides, N, N '-(3; 3-diethylammonium-5, the 5-dimethyl-)-4,4-phenylbenzene-methane bismaleimides, N, N '-4,4-ditan bismaleimides, 3; 3-sulfobenzide bismaleimides, 4,4-sulfobenzide bismaleimides, N, N '-to UVNUL MS-40 bismaleimides, N, N '-diphenylethane bismaleimides, N, N '-diphenyl ether bismaleimides, N; N '-(methylene radical two-two tetrahydrochysene phenyl) bismaleimides, N, N '-(3-ethyl)-4,4-ditan bismaleimides, N, N '-(3, the 3-dimethyl-)-4; 4-ditan bismaleimides, N, N '-(3, the 3-diethylammonium)-4,4-ditan bismaleimides, N, N '-(3; The 3-dichloro)-4,4-ditan bismaleimides, N, N '-isophorone bismaleimides, N, N '-tolidine bismaleimides, N, N '-diphenyl propane bismaleimides, N; N '-naphthalene bismaleimides, N, N '-meta-phenylene bismaleimide, N, N '-5-methoxyl group-1,3-phenylene bismaleimides, 2, two (4-(the 4-maleimide phenoxy) phenyl) propane, 2 of 2-; Two (3-chloro-4-(the 4-maleimide phenoxy) phenyl) propane, 2 of 2-, two (3-bromo-4-(the 4-maleimide phenoxy) phenyl) propane, 2 of 2-, two (3-ethyl-4-(the 4-maleimide phenoxy) phenyl) propane, 2 of 2-, two (3-propyl group-4-(the 4-maleimide phenoxy) phenyl) propane, 2 of 2-; Two (3-sec.-propyl-4-(the 4-maleimide phenoxy) phenyl) propane, 2 of 2-, two (3-butyl-4-(the 4-maleimide phenoxy) phenyl) propane, 2 of 2-, two (3-methoxyl group-4-(the 4-maleimide phenoxy) phenyl) propane, 1 of 2-, two (4-(the 4-maleimide phenoxy) phenyl) ethane, 1 of 1-; Two (3-methyl-4-(the 4-maleimide phenoxy) phenyl) ethane, 1 of 1-, two (3-chloro-4-(the 4-maleimide phenoxy) phenyl) ethane, 1 of 1-, two (3-bromo-4-(the 4-maleimide phenoxy) phenyl) ethane, 3 of 1-, two (4-(the 4-maleimide phenoxy) phenyl) pentanes, 1 of 3-; 1,1,3,3; 3-hexafluoro-2, two (4-(the 4-maleimide phenoxy) phenyl) propane, 1,1 of 2-, 1; 3,3,3-hexafluoro-2,2-two (3; 5-dimethyl--4-(4-maleimide phenoxy) phenyl) propane, 1,1,1,3; 3,3-hexafluoro-2, two (3,5-two bromo-4-(the 4-maleimide phenoxy) phenyl) propane of 2-, N; N '-ethylene maleimide, N, N '-hexa-methylene bismaleimides, N, N '-ten dimethylene bismaleimides, N, a N '-benzene two methylene bismaleimidess, N; N '-terephthaldehyde supports bismaleimides, N, N '-1,3-dimethylene hexanaphthene bismaleimides, N, N '-2; 4-toluene bismaleimides, N, N '-2,6-toluene bismaleimides, or the like.These bismaleimide compounds are not confined to above-claimed cpd especially.These can use separately or composition combination use more than 2 kinds.
In these bismaleimidess, preferred 2, two (4-(the 4-maleimide phenoxy) phenyl) propane of 2-, N; N '-4,4-ditan bismaleimides, N, N '-(3; 3-diethylammonium-5, the 5-dimethyl-)-4,4-phenylbenzene-aromatic series bismaleimidess such as methane bismaleimides.
In addition, in these aromatic series bismaleimidess, in order to obtain higher smooth voltinism, preferred molecular weight is the aromatic series bismaleimides below 1,000.
About the usage ratio of the bismaleimide compound of composition among the present invention (C), preferably the polyester with respect to 100 mass parts compositions (A) is the 0.5-50 mass parts, and more preferably the 1-30 mass parts is preferably the 2-20 mass parts especially.Under the too small situation of this ratio, the smooth voltinism that is formed the cured film that obtains with polymer blend by the thermofixation film reduces sometimes, under excessive situation, and the transsmissivity of the cured film cracking sometimes that reduces sometimes, films.
< solvent >
Thermofixation film of the present invention forms with polymer blend and often uses under the solution state in being dissolved in solvent.The solvent that uses this moment be used for solvent components (A) and composition (B), composition as required (C) and/or after state the solvent of other additive, then its kind and structure etc. are not just limited especially so long as have the solvent of such dissolving power.
As such solvent, can enumerate the solvent or the following solvents that are used for polymerization composition (A).Can enumerate for example acetic acid methyl cellosolve, acetate ethyl cellosolve, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, propylene glycol monomethyl ether, Ucar 35 propyl ether, ethyl lactate, n-Butyl lactate, hexalin, ETHYLE ACETATE, butylacetate, ethyl lactate, n-Butyl lactate etc.
These solvents can use a kind of separately, or combination is used more than two kinds.
< other additive >
In addition; Only otherwise destroy effect of the present invention; Thermofixation film formation of the present invention can comprise bonding auxiliarys such as tensio-active agent, rheology control agent, silane coupling agent as required with polymer blend; Pigment, dyestuff, storage stabilizing agent, skimmer, or dissolution accelerators such as multivalence phenol, polyvalent carboxylic acid, inhibitor etc.
As the preferred especially phenols of inhibitor,, can enumerate 2 as concrete example; 6-di-t-butyl-4-cresols, 2,6 di t butyl phenol, 2,4; 6-three (3 ', 5 '-di-t-butyl 4 '-hydroxybenzyl) mesitylene, tetramethylolmethane four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester], acetone two (3; The 5-di-tert-butyl-hydroxy phenyl) mereaptol, 4,4 '-methylene-bis (2,6 di t butyl phenol), 3-(3; The 5-di-tert-butyl-hydroxy phenyl) methyl propionate, 4,4 '-sulfo-two (2,6 di t butyl phenol), three (3; The 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide etc.
< the thermofixation film forms and uses polymer blend >
It is the polyester that can comprise composition (A), the epoxy compounds with 2 above epoxy group(ing) of composition (B) that thermofixation film of the present invention forms with polymer blend; And can also comprise the bismaleimide compound of composition (C) as required, and more than one the compsn in other additive.Usually, these often are dissolved in the solvent, use as solution.
Wherein, thermofixation film of the present invention forms following with the preferred embodiment of polymer blend.
[1]: based on 100 mass parts compositions (A), the thermofixation film that contains the composition (B) of 3-50 mass parts forms uses polymer blend.
[2]: based on 100 mass parts compositions (A), the thermofixation film that contains composition (B), the solvent of 3-50 mass parts forms uses polymer blend.
[3]: based on 100 mass parts compositions (A), the thermofixation film of composition (C) that contains composition (B), the 0.5-50 mass parts of 3-50 mass parts forms uses polymer blend.
[4]: based on 100 mass parts compositions (A), the thermofixation film that comprises composition (C), the solvent of composition (B), the 0.5-50 mass parts of 3-50 mass parts forms uses polymer blend.
Hereinafter will be described in detail in thermofixation film of the present invention will be formed cooperation ratio when using as solution with polymer blend, compound method etc.
Form with the solids ratios in the polymer blend for thermofixation film of the present invention,, can be 1-80 quality %, preferably 5-60 quality %, more preferably 10-50 quality % so long as each composition is dissolved in just not special restriction in the solvent equably.Among this paper, solid is meant from the thermofixation film and forms with removing the rest part that desolvates whole compositions of polymer blend.
Thermofixation film of the present invention forms with the not special restriction of the compound method of polymer blend; As its preparation method; For example can enumerate that composition (A) is dissolved in the solvent, this solution with composition (B), mix with predetermined proportion with composition (C), is formed the method for homogeneous solution again; Perhaps, add other additive and method of mixing as required again in the suitable stage of this preparation method.
When preparation thermofixation film of the present invention forms when use polymer blend, the solution of the polyester through the acquisition of the polyreaction in the solvent can intactly use.In this case, when in the solution of this composition (A), forming homogeneous solution,, can also add solvent again in order to regulate concentration with above-mentioned added ingredients likewise (B), composition (C) etc.At this moment, the solvent that uses in the generative process of polyester and thermofixation film can be identical in order to the solvent of regulating concentration when forming with the preparation of polymer blend, also can difference.
And the thermofixation film of preparation forms the solution that uses polymer blend and preferably after adopting the aperture to be the filtrations such as strainer about 0.2 μ m, uses.
< film, cured film and liquid crystal orientation film >
Thermofixation film of the present invention formed with polymer blend coat on substrate (for example silicon/silicon dioxide coat substrate, silicon nitride substrate, metal for example aluminium, molybdenum, chromium etc. coat substrate, glass substrate, quartz base plate, ito substrates etc.) or the film (for example resin moldings such as tri acetyl cellulose membrane, polyester film, acrylic film) etc. with spin coating, ink-jet application, printing etc., can form and film through carry out predrying (prebake conditions) with hot plate or baking oven etc. then through spin coating, flow coat, roller coat, slot coated, slot coated are follow-up.After this, carry out heat treated through this is filmed and to form coating.
As the condition of this heat treated, can adopt from for example temperature is 70 ℃-160 ℃, and the time is Heating temperature and the heat-up time of suitably selecting in 0.3-60 minute the scope.Are preferably Heating temperature and heat-up time 80 ℃-140 ℃, 0.5-10 minute.
In addition, form by the thermofixation film and to use the thickness of the coating that polymer blend forms for example to be 0.1-30 μ m, can consider the differential or optics, electrical properties of employed substrate and suitably select.
As back baking, adopt the Heating temperature of selecting 140 ℃-250 ℃ the scope to be usually from temperature, adopt situation on the hot plate for handling 5-30 minute, the situation in the baking oven is for handling 30-90 minute such method.
According to aforesaid condition, form the coating curing that obtains with polymer blend through making by thermofixation film of the present invention, the differential abundant planarization of substrate can be made, and cured film can be formed with high transparent.
Carry out friction treatment through the cured film that will form thus and can make it have the function as the liquid crystal material alignment films, that is, the layer that is orientated as the compound with the liquid crystal liquid crystal property of making plays a role.
As the condition of friction treatment, adopting speed of rotation usually is 300-1000rpm, and speed of feed is 3-20mm/ second, and the amount of pushing is the such condition of 0.1-1mm.
Adopt pure water etc. through ultrasonic cleaning remove by fricative residue thereafter.
Behind coating phase differential material on the liquid crystal orientation film that forms thus, be mesomorphic state with phase differential material photocuring, have optically anisotropic layer thereby can form.
As the phase differential material, can adopt the liquid crystal monomer that for example has polymerizable group or contain compsn of this liquid crystal monomer etc.
Base material forming liquid crystal aligning layer is under the situation of film, can be used as optical anisotropic film.
In addition, 2 plate bases that will have as stated a liquid crystal aligning layer that forms be situated between by spacer with the relative mode of liquid crystal orientation film bonding after, between these substrates, inject liquid crystal, can form the liquid crystal display device of liquid crystal aligning.
Therefore, thermofixation film of the present invention forms and can be suitable for various optical anisotropic films, liquid crystal display device with polymer blend.
In addition; Thermofixation film of the present invention forms with polymer blend owing to have the smooth voltinism of desired level at least; Therefore also can be particularly suitable for as the outer material that covers part, the interlayer dielectric of TFT type liquid crystal cell, the insulating film of organic EL etc. that forms colour filter as the material of cured film such as the protective membrane in the various indicating meters such as formation thin film transistor (TFT) type liquid crystal display device, organic EL, planarization film, insulating film.
Embodiment
Enumerate embodiment below and illustrate in greater detail the present invention, but the invention is not restricted to these embodiment.
[dummy suffix notation that uses among the embodiment]
The meaning of the dummy suffix notation that uses in following examples is following.
< polyester raw material >
HBPDA:3,3 '-4,4 '-dicyclohexyl tetracarboxylic dianhydride
HPMDA:1,2,4,5-cyclohexyl tetracarboxylic dianhydride
BPDA: biphenyl tetracarboxylic dianhydride
TDA:4-(2,5-dioxo THF-3-yl)-1,2,3,4-tetralin-1, and the 2-dicarboxylic anhydride [4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride]
6FDA:4,4 '-(hexafluoro isopropylidene) O-phthalic acid dianhydride
PMDA: pyromellitic acid dianhydride
ODPA: two (3,4-dicarboxyl phenyl) ether dianhydride
Acid dianhydride
HBPA: Hydrogenated Bisphenol A 99
CHDO:1, the 4-cyclohexanediol
PXG: terephthalyl alcohol
THPA:1,2,5, the 6-Tetra Hydro Phthalic Anhydride
< catalyzer >
BTEAC: benzyltriethylammoinium chloride
< polyimide precursor raw material >
CBDA: hexanaphthene tetracarboxylic dianhydride
PDA: Ursol D
< acrylic acid copolymer raw material >
MAA: methylacrylic acid
MMA: TEB 3K
HEMA: 2-hydroxyethyl methacrylate
CHMI:N-cyclohexyl maleimide
AIBN: Diisopropyl azodicarboxylate
< epoxy compounds >
CEL: ダ イ セ Le chemistry system セ ロ キ サ イ De P-2021 (goods name) (compound name: 3,4-oxidation cyclohexyl methyl-3 ', 4 '-epoxy cyclohexane manthanoate)
<bismaleimide compound >
BMI1:N, N '-(3,3-diethylammonium-5,5-dimethyl-)-4,4-phenylbenzene-methane bismaleimides
< solvent >
PGMEA: propylene glycol monomethyl ether
The NMP:N-SL 1332
The number-average molecular weight of polyester, polyimide precursor and the PEMULEN TR2 that obtains according to following synthetic example and weight-average molecular weight adopt Japanese beam split (strain) system GPC device (Shodex (registered trademark) chromatographic column KF803L and KF804L), are to measure under the such condition of (column temperature is 40 ℃) and elution in 1ml/ minute chromatographic column of flowing through with the flow at the eluting solvent THF.In addition, following number-average molecular weight (below be called Mn.) and weight-average molecular weight (below be called Mw.) with the polystyrene conversion value representation.
< synthetic example 1 >
Through make 12.0g HBPDA, 10.2g HBPA, 0.95g THPA and 0.22g as the BTEAC of catalyzer in 54.48g PGMEA 120 ℃ of reactions 19 hours down, thereby obtain polyester liquid (solids concn: 30.0 quality %) (P1).The Mn of gained polyester is 2,280, and Mw is 4,200.
< synthetic example 2 >
Through make 18.0g HBPDA, 4.54g BPDA, 15.9g HBPA, 2.01g THPA and 0.19g as the BTEAC of catalyzer in 95.1g PGMEA 120 ℃ of reactions 19 hours down, thereby obtain polyester liquid (solids concn: 30.0 quality %) (P2).The Mn of gained polyester is 1,510, and Mw is 3,570.
< synthetic example 3 >
Through make 14.0g HPMDA, 4.60g BPDA, 16.9g HBPA, 2.14g THPA and 0.09g as the BTEAC of catalyzer in 88.6g PGMEA 120 ℃ of reactions 19 hours down, thereby obtain polyester liquid (solids concn: 30.0 quality %) (P3).The Mn of gained polyester is 1,643, and Mw is 2,380.
< synthetic example 4 >
Through 40.0g BPDA, 35.3g HBPA, 0.77g BTEAC were reacted 1 hour down at 120 ℃ in 175.7g PGMEA, add 3.31g THPA reaction 19 hours then, thereby obtain polyester polymers solution (solids concn: 30.0 quality %) (P4).The Mn of gained polyester polymers is 1,100, and Mw is 2,580.
< synthetic example 5 >
Through 15.0g TDA, 7.25g pXG, 0.28g BTEAC were reacted 1 hour down at 120 ℃ in 51.9g PGMEA, add 0.76g THPA reaction 19 hours then, thereby obtain polyester polymers solution (solids concn: 30.0 quality %) (P5).The Mn of gained polyester polymers is 1,200, and Mw is 2,800.
< synthetic example 6 >
Through 40.0g 6FDA, 11.3g CHDO, 0.51g BTEAC were reacted 1 hour down at 120 ℃ in 119.7g PGMEA, add 2.19g THPA reaction 19 hours then, thereby obtain polyester polymers solution (solids concn: 30.0 quality %) (P6).The Mn of gained polyester polymers is 2,100, and Mw is 3,800.
< synthetic example 7 >
Through 40.0g PMDA, 47.6g HBPA, 1.04g BTEAC were reacted 1 hour down at 120 ℃ in 204.4g PGMEA, add 4.46g THPA reaction 19 hours then, thereby obtain polyester polymers solution (solids concn: 30.0 quality %) (P7).The Mn of gained polyester polymers is 1,100, and Mw is 2,850.
< synthetic example 8 >
Through 20.0g ODPA, 8.10g CHDO, 0.37g BTEAC were reacted 1 hour down at 120 ℃ in 65.5g PGMEA, add 1.57g THPA reaction 19 hours then, thereby obtain polyester polymers solution (solids concn: 30.0 quality %) (P8).The Mn of gained polyester polymers is 1,400, and Mw is 2,730.
< synthetic example 9 >
Through make 17.7g CBDA, 10.2g pDA in 66.4g NMP 23 ℃ of down reactions 24 hours, thereby obtain polyimide precursor solution (solids concn: 30.0 quality %) (P9).The Mn of gained polyimide precursor is 5,800, and Mw is 12,500.
< synthetic example 10 >
Use 10.9g MAA, 35.3g CHMI, 25.5g HEMA, 28.3g MMA as monomer component; Use 5g AIBN as radical polymerization initiator; Is 60 ℃-100 ℃ under to carry out polyreaction in temperature through making these in 150g solvent PGMEA, thereby obtains acrylic acid copolymer soln (solids concn: 40.0 quality %) (P10).The Mn of the solution of gained PEMULEN TR2 is 3,800, and Mw is 6,700.
[table 1]
* molecular weight is the polystyrene conversion value
< embodiment 1-embodiment 10 and comparative example 1-comparative example 3 >
To form each compsn of preparation embodiment 1-embodiment 10 and comparative example 1-3 shown in the table 2, respectively its smooth voltinism, solvent resistance, transsmissivity and orientation are estimated.
[table 2]
| (A) composition ※Solution (g) | (B) composition (g) | (C) composition (g) | Solvent (g) | |
| Embodiment 1 | P1 20 | CEL 1.2 | - | PGMEA 5.47 |
| Embodiment 2 | P1 20 | CEL 1.2 | BM?I1 0.6 | PGMEA 5.47 |
| Embodiment 3 | P2 20 | CEL 1.2 | BMI1 0.6 | PGMEA 5.47 |
| Embodiment 4 | P3 20 | CEL 1.2 | BMI1 0.6 | PGMEA 5.47 |
| Embodiment 5 | P4 20 | CEL 1.2 | PGMEA 5.47 | |
| Embodiment 6 | P5 20 | CEL 1.2 | PGMEA 5.47 | |
| Embodiment 7 | P6 20 | CEL 1.2 | PGMEA 5.47 | |
| Embodiment 8 | P7 20 | CEL 1.2 | PGMEA 5.47 | |
| Embodiment 9 | P8 20 | CEL 1.2 | PGMEA 5.47 | |
| Embodiment 10 | P4 20 | CEL 1.2 | BMI1 0.6 | PGMEA 7.09 |
| Comparative example 1 | P1 20 | - | - | PGMEA 2.22 |
| Comparative example 2 | P9 20 | CEL 1.2 | - | NMP 2.97 |
| Comparative example 3 | P10 20 | CEL 1.2 | - | PGMEA 2.80 |
※ P1～P8: polyester liquid P9: polyimide precursor solution P10: acrylic acid copolymer soln
[evaluation of smooth voltinism]
Adopting the rotary coating machine that each compsn of embodiment 1-embodiment 10 and comparative example 1-comparative example 3 is coated highly is that 0.5 μ m, live width are that 10 μ m, distance between centers of tracks are on the differential substrate (glass) of 50 μ m; Be on hot plate, to carry out prebake conditions 120 seconds under 100 ℃ in temperature then, forming thickness is filming of 2.8 μ m.Thickness adopts the system F20 of FILMETRICS society to measure.Through this being filmed in temperature is that the back baking was carried out in 230 ℃ of following heating in 30 minutes, and forming thickness is the cured film of 2.5 μ m.
Measure on the differential plate line film with at interval on the film thickness difference of filming (with reference to Fig. 1), adopt the formula of planarization rate (DOP)=100 * [height of the film thickness difference that 1-{ films (μ m)/differential substrate (0.5 μ m) }] to obtain the planarization rate.
[evaluation of solvent resistance]
Adopting the rotary coating machine that each compsn of embodiment 1-embodiment 10 and comparative example 1-comparative example 3 is coated silicon wafer, is prebake conditions 120 seconds on the hot plate 100 ℃ under in temperature then, and the formation thickness is filming of 2.8 μ m.Thickness adopts the system F20 of FILMETRICS society to measure.This is filmed in temperature is on hot plate, to carry out back baking 30 minutes under 230 ℃, and forming thickness is the cured film of 2.5 μ m.
This cured film was flooded 60 seconds in PGMEA or NMP, was 100 ℃ of following dryings 60 seconds in temperature respectively then, measured thickness.PGMEA or the unconverted cured film of NMP dipping back thickness are designated as zero, the cured film of observing the thickness minimizing behind the dipping is designated as *.
[evaluation of optical transmittance (transparency)]
Adopting the rotary coating machine that each compsn of embodiment 1-embodiment 10 and comparative example 1-comparative example 3 is coated on the quartz base plate, is on hot plate, to carry out prebake conditions 120 seconds under 100 ℃ in temperature then, and forming thickness is filming of 2.8 μ m.Thickness adopts the system F20 of FILMETRICS society to measure.This is filmed in temperature is on hot plate, to carry out the back under 230 ℃ to toast 30 minutes to form cured film.
Adopt ultraviolet-visible pectrophotometer (the system SHIMADSU UV-2550 of (strain) Shimadzu Seisakusho Ltd. model) to measure the transsmissivity of this cured film when wavelength is 400nm.
[evaluation of orientation]
Adopt the rotary coating machine that each compsn of embodiment 1-embodiment 10 and comparative example 1-comparative example 3 is coated on the ito substrate, then temperature be under 100 ℃ on hot plate prebake conditions 120 seconds, forming thickness is filming of 2.8 μ m.Thickness adopts the system F20 of FILMETRICS society to measure.This is filmed in temperature is on hot plate, to carry out the back under 230 ℃ to toast 30 minutes to form cured film.
With this cured film is that 700rpm, speed of feed are that 10mm/ second, the amount of pushing are that 0.45mm carries out friction treatment with the speed of rotation.With the substrate after the friction treatment with pure water ultrasonic cleaning 5 minutes.Adopt the rotary coating machine to be coated on this substrate by the phase differential material that liquid crystal monomer is processed, under 100 ℃, on hot plate, carried out prebake conditions 40 seconds then, under 55 ℃, carrying out prebake conditions was filming of 1.1 μ m to form thickness in 30 seconds.With 2,000mJ is exposed under the nitrogen atmosphere with this substrate.The substrate of processing is clamped between deflector plate the Visual Confirmation orientation.The tilt substrate of the 45 optical transmission property noticeable changes when not tilting when spending of substrate is designated as zero, indeclinable substrate is designated as *.
[stable on heating evaluation]
Adopt the rotary coating machine that each compsn of embodiment 1-embodiment 4 and comparative example 1-comparative example 3 is coated on the quartz base plate; Then temperature be under 100 ℃ on hot plate prebake conditions 120 seconds; Under 230 ℃, on hot plate, carry out the back then and toast 30 minutes to form cured film, thickness adopts the system F20 of FILMETRICS society to measure.Then, again cured film is burnt till 60 minutes and measured once more thickness under 230 ℃ of temperature on hot plate, calculate the velocity of variation of the thickness after the baking of back.In addition, be considered to have stable on heating cured film, expectation has at least that the Thickness Variation rate is lower than ± 5% performance.
[result of evaluation]
The result who carries out above evaluation is as shown in table 3 below.
[table 3]
※ 1 undetermined
※ 2 can't not measure because of forming cured film.
Demonstrate in embodiment 1-embodiment 10 that the planarization rate is high, any all has patience in to PGMEA, NMP.In addition, in embodiment 1-embodiment 10, all show good orientation, also show high-transmission rate (transparency) after high temperature burns till.Particularly in embodiment 1-embodiment 4, obtain the Thickness Variation rate to be lower than ± 5% cured film, and confirm to have thermotolerance.
On the other hand, comparative example 1 can not form cured film.
In addition, the result of comparative example 2 shows that solvent resistance, thermotolerance and orientation are good, but the planarization rate is very low.
The result of comparative example 3 shows that planarization rate, thermotolerance, solvent resistance and transsmissivity are good, but poor orientation.
As stated; Thermofixation film formation of the present invention can be used glycolic solvents such as propylene glycol monomethyl ether when cured film forms with polymer blend, and any performance of gained cured film in transmitance, solvent resistance, thermotolerance, smooth voltinism and the orientation of excellence is all good.
The industry utilizability
Thermofixation film of the present invention forms very useful as the liquid crystal orientation film of optical anisotropic film or liquid crystal display device with polymer blend; In addition; Also be suitable as the material of the cured film of protective membrane in the various indicating meters such as forming thin film transistor (TFT) type liquid crystal display device, organic EL, planarization film, insulating film etc., be particularly suitable for the material of the interlayer dielectric as TFT type liquid crystal cell, the protective membrane of colour filter, the insulating film of organic EL etc.
Description of drawings
Fig. 1 is the model diagram of the cured film that forms when being presented at coated heat curable polyester compsn on the differential substrate.
Fig. 2 be with the liquid crystal cell (a) that adopts technology in the past to form liquid crystal orientation film with adopt thermofixation film of the present invention to form to form the model diagram that the liquid crystal cell (b) of liquid crystal orientation film compares with polymer blend.
Claims (7)
1. adopt the thermofixation film to form the liquid crystal orientation film that obtains with polymer blend, said thermofixation film forms and contains composition (A) and composition (B) with polymer blend,
Composition (A): comprise the polyester of the represented structural unit of following formula (1),
Composition (B): have the epoxy compounds of 2 above epoxy group(ing),
In the formula, A is selected from least a in the represented group of following formula (A-1)-Shi (A-15), and B is selected from least a in the represented group of following formula (B-1)-Shi (B-5).
2. employing thermofixation film according to claim 1 forms the liquid crystal orientation film that obtains with polymer blend, and in above-mentioned formula (1), A is selected from least a in the represented group of following formula (A-1)-Shi (A-8).
3. employing thermofixation film according to claim 1 forms the liquid crystal orientation film that obtains with polymer blend; Composition (A) is through making the tetracarboxylic acid composition and the (ii) represented diol compound of following formula that comprise the represented tetracarboxylic dianhydride of following formula (i) react the polyester that obtains
In the formula, A is identical with the definition in the above-mentioned formula (1) with B.
4. employing thermofixation film according to claim 1 forms the liquid crystal orientation film that obtains with polymer blend, and the weight-average molecular weight of composition (A) polyester is 1 with polystyrene conversion, 000-30,000.
5. employing thermofixation film according to claim 1 forms the liquid crystal orientation film that obtains with polymer blend, further contains bismaleimide compound as composition (C).
6. employing thermofixation film according to claim 1 forms the liquid crystal orientation film that obtains with polymer blend, comprises the composition (B) of 3-50 mass parts based on 100 mass parts compositions (A).
7. form the liquid crystal orientation film that obtains with polymer blend according to claim 5 or 6 described employing thermofixation films, comprise the composition (C) of 0.5-50 mass parts based on 100 mass parts compositions (A).
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| PCT/JP2008/068766 WO2009051186A1 (en) | 2007-10-19 | 2008-10-16 | Polyester composition for production of thermally cured film |
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| WO2009051186A1 (en) * | 2007-10-19 | 2009-04-23 | Nissan Chemical Industries, Ltd. | Polyester composition for production of thermally cured film |
| WO2010110221A1 (en) * | 2009-03-23 | 2010-09-30 | 日産化学工業株式会社 | Polyester composition for forming heat-cured film |
| KR101943401B1 (en) * | 2010-08-11 | 2019-01-29 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal orientation material |
| JP5884442B2 (en) | 2011-11-25 | 2016-03-15 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, method for forming liquid crystal alignment film, and liquid crystal display element |
| JP6128804B2 (en) * | 2012-09-28 | 2017-05-17 | 株式会社ダイセル | Thermosetting liquid crystal polyester composition and cured product thereof |
| CN105793354B (en) * | 2013-11-18 | 2018-05-29 | 东丽株式会社 | Thermoplastic polyester resin composition and molded product |
| TWI525127B (en) * | 2014-09-25 | 2016-03-11 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device having the same |
| CN105440285B (en) * | 2016-01-07 | 2018-10-16 | 中国科学院长春应用化学研究所 | A kind of polyimides and its preparation method and application |
| KR102202056B1 (en) * | 2018-02-21 | 2021-01-11 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
| JP6950573B2 (en) | 2018-02-26 | 2021-10-13 | Jnc株式会社 | Thermosetting composition |
| JP6947102B2 (en) | 2018-03-29 | 2021-10-13 | Jnc株式会社 | Thermosetting composition |
| JP7047559B2 (en) | 2018-04-12 | 2022-04-05 | Jnc株式会社 | Thermosetting composition |
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| CN85107222A (en) * | 1984-11-16 | 1986-05-10 | 三菱电机股份有限公司 | Epoxy resin composition |
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| JPS5146559B2 (en) * | 1973-08-20 | 1976-12-09 | ||
| JPS5388097A (en) * | 1977-03-04 | 1978-08-03 | Nitto Electric Ind Co Ltd | Epoxy resin composition |
| JPS54142244A (en) * | 1978-04-28 | 1979-11-06 | Toagosei Chem Ind Co Ltd | Adhesive |
| JPS61120825A (en) * | 1984-11-16 | 1986-06-07 | Mitsubishi Electric Corp | Epoxy resin composition |
| JP4390028B2 (en) * | 2000-10-04 | 2009-12-24 | 日産化学工業株式会社 | Positive photosensitive polyimide resin composition |
| JP4569233B2 (en) * | 2003-09-09 | 2010-10-27 | チッソ株式会社 | Thermosetting resin composition and cured film |
| JP4779670B2 (en) * | 2005-03-08 | 2011-09-28 | Ｊｎｃ株式会社 | Thermosetting polymer composition |
| KR100782437B1 (en) * | 2005-12-30 | 2007-12-05 | 제일모직주식회사 | Alignment Agent of Liquid Crystal |
| JP5061709B2 (en) * | 2006-06-29 | 2012-10-31 | Ｊｎｃ株式会社 | Composition for liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element |
| JP5018197B2 (en) * | 2007-04-09 | 2012-09-05 | Ｊｎｃ株式会社 | Thermosetting resin composition and cured film |
| WO2009051186A1 (en) * | 2007-10-19 | 2009-04-23 | Nissan Chemical Industries, Ltd. | Polyester composition for production of thermally cured film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85107222A (en) * | 1984-11-16 | 1986-05-10 | 三菱电机股份有限公司 | Epoxy resin composition |
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| Title |
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| JP昭53-88097A 1978.08.03 |
| JP特开昭50-41998A 1975.04.16 |
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| Publication number | Publication date |
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| CN101809057A (en) | 2010-08-18 |
| JP2013253263A (en) | 2013-12-19 |
| JP5477607B2 (en) | 2014-04-23 |
| TWI462946B (en) | 2014-12-01 |
| JPWO2009051186A1 (en) | 2011-03-03 |
| KR101521107B1 (en) | 2015-05-18 |
| WO2009051186A1 (en) | 2009-04-23 |
| CN102731975B (en) | 2014-10-15 |
| JP5435230B2 (en) | 2014-03-05 |
| CN102731975A (en) | 2012-10-17 |
| TWI512040B (en) | 2015-12-11 |
| TW201502197A (en) | 2015-01-16 |
| KR20100098372A (en) | 2010-09-06 |
| TW200934804A (en) | 2009-08-16 |
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