CN105219000B - Resin combination, liquid crystal aligning material and phase difference material - Google Patents

Resin combination, liquid crystal aligning material and phase difference material Download PDF

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Publication number
CN105219000B
CN105219000B CN201510671744.0A CN201510671744A CN105219000B CN 105219000 B CN105219000 B CN 105219000B CN 201510671744 A CN201510671744 A CN 201510671744A CN 105219000 B CN105219000 B CN 105219000B
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composition
liquid crystal
resin combination
crystal aligning
polymer
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CN105219000A (en
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畑中真
安达勲
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Nissan Chemical Corp
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Nissan Chemical Corp
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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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133635—Multifunctional compensators
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric
    • G02F2202/023—Materials and properties organic material polymeric curable

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  • Compositions Of Macromolecular Compounds (AREA)
  • Optical Filters (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

The problem of the present invention, which is to provide, to be coated with the thickness for more than 1 μm after being solidified using heat curing techniques, in addition, the resin combination of display high transparency, high solvent resistance and excellent liquid crystal aligning ability.As the method for problem of the present invention is solved for a kind of resin combination, the resin combination contains the polymer that side chain has cyclohexene ring, or contains the compound and binder polymer in the end shown in formula (1) with cyclohexene ring.[in formula (1), R represents the organic group of carbon number 1~20, and X represents hydrogen atom, methyl or halogen atom.]

Description

Resin combination, liquid crystal aligning material and phase difference material
The present invention is the applying date for August in 2011 10 days, Application No. 201180039058.1, entitled " resin The divisional application of the patent application of composition, liquid crystal aligning material and phase difference material ".
Technical field
The present invention relates to resin combination, liquid crystal aligning material and phase difference material.
Background technology
In general, in the optical devices such as liquid crystal display cells, organic EL (electroluminescent) elements and solid-state imager, The diaphragm for protection element surface is provided with against the solvent of manufacturing process, the infringement of heat.For the diaphragm, it is desirable to Not only solvent resistance, heat resistance are high, and high with the tack of protected substrate, and the transparency is high.
Said protection film is as example, the protection of colour filter used in color liquid crystal display arrangement, solid-state imager Film is used.In this case, diaphragm in order to by the colour filter of substrate, black matrix" planarization, it is desirable to be able to for example, 1 μm Thickness above is formed.Particularly, when manufacturing STN modes, the color liquid crystal display device of TFT modes, due to needing very Fitting for filter substrate and counter substrate is closely carried out, therefore the unit interval between substrate is uniformly necessary, is protected Cuticula also requires there is high planarization capability to substrate.In addition, the transmissivity in order to maintain the light through colour filter, diaphragm is also Need high transparency.
In recent years, carried out by importing phase difference material in the unit (cell) in liquid crystal display, so as to realize low Cost and light-weighted research.
Fig. 2 is the schematic configuration for the liquid crystal cells 200 that liquid crystal orientation film is formd by conventional art.In the figure In, liquid crystal layer 208 is clamped between 2 pieces of substrates 201,211.ITO210 and alignment films 209 are formd on substrate 211.In addition, On substrate 201, outer covering layer (the hereinafter referred to as CF outer covering layers of colour filter 202, colour filter (CF) have been sequentially formed.) 203, take To film 204, phase difference material 205, ITO206 and alignment films 207.
In conventional liquid crystal cells, in order that the polymerizable liquid crystal for above-mentioned phase difference material formation takes before curing To, it is necessary to which the film of liquid crystal aligning can be made by being set in addition in its lower floor, i.e. alignment films.Alignment films are shone by milled processed, polarisation The process such as penetrate to be formed.That is, as shown in Fig. 2 in the past, it is however generally that formed on CF outer covering layers 203 after alignment films 204, at it It is upper to form the phase difference material 205 obtained by polymerizable liquid crystals such as liquid crystal monomers.That is, it needs to after colour filter 202 is formd, enter This 2 layers of one step lamination CF outer covering layers 203 and alignment films 204 are formed, as making the complicated process of manufacturing process.
It is strong to expect to provide the film for meeting multiple different requirement characteristics simultaneously and form the film based on the reason for such Material.In particular, it is desirable to have the film of alignment films and CF outer covering layers concurrently and form the material of the film.Thus, in manufacture liquid crystal In terms of showing device, the very big advantage such as cost degradation, the reduction of technique number, raising of handling capacity can be enjoyed.
In general, CF outer covering layers have used transparent high acrylic resin.On these acrylic resins, from From the viewpoint of operability and coating, the glycol such as propylene glycol monomethyl ether, propylene glycol monomethyl ether are widely used for The solvent of system, the solvent of the ester system such as ethyl lactate, butyl lactate, the solvent of the ketone system such as cyclohexanone, methyl amyl ketone.Moreover, logical Cross solidifies acrylic resin using heat, light, thus show heat resistance, solvent resistance (for example, referring to patent document 1 or 2。)
However, being shown according to the research of the present inventor etc., in the past by thermosetting, the acrylic resin of photo-curable The CF outer covering layers of composition, although the transparency, planarization property are obtained, even if implementing milled processed to it can not show fully Liquid crystal aligning.Therefore, it is interpreted as conventional CF outer covering layers can not being directly applied to and above-mentioned has alignment films concurrently and CF is cladded with The film of layer.
On the other hand, as alignment films, all the time, used and formed by solvent-soluble polyimide, polyamic acid Material.There is report to claim：By by these materials in rear baking by fully imidizate, so as to obtain solvent resistance, together When sufficient orientation (with reference to patent document 3) can also be realized by milled processed.However, treating as CF outer covering layers In the case of, have due to film is thickened and the problems such as the transparency is greatly reduced.In addition, although polyimides, polyamic acid dissolve in 1-METHYLPYRROLIDONE, gamma-butyrolacton equal solvent, but solvent relative to glycol system, the dissolubility of the solvent of ester system are low, because This also has the problems such as being difficult to be applicable the production line of CF outer covering layers.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-103937 publications
Patent document 2：Japanese Unexamined Patent Publication 2000-119472 publications
Patent document 3：Japanese Unexamined Patent Publication 2005-037920 publications
The content of the invention
Invent problem to be solved
The present invention be based on more than understanding, result of study and propose.That is, it is an object of the invention to provide can be formed With excellent orientation, solvent resistance, heat resistance and the transparency, the resin group for the cured film that can be applied as CF outer covering layers Compound.
Other objects and advantages of the present invention can clearly be seen by following record.
Method for solving problem
The 1st mode of the present invention is related to a kind of resin combination, it is characterised in that it, which contains side chain, has cyclohexene ring Polymer (A compositions).
In the 1st mode of the present invention, the main chain preferably as the polymer of A compositions is the monomer with unsaturated double-bond Polymer.
In the 1st mode of the present invention, the main chain preferably as the polymer of A compositions is acrylic acid series polymeric compounds.
In the 1st mode of the present invention, polyvinyl alcohol is derived from preferably as the polymer of A compositions.
In the 1st mode of the present invention, ring structure is included preferably as the main chain of the polymer of A compositions.
In the 1st mode of the present invention, the main chain preferably as the polymer of A compositions is polyester resin.
In the 1st mode of the present invention, the main chain preferably as the polymer of A compositions is novolac resin.
In the 1st mode of the present invention, the polymer preferably as A compositions is cyclic olefin polymer.
The present invention the 1st mode in, preferably as A compositions polymer have as crosslinked group side chain.
It is selected from hydroxyl, carboxylic preferably as the crosslinked group that the polymer of A compositions has in the 1st mode of the present invention At least one functional group in base, epoxy radicals and acryloyl group.
In the 1st mode of the present invention, preferably further containing the crosslinking agent (C compositions) that can be reacted by heat.
In the 1st mode of the present invention, preferably further containing crosslinking catalyst (E compositions).
The 2nd mode of the present invention is related to a kind of resin combination, and it contains：There is cyclohexene in the end shown in formula (1) The compound (B component) of ring, and
Binder polymer (D compositions),
[in formula (1), R represents the organic group of carbon number 1~20, and X represents hydrogen atom, methyl or halogen atom.]
In the 2nd mode of the present invention, preferably (D) composition is the polyester resin for including the construction unit shown in formula (2).
[in formula (2), A represents to be combined with 4 valency organic groups of 4 connecting keys in alicyclic skeleton or aliphatic skeleton, B represents to be combined with the divalent organic group of 2 connecting keys in alicyclic skeleton or aliphatic skeleton.]
In the 2nd mode of the present invention, preferably (D) composition is acrylic acid series polymeric compounds.
In the 2nd mode of the present invention, preferably further containing the crosslinking agent (C compositions) that can be reacted by heat.
In the 2nd mode of the present invention, preferably further containing crosslinking catalyst (E compositions).
The 3rd mode of the present invention is related to a kind of liquid crystal aligning material, it is characterised in that it is the 1st He using the present invention Obtained by the resin combination of 2nd mode.
The 4th mode of the present invention is related to a kind of phase difference material, it is characterised in that it is used by the 1st He of the present invention Cured film obtained by the resin combination of 2nd mode is formed.
Invention effect
According to the resin combination of the 1st mode of the present invention, it can be formed with excellent orientation, solvent resistance, resistance to The hot and transparency, the cured film that can be applied as CF outer covering layers.
According to the resin combination of the 2nd mode of the present invention, it can be formed with excellent orientation, solvent resistance, resistance to The hot and transparency, the cured film that can be applied as CF outer covering layers.
The photopermeability of liquid crystal aligning material of the 3rd mode of the present invention, heat resistance, solvent resistance and orientation are excellent.
The phase difference material of the 4th mode of the present invention can be configured in liquid crystal cells.For having used the phase difference material The liquid crystal cells of material, can improve contrast.
Brief description of the drawings
Fig. 1 is the schematic configuration of the liquid crystal cells obtained by embodiments of the present invention.
Fig. 2 is the schematic configuration of conventional liquid crystal cells.
Embodiment
The present invention relates to resin combination, using liquid crystal aligning material formed by the resin combination and using by this Phase difference material formed by the cured film that resin combination is obtained.Taken more specifically to that can be formed with excellent Tropism, solvent resistance, heat resistance and the transparency, the resin combination for the cured film that can be applied as CF outer covering layers, use this Liquid crystal aligning material formed by resin combination and use phase difference material formed by the liquid crystal aligning material.By this hair The cured film of bright resin combination formation is suitable as the film for possessing the function as the CF outer covering layers in liquid crystal display, this Outside, possess orientation function due to being formed relative to the polymerizable liquid crystal of phase separation layer, therefore be also suitable for built-in phase difference The formation of layer.
That is, according to the resin combination of the present invention, it can be coated with such as more than 1 μm of thickness, can be formed and removed Beyond high transparency, high solvent resistance, the cured film with liquid crystal aligning ability.Therefore, the resin combination can conduct The formation materials'use of liquid crystal orientation film, planarization film.Particularly can be by the liquid crystal orientation film being separately formed and filter in the past The outer covering layer of color device is arranged at liquid crystal cells as " liquid crystal aligning layer (the CF outer covering layers) " for having both the characteristic of both (cell) in.It therefore, it can the simplification by manufacturing process and the reduction of technique number to realize cost degradation etc..
In addition, the resin combination of the present invention is due to dissolving in the solvent of glycol system and the solvent of lactate system, thus it is suitable Together in the production line for the planarization film for mainly using these solvents.
Hereinafter, to resin combination, liquid crystal aligning material and the phase difference material of the present invention, enumerate concrete example and carry out in detail Ground explanation.
The composition that the resin combination of embodiments of the present invention can contain is as described below.
(A) composition：Side chain has the polymer of cyclohexene ring
(B) composition：End has the compound of cyclohexene ring
(C) composition：Crosslinking agent
(D) composition：Other polymer (in present specification, also referred to as binder polymer.)
(E) composition：Crosslinking catalyst
In addition, in the resin combination of embodiments of the present invention, the combination of composition preferably is as follows.
[1]：Based on the mass parts of (A) composition 100, the resin combination containing 1~100 mass parts (C) composition.
[2]：The mass parts of total amount 100 based on (B) composition He (D) composition, the tree containing 1~100 mass parts (C) composition Oil/fat composition.
[3]：Based on the mass parts of (A) composition 100, the resin combination containing 1~100 mass parts (C) composition and solvent.
[4]：The mass parts of total amount 100 based on (B) composition He (D) composition, containing 1~100 mass parts (C) composition and The resin combination of solvent.
[5]：Based on 100 mass parts of (A) composition, containing 1~100 mass parts (C) composition, 0.01~5 mass parts (E) into Point and solvent resin combination.
[6]：The mass parts of total amount 100 based on (B) composition He (D) composition, containing 1~100 mass parts (C) composition, The resin combination of 0.01~5 mass parts (E) composition and solvent.
Hereinafter, it is described for the details of each composition for the resin combination for constituting the present invention.
(A) composition
(A) composition contained by the resin combination of embodiments of the present invention has the polymerization of cyclohexene ring for side chain Thing.There is no particular limitation for skeleton for main polymer chain etc..The polymer preferably have carried out by hot autoreaction or The reactive group being crosslinked with crosslinking agent.
As the example of the polymer of (A) composition, can enumerate acrylic acid series polymeric compounds, polyvinyl, polyester resin, Novolac resin and cyclic olefin polymer etc..
As the method for importing cyclohexene ring in the polymer, the addition hexamethylene on the polymer with epoxy radicals can be enumerated The method of zinecarboxylic acid；The method for making the polymer with hydroxyl carry out condensation reaction with cyclohexene dicarboxylic acid acid anhydride；Make with hydroxyl Or the method that the polymer of amino is reacted with cyclohexene formyl chloride, or polymerize using the monomer with cyclohexene ring Method etc..
Hereinafter, the concrete example of the polymer as (A) composition is shown.
In above-mentioned formula (A-1)~(A-7), X1Represent hydrogen atom or carboxyl, Y1Represent hydrogen atom or methyl, R1Represent hydrogen Atom, alkyl or acetyl group, R2Represent hydrogen atom or glycidyl.In addition, n and m ratio is n/m=100/0~30/ 70.In formula (A-7), A1Represent ester ring type base, the group formed by ester ring type base and fatty group or the base containing benzene ring structure Group, B1Represent ester ring type base, the group formed by ester ring type base and fatty group or the group containing benzene ring structure.
(A) weight average molecular weight of composition is preferably calculated as 1,000~50,000 with polystyrene conversion.
On (A) composition of acrylic acid series, illustrate its synthetic method.
There is no particular limitation for the method for the acquisition acrylic acid series polymeric compounds as described above with cyclohexene ring, for example, Acrylic acid series polymeric compounds with glycidyl or hydroxyl can be generated, then, by making by advance radical polymerization etc. It is reacted with cyclohexenecarboxylic acid, cyclohexene formyl chloride or cyclohexene dicarboxylic acid anhydride etc., so as to be made as the third of (A) composition Olefin(e) acid based polymer.
As the free radical polymerization monomer with glycidyl, can enumerate for example, GMA, Glycidyl acrylate, acrylic acid 4- hydroxybutyls glycidyl ether and methacrylic acid 4- hydroxybutyl glycidols Base ether etc..
As the free radical polymerization monomer with hydroxyl, it can enumerate for example, hydroxy styrenes, N- (hydroxy phenyl) third Acrylamide, N- (hydroxy phenyl) Methacrylamide, N- (hydroxy phenyl) maleimide, acrylic acid 2- hydroxy methacrylates, third Olefin(e) acid 2- hydroxy propyl esters, 5- acryloxy -6- hydroxy norbomene -2- formic acid -6- lactones, methacrylic acid 2- hydroxy methacrylates, methacrylic acid 2- hydroxy propyl esters and 5- methacryloxy -6- hydroxy norbomene -2- first Acid -6- lactones etc..
On the resin combination of embodiments of the present invention, there is glycidyl, hydroxyl etc. for hexamethylene obtaining During the acrylic acid series polymeric compounds of the effective particular functional group of importing of alkene ring, can be used together can be with the list with particular functional group Body carries out the monomer of copolymerization.The concrete example of such monomer is enumerated below, but is not limited to this.
As the monomer of copolymerization can be carried out with the monomer with particular functional group, it can enumerate for example, acrylate chemical combination Thing, methacrylate compound, maleimide compound, acrylonitrile, maleic anhydride, distyryl compound and vinylated Compound etc..
As the concrete example of above-mentioned monomer, can enumerate acrylic acid, methacrylic acid, crotonic acid, phthalic acid list- (2- (acryloxy) ethyl) ester, phthalic acid list-(2- (methacryloxy) ethyl) ester, N- (carboxyl benzene Base) maleimide, N- (carboxyl phenyl) Methacrylamide, N- (carboxyl phenyl) acrylamide, methyl acrylate, propylene Acetoacetic ester, isopropyl acrylate, benzyl acrylate, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthracene methyl esters, phenyl acrylate, Acrylic acid 2,2,2- trifluoro ethyl esters, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2- methoxies Base ethyl ester, methoxy triglycol acrylate, acrylic acid 2- ethoxy ethyl esters, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxies Base butyl ester, 2- methyl -2- adamantyl acrylates, 2- propyl group -2- adamantyl acrylates, acrylic acid 8- first Base -8- tricyclodecyls, acrylic acid 8- ethyl -8- tricyclodecyls, methyl methacrylate, EMA, methyl Isopropyl acrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthracene methyl esters, first Base phenyl acrylate, methacrylic acid 2,2,2- trifluoro ethyl esters, Tert-butyl Methacrylate, cyclohexyl methacrylate, methyl Isobornyl acrylate, methacrylic acid 2- methoxy acrylates, methoxy triglycol methacrylate, methacrylic acid 2- Ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyls, 2- methyl -2- adamantyl first Base acrylate, gamma-butyrolacton methacrylate, 2- propyl group -2- adamantyl methacrylates, methacrylic acid 8- methyl -8- tricyclodecyls and methacrylic acid 8- ethyl -8- tricyclodecyls, divinyl ether, methyl vinyl ether, Benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, 2- hydroxyethyl vinyl ethers, Vinyl phenyl ether and Propyl vinyl ether, styrene, methyl styrene, chlorostyrene, bromstyrol, maleimide, N- methyl maleimides Amine, N-phenylmaleimide and N- N-cyclohexylmaleimides etc..
The acrylic acid series polymeric compounds with cyclohexene ring used in the resin combination for obtaining embodiments of the present invention Method there is no particular limitation, for example, by make the monomer with particular functional group, other monomer for being capable of copolymerization and Polymerization initiator as needed etc. carries out polymerisation to obtain in the solvent coexisted at a temperature of 50~110 DEG C.This When, if solvent used make composition have particular functional group acrylic acid series polymeric compounds monomer with particular functional group Acrylic polymeric dissolves, and there is no particular limitation.As concrete example, solvent described later can be enumerated.
The acrylic acid series polymeric compounds with particular functional group being achieved in that are usually the solution state being dissolved in solvent.
Then, the acrylic acid series polymeric compounds with particular functional group and the compound with cyclohexene ring of gained can be made Reacted, as the acrylic acid series polymeric compounds with cyclohexene ring of (A) composition (hereinafter also referred to as specific copolymerization Thing.).Now, usually using the solution of the acrylic acid series polymeric compounds with particular functional group.Specifically, have for example, following institute Synthetic method shown etc..
By in the solution of the acrylic acid series polymeric compounds with hydroxyl, existing in catalyst such as benzyltriethylammoinium chlorides Under, reacted cyclohexenecarboxylic acid at a temperature of 80 DEG C~150 DEG C, it is hereby achieved that specific copolymer.Now, it is used Solvent be dissolving constitute specific copolymer monomer and specific copolymer, there is no particular limitation., can as concrete example Enumerate solvent described later.
By in the solution of the acrylic acid series polymeric compounds with hydroxyl, existing in catalyst such as benzyltriethylammoinium chlorides Under, reacted cyclohexene dicarboxylic acid anhydride at a temperature of 80 DEG C~150 DEG C, it is hereby achieved that specific copolymer.Now, Solvent used constitutes the monomer of specific copolymer and the solvent of specific copolymer for dissolving, preferably without the molten of hydroxyl Agent.
By in the solution of the acrylic acid series polymeric compounds with hydroxyl, in the presence of the tertiary amines such as triethylamine, 0 DEG C~40 Make after cyclohexene dimethyl chloride reacted, the salt and amine of generation to be removed, it is hereby achieved that specific copolymer at a temperature of DEG C. Now, solvent used constitutes the monomer of specific copolymer and the solvent of specific copolymer for dissolving, preferably without hydroxyl Solvent.
The specific copolymer obtained as described above is usually the solution state that specific copolymer is dissolved in solvent.
In addition, being made by making the solution of the above-mentioned specific copolymer obtained like that put into ether, water under stirring etc. Their reprecipitations, after the sediment filtering of generation, washing, under normal or reduced pressure, carry out normal temperature or heat drying, so as to So that the powder of specific copolymer is made.By such operation, so as to remove and specific copolymer coexists polymerize initiation Agent, unreacted monomer, the result is that obtaining the powder of specific copolymer after purification.In addition, can not be abundant with once-through operation In the case that ground is purified, as long as making the powder of gained be redissolved in a solvent, repeat aforesaid operations.
In the resin combination of embodiments of the present invention, the powder of specific copolymer can be directly used, or can be by The powder is re-dissolved in for example, being used in solvent described later with the state of solution.
In addition, in the resin combination of embodiments of the present invention, the acrylic acid series polymeric compounds of (A) composition can be a variety of The mixture of specific copolymer.
Next, the synthetic method of (A) composition of Pyrogentisinic Acid's phenolic varnish type is illustrated.
By in the presence of the catalyst such as benzyltriethylammoinium chloride, making epoxidation benzene at a temperature of 80 DEG C~150 DEG C Phenol novolac resin or epoxidized cresol novolac resin, reacted with cyclohexenecarboxylic acid, it is hereby achieved that having The polymer of cyclohexene ring.Now, as long as solvent dissolving used constitutes the monomer and specific copolymer of specific copolymer, There is no particular limitation.As concrete example, solvent described later can be enumerated.
In the resin combination of embodiments of the present invention, the commercially available epoxidized phenol that can be used as (A) composition Novolac resin, has for example, エ ピ コ ー ト 152, エ ピ コ ー ト 154 are ((existing for oiling シ ェ Le エ Port キ シ (strain) above ジ ャ パ Application エ Port キ シ レ ジ Application (strain)) system), the phenol such as EPPN201 and EPPN 202 (being made above for Japanese chemical drug (strain)) Phenolic resin varnish type epoxy resin etc..In addition, as the example of commercially available cresol novolak type epoxy resin, EOCN- can be enumerated 102nd, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (are above Japanese chemical drug (strain) System) and エ ピ コ ー 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. cresol novolak type epoxy resin etc..
(B) composition
(B) composition contained by the resin combination of embodiments of the present invention is in end tool shown in following formula (1) There is the compound of cyclohexene ring.
In formula (1), R represents the organic group of carbon number 1~20, and X represents hydrogen atom, methyl or halogen atom.As (B) end of composition has the compound of cyclohexene ring, by making multi-functional epoxy compound be reacted with cyclohexenecarboxylic acid Method, or make the method that polyfunctional alcohol's compound is reacted with cyclohexene formyl chloride or cyclohexene dicarboxylic acid anhydride to obtain.
There is the example of the compound of cyclohexene ring as the end of (B) composition, following compound can be enumerated.
(C) composition
(C) composition contained by the resin combination of embodiments of the present invention is crosslinking agent.As the crosslinking agent, it can lift Go out for example, epoxide, methylol compound and isocyanate compound etc..
In the case where above-mentioned (A) composition or aftermentioned (D) composition are the polymer with hydroxyl, (C) composition is preferably hydroxyl Methyl compound or isocyanate compound.In addition, in the case where (A) composition or (D) composition are the polymer with carboxyl, (C) composition is preferably epoxide, methylol compound or isocyanate compound.
As epoxide, it can enumerate for example, three (2,3- glycidyl) isocyanuric acid esters, BDO two contract Water glyceryl ether, 1,2- epoxies -4- (epoxy ethyl) hexamethylene, glycerine triglycidyl group ether, diethylene glycol (DEG) 2-glycidyl Base ether, 2,6- diglycidyls phenylglycidyl ether, 1,1,3- tri- [to (2,3- glycidoxies) phenyl] third Alkane, 1,2- cyclohexane cyclohexanedimethanodibasic 2-glycidyls base ester, 4,4 '-di-2-ethylhexylphosphine oxide (N, N- diglycidylaniline), 3, 4- epoxycyclohexyl-methyl -3,4- 7-oxa-bicyclo[4.1.0s formic acid esters, trimethylolethane trimethacrylate glycidyl ether, bisphenol-A - Diglycidyl ether and pentaerythrite polyglycidyl ether etc..
Epoxide can use the compound of commercially available product from obtaining easy aspect.Its concrete example is enumerated below (trade name), but it is not limited to this.It can enumerate for example, YH-434 and YH434L (Dongdu chemical conversion (strain) system) etc. have amino Epoxy resin, エ ポ リ ー De GT-401, エ ポ リ ー De GT-403, エ ポ リ ー De GT-301, エ ポ リ ー De GT-302, セ ロ キ サ イ De 2021 and セ ロ キ サ イ De 3000 (ダ イ セ Le chemical industry (strain) system) etc. have cyclohexene oxide knot Epoxy resin, エ ピ コ ー ト 1001, エ ピ コ ー ト 1002, エ ピ コ ー ト 1003, エ ピ コ ー ト 1004, the エ ピ コ ー of structure ト 1007, エ ピ コ ー ト 1009, エ ピ コ ー ト 1010 and エ ピ コ ー ト 828 (are above oiling シ ェ Le エ Port キ シ (strain) (existing ジ ャ パ Application エ Port キ シ レ ジ Application (strain)) system) etc. bisphenol A type epoxy resin, (the oiling シ ェ Le エ of エ ピ コ ー ト 807 Port キ シ (strain) (existing ジ ャ パ Application エ Port キ シ レ ジ Application (strain)) systems) etc. bisphenol f type epoxy resin, デ ナ コ ー Le EX- 252 (Na ガ セ ケ system テ ッ Network ス (strain) systems), CY175, CY177, CY179, ア ラ Le ダ イ ト CY-182, ア ラ Le ダ イ ト CY-192, ア ラ Le ダ イ ト CY-184 (being above CIBA-GEIGY A.G (existing BASF) system), エ ピ Network ロ Application 200, エ ピ Network ロ Application 400 (more than, big Japan イ Application キ chemical industry (strain) (existing DIC (strain)) is made), エ ピ コ ー ト 871, エ ピ コ ー ト 872 (being oiling シ ェ Le エ Port キ シ (strain) (existing ジ ャ パ Application エ Port キ シ レ ジ Application (strain)) systems above), ED-5661, Alicyclic epoxy resin, the デ ナ コ ー Le EX- such as ED-5662 (being made above for セ ラ ニ ー ズ コ ー テ ィ Application グ (strain)) 611st, デ ナ コ ー Le EX-612, デ ナ コ ー Le EX-614, デ ナ コ ー Le EX-622, デ ナ コ ー Le EX-411, デ ナ コ ー Le EX-512, デ ナ コ ー Le EX-522, デ ナ コ ー Le EX-421, デ ナ コ ー Le EX-313, デ Na The aliphatic polyglycidyl ethers such as コ ー Le EX-314, デ ナ コ ー Le EX-321 (Na ガ セ ケ system テ ッ Network ス (strain) systems) Deng.
In addition, as the compound with least two epoxy radicals, being not particularly limited, can using with epoxy radicals Polymer.As such polymer with epoxy radicals, it is, for example, possible to use the polyaddition monomer with epoxy radicals, passes through Addition polymerization is manufactured.As one, polyglycidyl acrylate and GMA and methyl can be enumerated Copolymer, GMA and the styrene of ethyl acrylate and the copolymerization of 2-hydroxyethyl methacrylate The addition polymers such as thing, or the condensation polymer such as epoxy phenolic varnish etc..
In addition, the above-mentioned polymer with epoxy radicals can also by the high-molecular compound with hydroxyl and epichlorohydrin and There is glycidyl tosylat etc. the reaction of the compound of epoxy radicals to be manufactured.Weight as such polymer is equal Molecular weight, for example, being calculated as 300~200,000 with polystyrene conversion.
As the example of the methylol compound that can be used of (C) composition, methoxymethylated glycoluril, methoxy can be enumerated Ylmethyl benzoguanamine and methoxymethylated melamine etc..As concrete example, can enumerate HMMM, Tetramethoxymethyl benzoguanamine, 1,3,4,6- tetra- (butoxymethyl) glycoluril, 1,3,4,6- tetra- (hydroxymethyl) glycoluril, 1, Double (hydroxymethyl) ureas of 3-, 1,1,3,3- tetra- (butoxymethyl) urea, 1,1,3,3- tetra- (methoxy) urea, 1,3- are double (hydroxymethyl) -4,5- dihydroxy -2- imidazolones and double (the methoxy) -4,5- dimethoxys -2- of 1,3- Imidazolone etc..In addition, as commercially available product, three well サ イ テ ッ Network (strain) methoxy methyl fundamental mode melamine chemical combination processed can be enumerated Thing (trade name サ イ メ Le 300, サ イ メ Le 301, サ イ メ Le 303, サ イ メ Le 350), butoxymethyl type melamine Amines (trade name マ イ コ ー ト 506, マ イ コ ー ト 508), glycoluril compounds (trade name サ イ メ Le 1170, パ ウ ダ ー リ Application Network 1174), the carbamide resin (trade name UFR65) that methylates, butylation carbamide resin (trade name UFR300, U- VAN10S60, U-VAN10R, U-VAN11HV), big Japan イ Application キ chemical industry (strain) (showing DIC (strain)) urea processed/formaldehyde system Resin (high condensed type, trade name ベ ッ カ ミ Application J-300S, ベ ッ カ ミ Application P-955, ベ ッ カ ミ Application N) etc..
In addition, as the example of isocyanate compound, following compound can be enumerated.For example, as having in 1 molecule The compound of more than 2 NCOs, can enumerate IPDI, 1, hexamethylene-diisocyanate, di-2-ethylhexylphosphine oxide (4- cyclohexyl isocyanates), trimethyl hexamethylene diisocyanate etc. or their dimer, tripolymer or they with Glycols, three alcohols, the reactant of Diamines or three amines.These isocyanate compounds are steady in order to improve the preservation in solution It is qualitative, preferably use the isocyanate compound being closed by sealer.
As sealer, it can enumerate for example, phenol, o-nitrophenol, parachlorophenol, orthoresol, metacresol or paracresol Etc. the lactams such as phenol, epsilon-caprolactams, acetoxime, methyl ethyl ketone oxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzene Pyrazoles, the dodecyl mercaptans such as the oximes such as acetophenone oxime and diphenyl-ketoxime, pyrazoles, 3,5- dimethyl pyrazoles, 3- methylpyrazoles With the thio-alcohol such as benzenethiol.
As the compound of (C) composition, example in detail below can be enumerated.
As the isocyanate compound as derived from IPDI, following examples can be enumerated.
[in formula (C-4)~formula (C-6), R represents polyether structure.]
As polyether structure, it can enumerate for example, from polyethylene glycol, divalent group of polypropylene glycol etc..
Crosslinking agent can be melamine compound, the urea for the hydrogen atom of amino is replaced by methylol or alkoxy methyl Compound, glycoluril compounds or compound obtained by benzoguanamine compound condensation.It can enumerate for example, being documented in U.S. Patent No. In No. 6323310, by melamine compound (trade name サ イ メ Le 303) and benzoguanamine compound (trade name サ イ メ Le 1123) manufacture high-molecular weight compounds.
In addition, as (C) composition, can also use and use N- hydroxymethylacrylamides, (N- methoxies) first Base acrylamide, (N- ethoxyl methyls) acrylamide, hydroxymethyl or the alkane such as (N- butoxymethyls) Methacrylamide The substituted acrylamide compound of epoxide methyl or methacrylamide compounds and polymer for manufacturing etc..As such Polymer, can be enumerated for example, poly- (N- butoxymethyls) acrylamide, (N- butoxymethyls) acrylamide and styrene Copolymer, the copolymer of (N- hydroxymethyls) Methacrylamide and methyl methacrylate, (N- ethoxyl methyls) methyl The copolymer and N- butoxy methyl acrylamides of acrylamide and benzyl methacrylate and benzyl methacrylate and first Copolymer of base acrylic acid 2- hydroxy propyl esters etc..The weight average molecular weight of such polymer with polystyrene conversion for example, be calculated as 1,000~500,000, preferably 2,000~200,000, more preferably 3,000~150,000, more preferably 3,000 ~50,000.
Above-described crosslinking agent can be used alone or two or more is applied in combination.
In the resin combination of embodiments of the present invention, on the content of the crosslinking agent as (C) composition, using (A) in the case of composition, the mass parts of (A) composition 100 are preferably based on for 1~100 mass parts.In addition, using the feelings of (B) composition The mass parts of total amount 100 under condition, being preferably based on (B) composition and (D) composition are 1~100 mass parts.If the ratio is too small, Then because the solvent resistance of cured film is reduced, therefore orientation is reduced, heat resistance reduction.On the other hand, if aforementioned proportion mistake Greatly, then orientation is reduced sometimes, storage stability reduction.
(D) composition
(D) composition contained by the resin combination of embodiments of the present invention is " other polymer ", be as Add the polymer (binder polymer) of the adhesive of (B) composition.There is no particular limitation for the species of " other polymer ", Can carry out self-crosslinking preferably by with heat cross-linking group, or with polymerizeing that the crosslinking agent as (C) composition is reacted Thing.As heat cross-linking group, carboxyl, hydroxyl, epoxy radicals, oxetanylmethoxy, acryloyl group and methylacryloyl etc. can be enumerated. In addition, the weight average molecular weight of (D) composition is preferably calculated as 1,000~100,000 with polystyrene conversion.
As the preference of other polymer, the polyester resin comprising the construction unit shown in following formula (2), tool can be enumerated Polyester resin shown in the acrylic acid series polymeric compounds or following formula (3) of crosslinking group etc..
[in formula (2), A represents the 4 valency organic groups with 4 connecting keys in alicyclic skeleton or aliphatic skeleton, B Represent the divalent organic group with 2 connecting keys in alicyclic skeleton or aliphatic skeleton.]
[in formula (3), A ' and B ' separately represent the band in alicyclic skeleton, aliphatic skeleton or fragrant ring skeleton There is the divalent organic group of 2 connecting keys, or with ehter bond, ester bond or amido link on these skeletons, and with 2 connecting keys Divalent organic group.]
Polymer shown in above-mentioned formula (2) can pass through following tetracarboxylic dianhydride'ss (formula (i)) and diol compound (formula (ii) polymerisation) is obtained.
HO-B-OH (ii)
In above-mentioned formula (i) and formula (ii), A represents 4 valencys with 4 connecting keys in alicyclic skeleton or aliphatic skeleton Organic group, B represents the divalent organic group with 2 connecting keys in alicyclic skeleton or aliphatic skeleton.
In the resin combination of embodiments of the present invention, the mixing ratio of (B) composition and (D) composition is preferably 5：95~ 50：50.If (B) composition is less than the ratio, orientation is reduced sometimes.On the other hand, if excessive, except solvent resistance Reduction, beyond orientation reduction, film forming is reduced sometimes.In addition, (D) composition can in the range of characteristic is not reduced with (A) Composition is mixed.
(E) composition
The resin combination of embodiments of the present invention can contain crosslinking catalyst as (E) composition.(E) composition is from rush It is effective from the aspect of the thermosetting for entering resin combination.
For example, in the case that the hydroxyl included in resin combination can be reacted with methylol compound, being used as (E) The crosslinking catalyst of composition, acid or thermal acid generator are useful.As such acid or thermal acid generator, it can enumerate containing sulfonic group Compound, hydrochloric acid or its salt, but as long as be in prebake conditions or rear baking thermal decomposition and produce the compound of acid, i.e. 80 ~250 DEG C thermally decompose and produce sour compound, and there is no particular limitation.
As above-mentioned sour concrete example, hydrochloric acid, methanesulfonic acid, ethyl sulfonic acid, propane sulfonic acid, fourth sulfonic acid, penta sulfonic acid, pungent sulphur can be enumerated Acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-hydroxybenzenyl sulfonate, 2- naphthalene sulfonic acids, 1,3,5- trimethyls Benzene sulfonic acid, paraxylene -2- sulfonic acid, meta-xylene -2- sulfonic acid, 4- ethyl phenenyl azochlorosulfonate acids, 1H, 1H, 2H, 2H- perfluors are pungent Alkyl sulfonic acid, perfluor (2- Ethoxyethanes) sulfonic acid, pentafluoroethane sulfonic acid, nine fluorine butane -1- sulfonic acid and DBSA Deng sulfonic acid or its hydrate, salt etc..
In addition, as thermal acid generator, can further enumerate double (tosyl epoxide) ethane, double (tosyl oxygen Base) propane, double (tosyl epoxide) butane, to nitrobenzyl tosylat, adjacent nitro benzyl toluene sulphonic acid ester, 1,2, 3- phenylenes three (metilsulfate), p-methyl benzenesulfonic acid pyridineSalt, p-methyl benzenesulfonic acid morpholineSalt, p-methyl benzenesulfonic acid second Ester, propyl p-toluenesulfonate, butyl p-toluenesulfonate, p-methyl benzenesulfonic acid isobutyl ester, methyl tosylate, p-methyl benzenesulfonic acid benzene Ethyl ester, cyano methyl-p-methyl benzenesulfonic acid ester, 2,2,2- trifluoroethyls-p-methyl benzenesulfonic acid ester, 2- hydroxybutyls-to toluene Sulphonic acid ester and N- ethyl -4- toluenesulfonamides etc., in addition, can also enumerate the compound shown in following formula.
The content of (E) composition in the resin combination of embodiments of the present invention relative to the mass parts of (A) composition 100, Or the mass parts of total amount 100 of (B) composition and (D) composition, preferably 0.01~5 mass parts.If the content of (E) composition is less than 0.01 mass parts, then do not observe the promotion heat cured effect of resin combination sometimes.On the other hand, if it exceeds 5 mass parts, The then storage stability reduction of resin combination sometimes.
＜ solvents ＞
The resin combination of embodiments of the present invention can be used with the solution state being dissolved in solvent.As used Solvent, it is desirable to be able to dissolve (A) composition or dissolving (B) composition and (D) composition.In addition, as needed for the molten of dissolving (C) composition Agent, or dissolve the solvent of (C) composition and (E) composition, or the individually solvent of dissolving (E) composition.In addition, after as needed for dissolving The solvent for the other additives stated.As long as the solvent with such solvability, its species and structure etc. are without special Restriction.
As above-mentioned solvent, it can enumerate for example, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, methyl cellosolve acetic acid Ester, ethyl cellosolve acetate, diethylene glycol monomethyl ether, carbiphene, propane diols, propylene glycol monomethyl ether, the third two Alcohol monomethyl ether acetate, propylene glycol propyl ether acetic acid esters, toluene, dimethylbenzene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2- Heptanone, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyls ethyl propionate, ethoxy ethyl acetate, hydroxyl Ethyl acetate, 2- hydroxy-3-methyls methyl butyrate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxies Base ethyl propionate, 3- ethoxypropanoates, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, lactic acid second Ester, butyl lactate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and 1-METHYLPYRROLIDONE etc..These solvents can Be used alone or two or more be applied in combination.
The other additive ＞ of ＜
As long as in addition, the resin combination of embodiments of the present invention does not damage the effect of the present invention, it is possible to according to need To contain silane coupler, surfactant, rheology control agent, pigment, dyestuff, preserving stabilizer, defoamer and antioxidant Deng.
＜ resin combinations ＞
The resin combination of embodiments of the present invention contains the polymer and work with cyclohexene ring as (A) composition There is any one of the compound of cyclohexene ring for the end of (B) composition.
In addition, the resin combination of embodiments of the present invention contains the crosslinking agent as (C) composition as needed.
In addition, in the case that the resin combination in embodiments of the present invention contains (B) composition, containing as (D) into The other polymer divided.
In addition, the resin combination of embodiments of the present invention can contain the crosslinking catalyst as (E) composition, this Outside, more than a kind in other additives can be contained.
The resin combination of embodiments of the present invention can be used by mentioned component dissolving in a solvent as solution.
The preference of the resin combination of embodiments of the present invention is as follows.
[1]：Based on the mass parts of (A) composition 100, the resin combination containing 1~100 mass parts (C) composition.
[2]：The mass parts of total amount 100 based on (B) composition He (D) composition, the tree containing 1~100 mass parts (C) composition Oil/fat composition.
[3]：Based on 100 mass parts of (A) composition, the resin combination containing 1~100 mass parts (C) composition and solvent Thing.
[4]：The mass parts of total amount 100 based on (B) composition He (D) composition, containing 1~100 mass parts (C) composition and The resin combination of solvent.
[5]：Based on 100 mass parts of (A) composition, containing 1~100 mass parts (C) composition, 0.01~5 mass parts (E) into Point and solvent resin combination.
[6]：The mass parts of total amount 100 based on (B) composition He (D) composition, containing 1~100 mass parts (C) composition, The resin combination of 0.01~5 mass parts (E) composition and solvent.
In the case where the resin combination of embodiments of the present invention is used as solution, its mixing ratio and modulation Method etc. is as follows.
As long as the ratio of the solid constituent in the resin combination of embodiments of the present invention makes each composition equably dissolve In solvent, there is no particular limitation, preferably 1~80 mass %, more preferably 3~60 mass %, further preferably For 5~40 mass %.Here, so-called solid constituent, refers to remove the material after solvent from total composition of resin combination.
There is no particular limitation for the modulator approach of the resin combination of embodiments of the present invention, can enumerate for example, by (A) Composition or (B) composition and (D) composition dissolve in a solvent, in the solution with defined ratio mixing (C) composition, (E) into Point, the method that uniform solution is made.In addition, in the appropriate stage of the modulator approach, can further add as needed Other additives are mixed.
In the modulation of the resin combination of embodiments of the present invention, it will can be obtained by the polymerisation in solvent The solution of polymer directly use.In this case, it is and above-mentioned in the solution of (A) composition or (B) composition and (D) composition When similarly adding (C) composition, (E) composition etc. and uniform solution is made, for the purpose of concentration is adjusted, can further it add Put into solvent.Now, adjusted during the modulation of solvent used in the generating process of polymer and resin combination for concentration Solvent can be with identical, can also be different.
The solution for the resin combination modulated as described above preferably uses filter that aperture is 0.2 μm or so etc. and carried out Filter is used later.
＜ films, cured film and liquid crystal aligning layer ＞
It can use the resin combination of embodiments of the present invention, form film by the following method.
It is possible, firstly, on substrate or film etc., by spin coating, flow coat, roller coat, slot coated, slot coated subsequently to revolve Painting, ink-jet application or printing etc. carry out coating resin composition.Then, carried out by using electric hot plate or baking oven etc. predrying (pre- Baking), so as to form film.Then, by the way that the film to be heated to (rear baking), so as to form cured film.
As the substrate of coating resin composition, can use for example, silicon/silicon dioxide is substrate coated, silicon nitride board, Glass substrate, quartz base plate and ito substrate etc..Additionally it is possible to using for example, being coated with the substrate of the metals such as aluminium, molybdenum or chromium. Additionally it is possible to using for example, resin film such as tri acetyl cellulose membrane, polyester film and acrylic acid mesentery etc. is used as substrate.
As the condition of the prebake conditions for forming film, it can use for example, from 70~160 DEG C of temperature, time 0.3~60 The heating-up temperature suitably selected in the scope of minute and heat time.Heating-up temperature and heat time be preferably 80~140 DEG C and 0.5~10 minute.
As rear baking, it can use from the scope of 140~250 DEG C of temperature, suitably be selected according to heating means etc. Heating-up temperature.In addition, for the heat time similarly, for example, can be 5~30 minutes in the case of on electric hot plate, Can be 30~90 minutes etc. in the case of in baking oven.
, can be fully by making the resin composition of embodiments of the present invention under the conditions of as described above The difference in height for the substrate that colour filter (CF) etc. is caused is covered, so as to be planarized, and the solidification with high transparency is formed Film.In addition, the thickness of cured film can be such as 0.1~30 μm, it can be considered that the difference in height of used substrate, optical Matter, electrical property are suitably selected.
The above-mentioned cured film obtained like that can be by being ground processing, so as to play liquid crystal aligning material, i.e. make tool There is the liquid crystal aligning layer of the molecularly oriented of liquid crystal liquid crystal property.
It is general to use rotary speed 300~1 on the condition of milled processed, 000rpm, feed speed 10~80mm/ seconds, Condition as 0.1~1mm of intrusion.After milled processed, by using pure water etc. carry out ultrasonic washing so that remove by Grind the residue produced.
By on the liquid crystal aligning layer so formed, after coating phase difference material, being heated to the phase transition temperature of liquid crystal, Phase difference material is set to turn into mesomorphic state.Then, photocuring is carried out, it is possible to form optically anisotropic as having The phase difference material of layer.
As phase difference material, it can be used for example, liquid crystal monomer with polymerizable group or containing the liquid crystal monomer Composition etc..It is useful as optical anisotropic film in the case where the base material for being formed with liquid crystal aligning layer is film.As Such phase difference material, is present with the orientation such as horizontal alignment, screw type orientation, vertical orientated, hybrid orientation, biaxial orientation The phase difference material of property, each of which can be used according to required phase difference to distinguish.
Further, it is also possible to make 2 pieces of substrates with the liquid crystal aligning layer formed as described above across pad with liquid crystal aligning Layer mode relative to each other is fitted, then, by between these substrates, liquid crystal being injected, so that the liquid of liquid crystal aligning is made Crystal display element.
So, the resin combination of embodiments of the present invention can perform well in constituting various optical anisotropies Film, liquid crystal display cells.
In addition, the resin combination of embodiments of the present invention is first as the liquid crystal display of thin film transistor (TFT) (TFT) type is formed The material of the cured films such as diaphragm, planarization film, dielectric film in the various displays such as part and organic EL element is also useful. Particularly, in addition to the outer covering layer material (CF outer covering layers) of colour filter (CF), it is used as the layer insulation for forming TFT type liquid crystal cells The material of film, the dielectric film of organic EL element etc. is also suitable.
In the case where the resin combination of embodiments of the present invention is used as CF outer covering layer materials, outside the CF of gained Coating not only can cover the difference in height of colour filter and be planarized, but also be worked as liquid crystal aligning material.Therefore, It can be used as the CF outer covering layers with orientation.
Fig. 1 is the schematic configuration figure of the liquid crystal cells 100 of embodiments of the present invention.In the figure, liquid crystal layer 108 is pressed from both sides Hold between 2 pieces of substrates 101,111.On substrate 111, ITO110 and alignment films 109 are formed.In addition, on the substrate 101, according to It is secondary to form colour filter 102, CF outer covering layers 103, phase difference material 105, ITO106 and alignment films 107.In this case, by Also worked in CF outer covering layers 103 as alignment films, thus can need not be corresponding with Fig. 2 alignment films 204 film.
Embodiment
Hereinafter, embodiment is enumerated, the present invention is illustrated in further detail, but the present invention is not limited to these embodiments.
[shorthand notation used in embodiment]
The implication of the shorthand notation used in following embodiment is as follows.
＜ polymer raw materials ＞
HEMA：2-hydroxyethyl methacrylate
MAA：Methacrylic acid
MMA：Methyl methacrylate
GMA：GMA
CHMI：N- N-cyclohexylmaleimides
AIBN：α, α '-azodiisobutyronitrile
BGOP：4,4 '-bisglycidyl ether epoxide benzene
CHECA：Cyclohexene -4- formic acid
BA：Benzoic acid
CHCA：Naphthenic acid
CHEDA：Cyclohexene -4,5- dicarboxylic acid anhydrides
BPAGE：Bisphenol-A diglycidyl ether
CHDCA：Cyclohexane cyclohexanedimethanodibasic
PVA：Polyvinyl alcohol
HBPDA：3,3 ' -4,4 '-connection cyclohexanetetracarboxylic acid dianhydride
HBPA：Hydrogenated bisphenol A
BTEAC：Benzyltriethylammoinium chloride
GT4：ダ イ セ Le chemical industry (strain) エ Port リ ー De GT-401 processed (product name) (chemical combination name：Epoxidation fourth Alkane tetracarboxylic acid four-(3- cyclohexenyl methyls) modifies 6-caprolactone)
＜ crosslinking agents ＞
CEL：ダ イ セ Le chemical industry (strain) セ ロ キ サ イ De P-2021 processed (product name) (chemical combination name：3,4- Epoxycyclohexyl-methyl -3 ', 4 ' -7-oxa-bicyclo[4.1.0 formic acid esters)
TMGU：1,3,4,6- tetra- (methoxy) glycoluril
PWL：Powder link1174 (three well サ イ テ ッ Network (strain) system)
＜ crosslinking catalysts ＞
PTSA：P-methyl benzenesulfonic acid monohydrate
＜ solvents ＞
CHN：Cyclohexanone
PGMEA：Propylene glycol monomethyl ether
PGME：Propylene glycol monomethyl ether
NMP：1-METHYLPYRROLIDONE
Using Japanese light splitting (strain) GPC devices processed (Shodex (registration mark) post KF803L and KF804L), it will elute Solvents tetrahydrofurane (40 DEG C of column temperature) is flowed through in post for 1mL/ minutes with flow with the conditions of as being eluted, determine according to The number-average molecular weight and weight average molecular weight for the polymer that following synthesis example is obtained.In addition, following number-average molecular weights is (below, Referred to as Mn.) and weight average molecular weight (hereinafter referred to as Mw.) represented with polystyrene scaled value.
The ＞ of ＜ synthesis examples 1
It is small in 80 DEG C of reactions 20 by making GMA 18.4g, HEMA 4.6g, AIBN 1.1g be dissolved in PGMEA 65.1g When, so as to obtain acrylic polymer solution (the mass % of solid component concentration 27) (P1).The acrylic acid series polymeric compounds of gained Mn 4,940, Mw to be 9,090.
The ＞ of ＜ synthesis examples 2
By adding CHECA 4.34g, PGMEA 12.0g, BTEAC 0.083g in P1 solution 25.0g, at 120 DEG C Reaction 10 hours, so as to obtain the polymer (the mass % of solid component concentration 27) (P2) with cyclohexene ring.The propylene of gained The Mn of sour based polymer is 19,440 for 8,240, Mw.
The ＞ of ＜ synthesis examples 3
By adding CHEDA 7.10g, PGMEA 31.6g, BTEAC in commercially available PVA (Mw31,000) 3.30g 0.125g, reacts 10 hours at 120 DEG C, so as to obtain the polymer (the mass % of solid component concentration 25) with cyclohexene ring (P3).The Mn of the polyvinyl of gained is 111,303 for 47,720, Mw.
The ＞ of ＜ synthesis examples 4
By adding CHECA 7.69g, PGMEA 53.6g, BTEAC 0.14g in BGOP 12.0g, in 120 DEG C of reactions 10 hours, so that obtaining end has the compound (the mass % of solid component concentration 27) (B1) of cyclohexene ring.
The ＞ of ＜ synthesis examples 5
By adding CHECA 9.62g, PGMEA 53.5g, BTEAC 0.18g in CEL 10.0g, in 120 DEG C of reactions 10 hours, so that obtaining end has the compound (the mass % of solid component concentration 27) (B2) of cyclohexene ring.
The ＞ of ＜ synthesis examples 6
By adding CHECA 3.30g, PGMEA 46.7g, BTEAC 0.06g in GT4 6.0g, 10 are reacted at 120 DEG C Hour, so that obtaining end has the compound (the mass % of solid component concentration 27) (B3) of cyclohexene ring.
The ＞ of ＜ synthesis examples 7
By the way that HBPDA 12.0g, HBPA 10.2g, BTEAC 0.22g are dissolved in PGMEA 54.48g, at 125 DEG C Reaction 19 hours, so as to obtain polyester liquid (solid component concentration：30.0 mass %) (P4).The Mn of the polyester of gained is 1, 980, Mw be 3,500.
The ＞ of ＜ synthesis examples 8
By the way that MAA 2.5g, MMA 9.2g, HEMA 5.0g, the AIBN 0.2g as polymerization catalyst are dissolved in into PGME In 50.7g, reacted 20 hours at 70 DEG C, so as to obtain acrylic acid series copolymer solution (the mass % of solid component concentration 25) (P5).The Mn of the acrylic acid series copolymer of gained is 45,200 for 19,600, Mw.
The ＞ of ＜ synthesis examples 9
It is anti-at 120 DEG C by adding BA 4.21g, PGMEA 11.6g, BTEAC 0.083g in P1 solution 25.0g Answer 10 hours, so as to obtain acrylic acid series polymeric compounds (the mass % of solid component concentration 27) (P6).The acrylic polymeric of gained The Mn of thing is 17,940 for 7,920, Mw.
The ＞ of ＜ synthesis examples 10
By adding CHCA 4.41g, PGMEA 12.2g, BTEAC 0.083g in P1 solution 25.0g, at 120 DEG C Reaction 10 hours, so as to obtain the acrylic acid series polymeric compounds (the mass % of solid component concentration 27) (P7) with cyclohexene ring.Institute The Mn of the acrylic acid series polymeric compounds obtained is 17,860 for 7,620, Mw.
The ＞ of ＜ synthesis examples 11
By adding CHCA 9.62g, PGMEA 53.5g, BTEAC 0.18g in CEL 10.0g, 10 are reacted at 120 DEG C Hour, so that obtaining end has the compound (the mass % of solid component concentration 27) (B4) of cyclohexane ring.
The ＞ of ＜ synthesis examples 12
By the way that CHMI 4.0g, HEMA 6.0g, the AIBN 0.5g as polymerization catalyst are dissolved in into PGMEA 24.5g In, reacted 20 hours at 80 DEG C, so as to obtain acrylic acid series copolymer solution (the mass % of solid component concentration 30) (P8).Gained Acrylic acid series copolymer Mn 3,500, Mw to be 7,500.
The ＞ of ＜ synthesis examples 13
By adding CHEDA 7.87g, PGMEA 22.9g, BTEAC 0.077g in P8 solution 50.0g, at 120 DEG C Reaction 10 hours, so as to obtain the polymer (the mass % of solid component concentration 30) (P9) with cyclohexene ring.The propylene of gained The Mn of sour based polymer is 24,990 for 8,243, Mw.
The ＞ of ＜ synthesis examples 14
By the way that BPAGE 15.0g, CHDCA 8.35g, BTEAC 0.10g are dissolved in PGMEA 54.71g, at 120 DEG C Reaction 20 hours, so as to obtain polyester liquid (solid component concentration：30.0 mass %) (P10).The Mn of the polyester of gained is 3, 650, Mw be 9,060.
The ＞ of ＜ synthesis examples 15
By adding CHEDA 6.86g, PGMEA 16.2g in P10 solution 50.0g, reacted 15 hours at 120 DEG C, So as to obtain the polymer (the mass % of solid component concentration 30) (P11) with cyclohexene ring.The Mn of the polyester of gained is 6, 960, Mw be 44,000.
1~embodiment of ＜ embodiments 8 and the ＞ of 1~comparative example of comparative example 3
With the composition shown in table 1, each composition of 1~embodiment of modulation embodiment 8 and 1~comparative example of comparative example 3, for Each example carries out the evaluation of solvent resistance, transmissivity and orientation respectively.
[table 1]
[evaluation of solvent resistance]
1~embodiment of spin coater coating Examples 8 and comparative example 1 are used on silicon wafer (silicon wafer) After each composition of~comparative example 3, in 100 DEG C of temperature, prebake conditions are carried out on electric hot plate 120 seconds, form the painting of 1.1 μm of thickness Film.Thickness is determined using FILMETRICS company systems F20.In 230 DEG C of temperature, the film is carried out in heated air circulation type baking oven Toast 30 minutes afterwards, so as to form the cured film of 1.0 μm of thickness.
Next, making the cured film be impregnated in CHN or NMP after 60 seconds, respectively in the drying 60 seconds of 100 DEG C of temperature, determine Thickness.The situation for not having Thickness Variation after CHN or NMP dippings is designated as zero, the situation of the reduction of thickness will be observed after dipping Be designated as ×.
[evaluation of transmissivity (transparency)]
On a quartz substrate using each of 1~embodiment of spin coater coating Examples 8 and 1~comparative example of comparative example 3 After composition, in 100 DEG C of temperature, prebake conditions are carried out on electric hot plate 120 seconds, form the film of 1.0 μm of thickness.Use FILMETRICS company systems F20 determines thickness.In 230 DEG C of temperature, heated air circulation type baking oven will the film carry out after toast 30 Minute, so as to form cured film.
Next, on the cured film, using ultraviolet-visual spectrometer ((strain) Shimadzu Seisakusho Ltd. SHIMADSU UV- 2550 models), determine transmissivity during wavelength 400nm.
[evaluation of orientation]
On an ito substrate using 1~embodiment of spin coater coating Examples 8 and each group of 1~comparative example of comparative example 3 After compound, in 100 DEG C of temperature, prebake conditions are carried out on electric hot plate 120 seconds, form the film of 2.8 μm of thickness.Use FILMETRICS company systems F20 determines thickness.Then, in 200 DEG C of temperature, in heated air circulation type baking oven will the film carry out after dry It is roasting 30 minutes, so as to form cured film.
Next, the cured film is ground with rotary speed 400rpm, feed speed 30mm/ seconds, intrusion 0.4mm Processing.By the pure water ultrasonic washing 5 minutes of the substrate after milled processed.Then, on the substrate, applied using spin coater The phase difference material that cloth is formed by liquid crystal monomer, then, at 80 DEG C, carries out prebake conditions 60 seconds on electric hot plate, forms thickness 1.4 μm film.Next, relative to the film on the substrate, 1,000mJ/cm is exposed in a nitrogen atmosphere2Light, make phase difference Material solidification.The substrate so made is sandwiched in Polarizer, orientation is confirmed using light microscope.Will be in crossed Nicol The situation for not having light leak under prism state is designated as zero, by produce light leak situation be designated as ×.
[evaluation of heat resistance]
On silicon using 1~embodiment of spin coater coating Examples 8 and each group of 1~comparative example of comparative example 3 After compound, in 100 DEG C of temperature, prebake conditions are carried out on electric hot plate 120 seconds, form the film of 1.1 μm of thickness.Use FILMETRICS company systems F20 determines thickness.Then, in 230 DEG C of temperature, in heated air circulation type baking oven will the film carry out after dry It is roasting 30 minutes, form the cured film of 1.0 μm of thickness.
Next, vertically irradiating 313nm linear polarization to the cured film.Then, further in 230 DEG C of temperature, heat The cured film is burnt till 3 hours in wind circulating baking oven, the aberration Ea*b* with the state after rear baking is determined.
[evaluation result]
The result evaluated and obtained more than is concluded, and is shown in table 2 below.
[table 2]
The cured film formed for the composition by 1~embodiment of embodiment 8, the orientation of liquid crystal is excellent.Therefore, it is known that The composition of 1~embodiment of embodiment 8 can form excellent liquid crystal aligning material.In addition, heat resistance and the transparency are high, In addition patience is also observed even if any one relative to CHN and NMP.
On the other hand, the cured film formed for the composition by 1~comparative example of comparative example 3, liquid crystal is not orientated completely, Or find light leak during with polarized light microscope observing.
Known as described above, the cured film obtained by the resin combination of the present invention has high liquid crystal aligning performance, in addition, With photopermeability, solvent resistance and heat resistance.Thus, it can be known that according to the resin combination of the present invention, using the teaching of the invention it is possible to provide above-mentioned each The cured film of excellent, i.e. liquid crystal aligning material, understands, can form phase difference material in addition.
Industry utilizability
The resin combination of the present invention is to have very much as the liquid crystal aligning layer of optical anisotropic film, liquid crystal display cells , in addition, being used as the guarantor formed in the various displays such as thin film transistor (TFT) (TFT) type liquid crystal display cells, organic EL element The material of the cured films such as cuticula, planarization film and dielectric film, particularly, forms interlayer dielectric, the colour filter of TFT type liquid crystal cells The material of the diaphragm of device or the dielectric film of organic EL element etc. is also suitable.
The explanation of symbol
100th, 200 liquid crystal cells
101st, 111,201,211 substrate
102nd, 202 colour filter
103rd, 203 CF outer covering layers
105th, 205 phase difference material
106、110、206、210 ITO
107th, 109,204,207,209 alignment films
108th, 208 liquid crystal layer.

Claims (6)

1. a kind of liquid crystal aligning material, it is characterised in that be by being ground using cured film obtained by resin combination Obtained from processing, the resin combination contains：Shown in formula (1) have in end compound i.e. (B) of cyclohexene ring into Point, and binder polymer is (D) composition,
In formula (1), R represents the organic group of carbon number 1~20, and X represents hydrogen atom, methyl or halogen atom.
2. liquid crystal aligning material according to claim 1, it is characterised in that (D) composition is comprising shown in formula (2) The polyester resin of construction unit,
In formula (2), A is represented to be combined with 4 valency organic groups of 4 associative keys in alicyclic skeleton or aliphatic skeleton, and B is represented The divalent organic group of 2 associative keys is combined with alicyclic skeleton or aliphatic skeleton.
3. liquid crystal aligning material according to claim 1, it is characterised in that (D) composition is acrylic acid series polymeric compounds.
4. described liquid crystal aligning material according to claim 1, it is characterised in that the resin combination is further containing favourable Crosslinking agent i.e. (C) composition reacted with heat.
5. described liquid crystal aligning material according to claim 1, it is characterised in that the resin combination is further containing friendship It is (E) composition to join catalyst.
6. a kind of phase difference material, it is characterised in that liquid crystal aligning material described in any one of usage right requirement 1~5 and Formed.
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