CN105899568A - Thermosetting resin composition, cured member and overcoat layer formed using same, polarizing element provided with said overcoat layer, and image display device - Google Patents

Thermosetting resin composition, cured member and overcoat layer formed using same, polarizing element provided with said overcoat layer, and image display device Download PDF

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Publication number
CN105899568A
CN105899568A CN201580003943.2A CN201580003943A CN105899568A CN 105899568 A CN105899568 A CN 105899568A CN 201580003943 A CN201580003943 A CN 201580003943A CN 105899568 A CN105899568 A CN 105899568A
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thermosetting resin
compositions
film
methyl
compound
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利光惠理子
内田直幸
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Mitsubishi Rayon Co Ltd
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Mitsubishi Kasei Corp
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    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • 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
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polarising Elements (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention addresses the problem of providing a thermosetting resin composition which can be cured at low temperatures, is capable of providing a cured member having excellent electrical reliability, and is also capable of forming a thin film having excellent surface properties. A thermosetting resin composition according to the present invention contains (A) a vinyl copolymer, (B) a non-latent imidazole-based epoxy curing agent, (C) an ethylenically unsaturated group-containing compound and (D) a radical polymerization initiator.

Description

Compositions of thermosetting resin, use said composition and the solidification component that formed and protective coating, Possess polarization element and the image display device of this protective coating
Technical field
The present invention relates to a kind of compositions of thermosetting resin, it requires the liquid of high electricity reliability for being formed at In crystal device, organic EL (Electro Luminescence) display device, organic semiconductor device etc. The components such as the protecting film of use, dielectric film, planarization film.Low temperature is had both more particularly, to obtaining Curable, electricity reliability and the cured film of good surface texture or the compositions of thermosetting resin of component, The solidification component using this compositions of thermosetting resin and formed and the image possessing this solidification component show Showing device.
Additionally, the present invention relates to protective coating compositions of thermosetting resin, there is this thermosetting tree of use Oil/fat composition and the polarization element of protective coating that formed and the image display dress possessing this polarization element Putting, described protective coating compositions of thermosetting resin is used for protective coating, and this protective coating is formed at logical On the anisotropy pigmented film crossing coating and formed.
Background technology
In recent years, meet lighting, impact resistance, flexural property etc. and just require the flexible display of characteristic Universal, as these flexible displays are used for being formed the substrate of component, employ the plastics base of flexibility Plate.It addition, based on reduction cost and the viewpoint of the printed electronic tackling a small amount of multi items, also to answering The flexible plastic substrates of roll-to-roll grade is studied.
As such flexible plastic substrates, have studied Merlon, polyethylene terephthalate etc., But such plastic base is poor heat resistance compared with conventional glass substrate.Therefore, in order to alleviate plastics The thermal stress that substrate applies, requires the most more low temperature in the manufacturing process of flexible display.As Require one of technique of the highest temperature when manufacturing flexible display, have for formed protecting film (protective coating), The roasting procedure of the components such as dielectric film, it is desirable to the low temperature of this roasting procedure.It addition, also by such as The light polarizing film (anisotropy pigmented film) forming liquid crystal display with cloth of coating-type seeks lighting and reduction The trend of cost, but should in the case of the protecting film etc. being formed in application type light polarizing film be also required to will not Light polarizing film, liquid crystal layer etc. are brought and is formed at a temperature of damage, it is desirable to low temperature.Additionally, such as In the color filter of image display device, as the method realizing high-contrast, for by color material by Pigment system is converted to dyestuff system and has carried out various research, and compared with pigment, dyestuff is thermo-labile, examines from this point Consider, also require that color filter formation material has curability at low temperatures.
As such curability at low temperatures material, it was recently reported that various make use of epoxide, oxetanes Cationic polymerization and the material that obtains and epoxide and the compositions of anhydride, amine system firming agent etc., Additionally, also have they various reports with free-radical polymerised combination of materials.
Such as, patent document 1 discloses that the group of the polymer containing epoxy radicals and cationic polymerization initiators Close；Patent document 2 discloses that the combination of the ester ring type polymer containing epoxy radicals and multi-anhydride；Patent Document 3 discloses the combination of polynary epoxy resin, polyamic acid and tetracarboxylic dianhydride；Patent documentation 4 Disclose copolymer containing epoxy radicals and oxetanyl withThe group of the photoinduction acid agents such as salt Close.
It addition, than that described above, patent documentation 5 and Patent Document 6 discloses radical polymerization syzygy and The combination that imidazoles solidification is, although they are not intended to low-temperature setting purposes.
On the other hand, for liquid crystal display (Liquid Crystal Display:LCD), in order to control Make the optical activity in display and birefringence etc., employ linear polarizer, circular polarizing disk, in the past, When manufacturing these polaroids (polarization element), it is widely used that following methods: make iodine or there is dichromatic Organic pigment dissolve or be adsorbed in the film base material surface of the macromolecular materials such as polyvinyl alcohol, then by it along single Direction of principal axis stretches and makes the orientations such as dichromatic pigment.But, according to the pigment used, macromolecular material Difference, thermostability, light resistance etc. are the most insufficient, therefore, it will usually carry out fit protecting film carry out The operation of lamination.
Such as, patent documentation 7 has been recorded following content: use the plastics such as Polyester, acrylic acid series, The resins of the thermohardening type such as polyurethane series, epoxy or ultraviolet hardening etc. are as protective layer；It addition, Following content has been recorded: use the film being made up of thermoplastic norbornene system resin to make in patent documentation 8 For protective layer.But, in the case of laminating protecting film carries out lamination, there is polaroid itself becomes The problems such as finished product rate variance when thickness and laminating protecting film.
It is directed to this, it is proposed that following methods: use the coating solution containing dichromatic pigment and make it do Dry wet type membrane formation process forms the very thin film containing dichromatic pigment on the base material such as glass or hyaline membrane, And utilize intermolecular interaction etc. and make dichromatic pigment be orientated, thus form anisotropic membrane layer.
But, in general, dichromatic pigment forms lysotropic liquid crystal phase in water, alcohol equal solvent, is taking Dichromatic pigment is made to be orientated under the effect in the outfields such as base material, field of flow, electric field, magnetic field, thus Arrive the function as polaroid, therefore there is resistance to water, the shortcoming of moisture-proof difference.
The anisotropy pigmented film that formed with wet type membrane formation process of lyotropic liquid crystalline pigment is used as improving Resistance to water, the method for moisture-proof, such as, propose use containing hydrophilic compounds in patent documentation 9 And the protective coating compositions of hydrophobic compound forms the side of protective layer on anisotropy pigmented film Method.
It addition, as improving the light polarizing film of mar proof, patent documentation 10 has been recorded in dichromatic Pigment association body there occurs in the thin film cell structure of orientation and is filled with polycarbonate resin, acrylic compounds Resins such as resin or comprise the radiation-curing type resin of acrylic resin and acrylic monomer Light polarizing film.
It addition, along with LCD use environment variation, to LCD require lightweight, slimming and The improvement of high durableization etc..It is thus possible, for instance as described in patent documentation 11, have studied LCD mono- The inside coating dichroic substance of organic system of unit and what is called embedded (In-Cell) the type polarizer that formed.
But, for the protective coating of the anisotropy pigmented film of interior insert-type polarizer, not yet carry out fully Research.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 11-5816 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-35660 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-292578 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-84415 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2008-291145 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2008-133329 publication
Patent documentation 7: Japanese Unexamined Patent Publication 10-62624 publication
Patent documentation 8: Japanese Unexamined Patent Publication 8-94833 publication
Patent documentation 9: Japanese Unexamined Patent Publication 2008-179702 publication
Patent documentation 10: Japanese Unexamined Patent Publication 2008-203754 publication
Patent documentation 11: Japanese Unexamined Patent Publication 2006-309185 publication
Summary of the invention
The problem that invention is to be solved
The present inventor etc. are found by research, though the curability at low temperatures material described in patent documentation 1～4 Expect that the film obtained by low-temperature setting, the physics of component, chemical strength are guaranteed, close to liquid Crystal device or the luminescent layer of organic EL display, charge transport layer, electric charge injection layer, crystal The semiconductor layer of pipe etc. and in the case of being formed, it is difficult to guarantee electricity reliability, such as liquid crystal display During device, there is the problems such as scorification.
In addition, it is found that the material itself described in patent documentation 5 and 6 is difficult to form thin film, i.e. allow to Form the thin film of thickness about 500nm with solvent dilution etc., formed and water, solvent are had impregnability Film, by coating in the purposes of stack membrane successively, there is the lower floor that is initially formed when corroding lamination Such problem such as functional layer.
On the other hand, in the polarization element of LCD etc., in order to the machinery protecting polarization element is strong Degree, the dissolution coming from the impurity of other layer and protection anisotropy pigmented film are by forming other layer Technique used in the impact of solvent etc., need, on anisotropy pigmented film, there is protective coating.
Such as, for the interior insert-type polarizing element as anisotropy pigmented film between electrode and liquid crystal layer For part, in order to form liquid crystal alignment films on anisotropy pigmented film, it is desirable to described alignment films shape One-tenth solvent (N-Methyl pyrrolidone), water as cleaning solvent have toleration, in addition, it is necessary to anti- Stop impurity from anisotropy pigmented film to the dissolution of liquid crystal layer.It addition, in order to suppress for liquid crystal display Scorification etc. when device, organic EL display, protective coating also needs to have electric reliability.Additionally, Under the effect of the heating when forming protective coating, as the performance of the polarization element of anisotropy pigmented film Reduce sometimes, need still to keep the performance as original polarization element after forming protective coating.
The present invention completes in view of above-mentioned prior art.That is, the present invention provides a kind of thermosetting resin Compositions, its be can the compositions of thermosetting resin of low-temperature setting, even if will be by this thermosetting resin group The solidification component that compound obtains is formed at the position close to liquid crystal, quasiconductor etc., it is also possible to forming electricity can By the thin film that property is excellent and surface texture is good.
The method solving problem
The present inventor etc. have carried out various research to solve above-mentioned problem, and it is it was found that contain spy Fixed ethylenic copolymer, specific imidazoles system epoxy hardener, chemical combination containing ethylenically unsaturated group The compositions of thermosetting resin of thing and radical polymerization initiator can solve the problem that above-mentioned problem, thus complete Become the present invention.
That is, the main points of the present invention are as follows.
[1] a kind of compositions of thermosetting resin, it contains:
(A) comprising the 1st side chain and the ethylenic copolymer of the 2nd side chain, described 1st side chain has epoxy Base, described 2nd side chain has alkyl or aromatic ring group, described alkyl or aromatic ring group and optionally has replacement Base；
(B) non-latency imidazoles system epoxy hardener；
(C) compound containing ethylenically unsaturated group；And
(D) radical polymerization initiator.
[2] compositions of thermosetting resin described in above-mentioned [1], wherein, the alkyl in described 2nd side chain is Cyclic alkyl.
[3] above-mentioned [1] or [2] described in compositions of thermosetting resin, wherein, (A) ethylenic copolymer has The glycidyl ether of more than 7, and weight average molecular weight is 1, more than 000.
[4] above-mentioned [1]～[3] according to any one of compositions of thermosetting resin, wherein, (A) vinyl is common Polymers be the unsaturated compound containing epoxy radicals and containing ethylenically unsaturated group compound copolymerization and Obtaining, the described compound containing ethylenically unsaturated group has alkyl or aromatic ring group, described alkyl Or aromatic ring group optionally has substituent group.
[5] above-mentioned [1]～[4] according to any one of compositions of thermosetting resin, wherein, (A) vinyl is common Polymers content ratio in all solids composition is 30～95 mass %.
[6] above-mentioned [1]～[5] according to any one of compositions of thermosetting resin, wherein, (B) non-latency Imidazoles system epoxy hardener content ratio in all solids composition is 1～15 mass %.
[7] above-mentioned [1]～[6] according to any one of compositions of thermosetting resin, wherein, (C) contain olefinic The compound of unsaturated group has more than 2 ethylenically unsaturated groups.
[8] above-mentioned [1]～[7] according to any one of compositions of thermosetting resin, wherein, (D) radical polymerization Close initiator comprising 10 hours half life temperatures is the azo-compound of 70～140 DEG C.
[9] above-mentioned [1]～[8] according to any one of compositions of thermosetting resin, wherein, (D) radical polymerization Close initiator and comprise oxime ester derivative class and at least one of alpha-aminoalkyl benzophenone derivatives apoplexy due to endogenous wind.
[10] above-mentioned [1]～[9] according to any one of compositions of thermosetting resin, it is possibly together with (A) vinyl Epoxide beyond copolymer is as (E) composition.
[11] above-mentioned [1]～[10] according to any one of compositions of thermosetting resin, its possibly together with Under 1013.25hPa, boiling point is that the organic solvent of 80～200 DEG C is as (F) composition.
[12] compositions of thermosetting resin described in above-mentioned [11], wherein, all solids composition is at thermosetting Content ratio in resin combination is 3～20 mass %.
[13] above-mentioned [1]～[12] according to any one of compositions of thermosetting resin, wherein, by this thermosetting Resin combination 180 DEG C, under conditions of 15 minutes solidification and obtain the thin film of thickness 500nm, will This thin film stands dipping thickness after 15 minutes at 25 DEG C in N-Methyl pyrrolidone and meets following formula (i),
95≤(thickness before thickness/dipping after dipping) × 100≤105 (i).
[14] above-mentioned [1]～[13] according to any one of compositions of thermosetting resin, its be used for protective coating.
[15] compositions of thermosetting resin described in above-mentioned [14], it is used for protective coating, and described protection is coated with Layer is formed on the anisotropy pigmented film formed by coating.
[16] a kind of solidification component, it is to use the thermosetting resin group according to any one of above-mentioned [1]～[15] Compound and formed.
[17] the solidification component described in above-mentioned [16], it is to be formed under the solidification temperature below 200 DEG C.
[18] a kind of cured film, it comprises the solidification component described in above-mentioned [16] or [17].
[19] protection using the compositions of thermosetting resin according to any one of above-mentioned [1]～[13] to be formed is coated with Layer, it is formed on the anisotropy pigmented film formed by coating.
[20] a kind of polarization element, it has the protective coating described in above-mentioned [19] and by coating The anisotropy pigmented film formed.
[21] a kind of image display device, it possesses the polarization element described in above-mentioned [20].
[22] a kind of image display device, it possesses the solidification component described in above-mentioned [16] or [17].
The effect of invention
Compositions of thermosetting resin according to the present invention, it is possible to obtain and can solidify at low temperatures and electric reliable Property excellent solidification component, furthermore it is possible to form the thin film that surface texture is good.
Accompanying drawing explanation
[Fig. 1] Fig. 1 is the chart of the absorbance of the substrate with thin film illustrating that embodiment 30 makes.
Detailed description of the invention
Hereinafter, embodiments of the present invention are described in detail.But, explanation set forth below is One example (typical example) of embodiment of the present invention, without departing from its purport, the present invention does not limits In these contents.
In the present invention, " (methyl) acrylic acid " refers to comprise the meaning of acrylic acid and methacrylic acid Thinking, " (methyl) acrylate ", " (methyl) acryloyl " etc. also illustrate that the same meaning.It addition, Before monomer names, labelling " (gathering) " refers to the meaning of this monomer and this polymer.
In the present invention, " all solids composition " refers to the composition of the compositions of thermosetting resin of the present invention The meaning of all the components in addition to solvent in composition.
It addition, polarization element is not limited in anisotropy pigmented film, it is also possible to by coating or laminating etc. And lamination forms adhesive layer or anti-reflection layer, alignment films, has the function as phase retardation film, as bright Degree improves the function of film, the function as reflectance coating, the function as Transflective film, conduct diffusion The layer of the optical functions such as the function of film etc. has the layer of various function and uses with the form of laminated body, thus Improve polarizing properties etc..
The polarization element of the present invention can be applicable to the purposes such as flexible display.
[compositions of thermosetting resin]
The compositions of thermosetting resin of the present invention contains: (A) comprises the 1st side chain and the ethylene of the 2nd side chain Base co-polymer, described 1st side chain has epoxy radicals, and described 2nd side chain has alkyl or aromatic ring group, Described alkyl or aromatic ring group optionally have substituent group；(B) non-latency imidazoles system epoxy hardener；(C) Compound containing ethylenically unsaturated group；And (D) radical polymerization initiator.
It addition, the compositions of thermosetting resin of the present invention can preferably further contain (E) epoxide, (F) organic solvent.
Additionally, the compositions of thermosetting resin of the present invention as required can also be containing various additives etc..
[(A) ethylenic copolymer]
(A) ethylenic copolymer contained in the compositions of thermosetting resin of the present invention comprise the 1st side chain and 2nd side chain, described 1st side chain has epoxy radicals, and described 2nd side chain has alkyl or aromatic ring group, Described alkyl or aromatic ring group optionally have substituent group.The compositions of thermosetting resin of the present invention is by containing (A) specific ethylenic copolymer, coating is not susceptible to cohesion when being dried, it is believed that can realize simultaneously Curability at low temperatures and the film quality of surface texture excellence.
The chemical constitution of the ethylenic copolymer comprising the 1st side chain with epoxy radicals is not particularly limited, Such as can enumerate and comprise the 1st side chain with epoxy radicals and the repetition list represented containing following formula (1) The material of meta structure.
[chemical formula 1]
In above-mentioned formula (1), R1Represent hydrogen atom or methyl.
X represents the link group of direct key or divalent.Wherein, the epoxy radicals in formula (1) not with X key The carbon atom closed can be bonded with X and form ring.
As the link group of the divalent in X, the alkylidene the most optionally with substituent group can be enumerated, Methylene in alkylidene can be selected from unsaturated bond, ehter bond, thioether bond, ester bond, thioester bond, acyl At least one key in amine key and amino-formate bond replaces.Such as can enumerate and comprise ester bond, amido link Link group.
The carbon number of alkylidene is not particularly limited, and from the viewpoint of synthesizing easy degree, is preferably More than 1, it addition, from the viewpoint of film property, preferably less than 9, more preferably less than 7.
The substituent group optionally having as alkylidene, can enumerate such as: halogen atom, carbon number The alkenyl of 2～8, the alkoxyl of carbon number 1～8, phenyl, sym-trimethylbenzene. base, tolyl, naphthyl, Cyano group, acetoxyl group, the alkyl carbonyl oxy of carbon number 2～9, sulfamoyl, carbon number 2～9 Alkylsulfamoyl group, the alkyl-carbonyl of carbon number 2～9, phenethyl, ethoxy, acetamido, key Close and have the di-alkyaminoethyl group of alkyl of carbon number 1～4, trifluoromethyl, carbon number 1～8 Trialkylsilkl, nitro, the alkylthio group etc. of carbon number 1～8, preferably carbon number 1～8 Alkoxyl, cyano group, acetoxyl group, the alkyl carbonyl oxy of carbon number 2～8, sulfamoyl, carbon former The alkylsulfamoyl group of subnumber 2～9, halogen atom.From the viewpoint of synthesizing easy degree, more preferably sub- Alkyl is unsubstituted.
In the middle of X, from the viewpoint of synthesizing easy degree, preferably direct key, the alkylene disconnected by ehter bond Base or the alkylidene disconnected by ester bond, the alkylidene more preferably disconnected by ester bond, further preferably -(C=O)-O-CH2-base.It should be noted that the alkylidene that what is called is disconnected by ehter bond, refer to constituting There is between the C-C key of alkylidene the alkylidene of ehter bond (-O-key).Similarly, what is called is disconnected by ester bond Alkylidene, refers to the alkylidene between the C-C key constituting alkylidene with ester bond (-CO-O-key).
Comprise the vinyl copolymer with the 2nd side chain optionally with the alkyl of substituent group or aromatic ring group The chemical constitution of thing is not particularly limited, and can enumerate such as: comprises and has the alkane optionally with substituent group Base or the 2nd side chain of aromatic ring group and comprise the vinyl of the repeat unit structure that following formula (2) represents Copolymer.
[chemical formula 2]
In above-mentioned formula (2), R2Represent hydrogen atom or methyl.
Y represents the link group of direct key or divalent.
R3Represent alkyl or the aromatic ring group optionally with substituent group.
As the link group of the divalent in Y, can enumerate such as: ehter bond, thioether bond, ester bond, sulfur Ester bond, amido link, amino-formate bond, optionally there is the alkylidene etc. of substituent group.The part of alkylidene Methylene can be selected from unsaturated bond, ehter bond, thioether bond, ester bond, thioester bond, amido link and amino At least one key in formic acid ester bond replaces.Such as can enumerate the link group comprising ester bond, amido link.
The carbon number of alkylidene is not particularly limited, and from the viewpoint of synthesizing easy degree, is preferably More than 1, it addition, from the viewpoint of film property, preferably less than 9, more preferably less than 7.
The substituent group optionally having as alkylidene, can enumerate such as: halogen atom, carbon number The alkenyl of 2～8, the alkoxyl of carbon number 1～8, phenyl, sym-trimethylbenzene. base, tolyl, naphthyl, Cyano group, acetoxyl group, the alkyl carbonyl oxy of carbon number 2～9, sulfamoyl, carbon number 2～9 Alkylsulfamoyl group, the alkyl-carbonyl of carbon number 2～9, phenethyl, ethoxy, acetamido, key Close and have the di-alkyaminoethyl group of alkyl of carbon number 1～4, trifluoromethyl, carbon number 1～8 Trialkylsilkl, nitro, the alkylthio group etc. of carbon number 1～8, preferably carbon number 1～8 Alkoxyl, cyano group, acetoxyl group, the alkyl carbonyl oxy of carbon number 2～8, sulfamoyl, carbon former The alkylsulfamoyl group of subnumber 2～9, halogen atom.From the viewpoint of synthesizing easy degree, more preferably sub- Alkyl is unsubstituted.
In the middle of Y, from synthesizing from the viewpoint of easy degree, preferably directly key, ehter bond, ester bond, by ether Alkylidene that key disconnects or the alkylidene that disconnected by ester bond, more preferably ester bond.It should be noted that institute The alkylidene that meaning is disconnected by ehter bond, refers to have ehter bond (-O-key) between the C-C key constituting alkylidene Alkylidene.Similarly, the so-called alkylidene disconnected by ester bond, refer at the C-C key constituting alkylidene Between there is the alkylidene of ester bond (-CO-O-key).
As R3In alkyl, straight-chain, branched or cyclic alkyl can be enumerated.In the middle of these, From the viewpoint of film-strength, preferably cyclic alkyl.Its carbon number is not particularly limited, strong from film From the viewpoint of degree, preferably more than 1, more preferably more than 2, more preferably more than 4, special Not You Xuanwei more than 6, it addition, from the viewpoint of the reactivity of polyvinyl, preferably 20 Below, more preferably less than 15.
Cyclic alkyl can be monocycle, it is also possible to be multi-ring, from the viewpoint of film-strength, is preferably many Ring.As the object lesson of cyclic alkyl, cyclohexyl, bicyclopentyl, adamantyl, fall can be enumerated Bornyl, Fourth Ring decyl etc., in the middle of these, from the viewpoint of film-strength, preferably bicyclopentyl or gold Just alkyl.
As R3In the substituent group that optionally has of alkyl, can enumerate hydroxyl, sulfydryl, amino, Halogen atom, the alkenyl of carbon number 2～8, the alkoxyl of carbon number 1～8, cyano group, nitro, carbon The aromatic ring group of atomic number 4～12, the alkylthio group etc. of carbon number 1～8, from the sight synthesizing easy degree Point considers, the most unsubstituted, hydroxyl or mercapto substituent are the most unsubstituted.
As R3In aromatic ring group, can enumerate aromatic cyclic hydrocarbon group group and aromatic heterocyclic group. From the viewpoint of film-strength, its carbon number is preferably less than 30, more preferably less than 12, and logical It is often more than 4.
As aromatic cyclic hydrocarbon group group, can be monocycle, it is also possible to be condensed ring, can enumerate such as: tool There are the phenyl ring of 1 free valency, naphthalene nucleus, anthracene nucleus, phenanthrene ring, ring, aphthacene ring, pyrene ring, benzopyrene Ring,The group of ring, benzo phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring etc..
It addition, as aromatic heterocyclic group, can be monocycle, it is also possible to for condensed ring, example can be enumerated As: have the furan nucleus of 1 free valency, benzofuran ring, thiphene ring, benzothiophene ring, pyrrole ring, Pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrrolo-imidazole ring, pyrrolo-pyrazole Ring, pyrrolopyrrole ring, Thienopyrroles ring, thienothiophene ring, furo pyrrole ring, furo Furan nucleus, thienofuran ring, benzisoxaAzoles ring, benzisothiazole ring, benzimidazole ring, pyridine Ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinolin ring, cinnolines (cinnoline) Ring, quinoxaline ring, phenanthridines ring, benzimidazole ring,Pyridine ring, quinazoline ring, quinazolinone ring, The group of ring etc..
As R3In the substituent group that optionally has of aromatic ring group, can enumerate such as: hydroxyl, mercapto Base, halogen atom, amino, the alkenyl of carbon number 2～8, the alkoxyl of carbon number 1～8, cyano group, Acetoxyl group, the alkyl carbonyl oxy of carbon number 2～9, sulfamoyl, the alkyl ammonia of carbon number 2～9 Sulfonyl, the alkyl-carbonyl of carbon number 2～9, phenethyl, ethoxy, acetamido, it is bonded with carbon The di-alkyaminoethyl group of alkyl of atomic number 1～4, trifluoromethyl, three alkane of carbon number 1～8 Base silicyl, nitro, the alkylthio group etc. of carbon number 1～8, from the viewpoint of synthesizing easy degree, The most unsubstituted, hydroxyl or mercapto substituent, the most unsubstituted or hydroxyl.
(A) ethylenic copolymer the most such as by the unsaturated compound containing epoxy radicals and containing olefinic not The compound copolymerization of saturated group and obtain, the described compound containing ethylenically unsaturated group has alkyl Or aromatic ring group, described alkyl or aromatic ring group optionally have substituent group.Will be containing epoxy radicals by using Unsaturated compound and to obtain (A) vinyl containing the compound copolymerization of ethylenically unsaturated group common Polymers, has the tendency of the excellent surface texture that can obtain curability at low temperatures and film, described containing alkene The compound of genus unsaturated group has alkyl or aromatic ring group, described alkyl or aromatic ring group and optionally has Substituent group.
As the unsaturated compound containing epoxy radicals, can enumerate: allyl glycidyl ether, (first Base) glycidyl acrylate, (methyl) acrylic acid α-ethyl glycidyl ester, (methyl) acrylic acid 4-hydroxyl Base butyl ester glycidyl ether, glycidyl ether butenoic acid ethylene oxidic ester, methacrylic acid glycidyl ester, Crotonyl glycidyl ether, itaconic acid monoalkyl list glycidyl esters, fumaric acid monoalkyl list contract The aliphatic unsaturation containing epoxy radicals such as water glyceryl ester, maleic acid mono alkyl list glycidyl esters Compound, (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate, (methyl) acrylic acid 2-(3,4-epoxycyclohexyl) Ethyl ester, (methyl) acrylic acid 2,3-epoxycyclopentyl methyl ester, (methyl) acrylic acid 7,8-epoxy [three rings [5.2.1.0] Decyl-2-yl] the ester ring type unsaturated compound etc. containing epoxy radicals such as oxygen methyl ester.These contain alkoxyl Unsaturated compound can be used alone one, it is also possible in any combination with ratio use 2 kinds with On.In the middle of these, from the cementability of substrate from the viewpoint of, fat containing epoxy radicals is preferably used Race's unsaturated compound, more preferably uses (methyl) acrylate compounds, further preferably uses (methyl) Glycidyl acrylate or (methyl) acrylic acid 4-hydroxybutyl glycidyl ether.
As with the above-mentioned unsaturated compound copolymerization containing epoxy radicals and comprise optionally there is substituent group Alkyl or the compound containing ethylenically unsaturated group of aromatic ring group, can enumerate styrene, Alpha-Methyl The compound of styryl such as styrene, hydroxy styrenes, (methyl) acrylic acid methyl ester., (methyl) acrylic acid Ethyl ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) third The own ester of olefin(e) acid, (methyl) dodecylacrylate, (methyl) 2-EHA, (methyl) propylene Acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid Bicyclopentyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid N, N-dimethylamino ethyl ester, N, N- (methyl) acrylic acid such as dimethyl (methyl) acrylamide, N, N-dimethyl aminoethyl (methyl) acrylamide The vinyl compounds such as ester based compound, vinyl acetate.These materials can be used alone one, also Can be used two or more in any combination with ratio.In the middle of these, from the viewpoint of reactivity, (methyl) acrylate compounds is preferably used, more preferably uses (methyl) acrylic acid and containing fatty group The ester that the alcohol of group is formed, further preferably uses the ester that (methyl) acrylic acid is formed with alicyclic alcohol.Wherein, In the case of using compositions of thermosetting resin to form cured film, component, from being readily available Tg (glass Change transition temperature) from the point of view of this point of high rock-steady structure thing, preferably (methyl) acrylic acid bicyclopentyl ester.It addition, From also the compositions of thermosetting resin of the present invention being given photo-curable, be patterned by development Time give developing time and the developer solution deterioration etc. (exposure latitude) of wide scope from the standpoint of, preferably (methyl) Acrylic acid bicyclopentyl ester.
As with above-mentioned (methyl) acrylic acid bicyclopentyl esters as material, can enumerate and such as have two Cyclopentadienyl skeleton, bicyclopentyl skeleton, dicyclopentenyl skeleton, dicyclopentenyl epoxide alkyl skeleton etc. The compound etc. described in Japanese Unexamined Patent Publication 2001-89533 publication such as (methyl) acrylate, from having energy From the standpoint of the desired physical property of enough impartings further, they are preferably used and replace (methyl) acrylic acid two Cyclopentyl ester.
It addition, styrene etc. do not have the compound of ester group due to have be difficult to degassing, can obtain stable The tendency of film, the most preferably.
(A) polyvinyl can also be except using the unsaturated compound containing epoxy radicals, containing appointing Choosing has beyond the alkyl of substituent group or the compound containing ethylenically unsaturated group of aromatic ring group, enters one Step uses other compound containing ethylenically unsaturated group to obtain.
As other the compound containing ethylenically unsaturated group, can enumerate such as: (methyl) propylene Morpholide, (methyl) acrylonitrile, (methyl) acrylamide, N-methylol (methyl) acrylamide, N-ethylene Base-2-Pyrrolidone etc..
When obtaining these (A) ethylenic copolymers, unsaturated compound containing epoxy radicals, containing appointing The compound containing ethylenically unsaturated group of alkyl or aromatic ring group that choosing has substituent group all can divide It is not used alone one, it is also possible to use two or more with ratio in any combination.
In order to make the solidfied material obtained by compositions of thermosetting resin guarantee, sufficient resistance to chemical reagents, electricity are reliable Property, the epoxide equivalent of (A) ethylenic copolymer be preferably below 600g/eq, more preferably 400g/eq with Under, particularly preferably below 300g/eq, and usually more than 100g/eq.Epoxide equivalent can be by closing Feeding quantity during one-tenth calculates, and can be measured by JIS K 7236 (2009).
In (A) polyvinyl, derive from the repetitive of the vinyl compound containing epoxy radicals Structure (repeat unit structure that above-mentioned formula (1) represents) content ratio is preferably more than 30mol%, more excellent Elect more than 40mol% as, more preferably more than 50mol%, particularly preferably more than 60mol%. Additionally, it is preferred that be below 97mol%, more preferably below 95mol%, more preferably 90mol% Hereinafter, the most preferably below 80mol%, particularly preferably below 70mol%.By for upper State more than lower limit, have and be able to ensure that exposure sensitivity, electricity reliability, the tendency of resistance to chemical reagents, logical Cross as below above-mentioned higher limit, there is the tendency of the film physical property being able to ensure that excellence.
(A), in polyvinyl, derive to comprise optionally there is the alkyl of substituent group or aromatic ring group Repeat unit structure (the repetitive that above-mentioned formula (2) represents of the compound containing ethylenically unsaturated group Structure) content ratio be preferably more than 5mol%, more preferably more than 10mol%, more preferably More than 20mol%, particularly preferably more than 30mol%.Additionally, it is preferred that be below 70mol%, more excellent Elect below 60mol% as, more preferably below 50mol%, the most preferably 40mol% with Under.More than for above-mentioned lower limit, there is the tendency that can improve film-strength, by for the above-mentioned upper limit Below value, there is the tendency being able to ensure that the excellent sensitivity brought because of epoxy radicals.
For the unsaturated compound containing epoxy radicals with comprise the alkyl or aromatic ring optionally with substituent group The method of the compound copolymerization containing ethylenically unsaturated group of group does not has any restriction, can be according to example As used radical polymerization initiator in organic solvent and being added as needed on chain-transferring agent, in freedom Under the active temperature of base polymerization initiator, the known method such as heating synthesizes.
The weight average molecular weight (Mw) of (A) ethylenic copolymer of the present invention be preferably more than 1,000, more excellent Elect 2 as, more than 000, more preferably 5, more than 000, and preferably 300, less than 000, more Be preferably less than 100,000, more preferably less than 60,000, much further preferably from 40,000 Below, particularly preferably less than 30,000.In the case of weight average molecular weight is more than above-mentioned lower limit, There is following tendency: resistance to chemical reagents is excellent, even in the case of forming thin film, it is also possible to easily landform Uniformly, very close to each other, water and solvent are difficult to the thin film being impregnated with.It addition, be below above-mentioned higher limit In the case of, there is following tendency: readily and stably synthesize (A) ethylenic copolymer, and be not likely to produce The film defect caused because of bumping when coating is dried.
It should be noted that the weight average molecular weight in the present invention is to use Shimadzu Scisakusho Ltd to manufacture " gel permeation chromatography system LS Solution " and use " the post that Shimadzu Scisakusho Ltd manufactures GPC-804 " record and be converted into the value of polystyrene.
Shrink sweet additionally, preferably one molecule of (A) ethylenic copolymer of the present invention has more than 7 Oil ether, more preferably there is more than 10 glycidyl ethers, further preferably there are more than 20 contractings Water glycerol ether, particularly preferably there are more than 30 glycidyl ethers, it addition, be generally of 70 Following glycidyl ether.More than for above-mentioned lower limit, have and be able to ensure that enough resistances to chemical reagents Tendency.The quantity of the glycidyl ether in one molecule can be by being applied in combination NMR and GPC Etc. measuring.
It should be noted that in the present invention, (A) ethylenic copolymer preferably has more than 7 shrinks Glycerol ether and weight average molecular weight are 1, more than 000, more preferably have more than 12 glycidyl ethers And weight average molecular weight is 3, more than 000, particularly preferably there is more than 15 glycidyl ethers and weight average Molecular weight is more than 4,000.By making glycidyl ether and the weight average molecular weight of (A) ethylenic copolymer It is satisfied by above-mentioned scope, there is the tendency of the surface texture that can have both curability at low temperatures and film.
[(B) non-latency imidazoles system epoxy hardener]
(B) non-latency imidazoles system epoxy hardener contained by the compositions of thermosetting resin of the present invention does not has It is particularly limited to, it is possible to use the arbitrary imidazoles system epoxy hardener of non-latency.It should be noted that So-called non-latency, refers to it is not the complexation that formed of such as carboxylate, epoxy adduct and slaine The latency imidazoles such as compound.Therefore, non-latency imidazoles may refer in imidazolium compounds except latency Material beyond imidazolium compounds.
In the present invention, as non-latency imidazolium compounds, preferably will be with liquid bisphenol A type epoxy Viscosity when viscosity after mixed with resin stirring is set to initial stage viscosity, then standing preserves at 25 DEG C Reach the imidazolium compounds that natural law is less than 30 days during 2 times of initial stage viscosity, more preferably 10 days with Under imidazolium compounds.The change of above-mentioned initial stage viscosity and viscosity can utilize Brookfield viscometer to measure.
In the present invention, non-latency imidazoles the most only formed by covalent bond composition and only by not with epoxy The material that the imidazolium compounds of the adductions such as resin (non-addition) is formed, preferably without with imidazoles beyond chemical combination The mixture that thing is formed.
It is believed that the compositions of thermosetting resin of the present invention can be by containing (B) non-latency imidazoles system ring Oxygen firming agent and guarantee the surface texture of curability at low temperatures and film.
As the object lesson of (B) non-latency imidazoles system epoxy hardener, can enumerate such as: 1-benzyl -2-methylimidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methyl imidazole, 1-cyanoethyl-2-ethyl-4- Methylimidazole., 1-benzyl-2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-undecyl imidazole, 1,2- Methylimidazole, 2-phenylimidazole, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole etc..From the point of view of in terms of heat stability (working life), the reaction temperature of firming agent Scope (field of activity) is preferably more than 100 DEG C, more preferably more than 120 DEG C.It addition, from heat stability And from the viewpoint of reactivity at processing temperatures, the reaction of firming agent starts temperature range and is preferably More than 80 DEG C, more preferably more than 90 DEG C.It addition, in order to ensure forming thin film, need equably Dissolve in organic solvent, from this point of view, be preferably used and coating solvent is had the most deliquescent Firming agent.It addition, from the standpoint of safety, firming agent cyano compound beyond is preferably used.
If considering above-mentioned aspect further, as the example being preferably used, 1-benzyl-2-can be enumerated Methylimidazole., 2-ethyl-4-methylimidazole, 1-isobutyl-2-methyl imidazole, 1-benzyl-2-phenylimidazole etc., More preferably 2-ethyl-4-methylimidazole.
It should be noted that imidazolium compounds also serve as dicyandiamide, anhydride, phenolic resin class epoxy solid The accelerator of agent etc. uses, but from the viewpoint of working life, the thermosetting resin in the present invention combines In thing, the most not using these firming agent, imidazolium compounds uses preferably as single epoxy hardener.
It addition, imidazoles system epoxy hardener includes the latency imidazolium compounds for guaranteeing working life, But the imidazolium compounds used in the present invention is non-latency.In the case of latency, it is possible to create with Lower problem: when forming thin film, it is difficult to make the uniform film in surface, and, it is also difficult to guarantee low-temperature solid The property changed.It addition, in the case of wanting there is the curable as non-latency imidazoles, latency miaow Azoles must increase addition, has and electricity reliability is also brought dysgenic tendency.
The compositions of thermosetting resin of the present invention generally preferably uses that working life is short, be difficult to one pack system uses Non-latency imidazolium compounds as epoxy hardener, should in the case of, be positioned at molecule end with epoxy radicals Even if bisphenol-type epoxy resin, epoxy radicals be positioned at side chain also than copolymer chain apart from remote novolaks Type epoxy resin is compared, and the steric hindrance around the epoxy radicals of (A) ethylenic copolymer is big, therefore has following Tendency: reactivity when not heating is low, it is possible to use with one pack system, it can be ensured that enough working lives.
It should be noted that the imidazoles system epoxy hardener used in the present invention is different from six aryl di-s Imidazoles is the di-imidazoles system Photoepolymerizationinitiater initiater of representative.
[(C) compound containing ethylenically unsaturated group]
(C) contained in the compositions of thermosetting resin of the present invention chemical combination containing ethylenically unsaturated group Thing is the compound that intramolecular has at least one ethylenically unsaturated group.Thermosetting tree for the present invention For oil/fat composition, by comprising (C) containing compound of ethylenically unsaturated group, it is believed that except can Beyond the strengthening chemical strength of compositions of thermosetting resin, physical strength, it is also possible to give the roots such as patterning According to the bells and whistles needed.
Molecular memory ethylenically unsaturated group the most, crosslinking (solidification) time network become the finest and close, Have it is easy to ensure that resistance to chemical reagents, electricity reliability tendency.Even if it addition, making complete due to low-temperature bake Cross-linked ratio step-down in portion's ethylenically unsaturated group, from guaranteeing that appropriate network facet considers, be also Favourable.
By the above, the compound containing ethylenically unsaturated group of the present invention preferably has multiple olefinic Unsaturated group, specifically, preferably has more than 2 ethylenically unsaturated groups, more preferably has 3 Individual above ethylenically unsaturated group, particularly preferably has more than 5 ethylenically unsaturated groups.It addition, alkene Belong to unsaturated bond number and there is no a upper limit, but usually less than 6.
From the standpoint of reactivity, the alkene that the compound containing ethylenically unsaturated group of the present invention is had Belong to unsaturated group and be preferably pi-allyl and/or (methyl) acryloyl group.
The compound containing ethylenically unsaturated group of the present invention can only use one, it is also possible to arbitrarily Ratio be applied in combination two or more.It should be noted that it is multiple containing ethylenically unsaturated group using Compound in the case of, about the number of ethylenically unsaturated group, as long as making this multiple containing olefinic not The molar average value of the number of the ethylenically unsaturated group that the compound of saturated group is had is above-mentioned Preferably scope.
Hereinafter, compound particularly preferred in the compound containing ethylenically unsaturated group is said Bright.Specifically can enumerate such as: (C1) unsaturated carboxylic acid and the esters of polyol formation, (C2) Polyurethane (methyl) acrylic acid that hydroxyl (methyl) acrylate compounds is formed with polyisocyanate compound Esters and (C3) (methyl) acrylic acid or hydroxyl (methyl) acrylate compounds and polyepoxides shape Epoxy (methyl) esters of acrylic acid etc. become.
The esters formed with polyol as (C1) unsaturated carboxylic acid, can enumerate such as: insatiable hunger With carboxylic acid and the reactant of sugar alcohol, the reactant of unsaturated carboxylic acid and the oxyalkylene addition product of sugar alcohol, no Saturated carboxylic acid and the reactant etc. of hydramine.
Here, as unsaturated carboxylic acid, specifically can enumerate: acrylic acid, methacrylic acid, itaconic acid Deng.
As sugar alcohol, specifically can enumerate: ethylene glycol, Polyethylene Glycol (adduct number 2～14), propylene glycol, Polypropylene glycol (adduct number 2～14), trimethylene, tetramethylene glycol, hexamethylene glycol, three The polyhydric alcohol etc. such as hydroxymethyl-propane, glycerol, tetramethylolmethane, dipentaerythritol.
As the oxyalkylene addition product of sugar alcohol, addition oxidation second on above-mentioned sugar alcohol etc. specifically can be enumerated Alkene or propylene oxide etc. and the compound etc. that obtains.
As hydramine, the polyhydric alcohol amine such as diethanolamine, triethanolamine etc. specifically can be enumerated.
And, the esters formed with polyol as unsaturated carboxylic acid, specifically can enumerate: second Glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylic acid Ester, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three Hydroxymethyl-propane ethylene oxide addition three (methyl) acrylate, glycerol two (methyl) acrylate, third Triol three (methyl) acrylate, glycerol propylene oxide addition three (methyl) acrylate, tetramethylolmethane Two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc. and they Butenoate, methacrylate, maleate, itaconate, citraconate etc..Need explanation It is that the esters that unsaturated carboxylic acid and polyol are formed also includes the derivant etc. of these compounds.
It addition, the esters formed with polyol as unsaturated carboxylic acid, unsaturated carboxylic can be enumerated The aromatic polyhydroxy compounds such as acid and hydroquinone, resorcinol, pyrogaelol, Bisphenol F, bisphenol-A, Or the reactant etc. of their ethylene oxide adduct.Specifically can enumerate such as: bisphenol-A two (methyl) Acrylate, bisphenol-A double [oxygen ethylidene (methyl) acrylate], the double [glycidyl ether (first of bisphenol-A Base) acrylate] etc..
Furthermore it is also possible to enumerate the heterocycle such as above-mentioned unsaturated carboxylic acid and three (2-hydroxyethyl) chlorinated isocyanurates The reactant of formula polyol, two (methyl) acrylic acid of such as three (2-hydroxyethyl) chlorinated isocyanurates Ester, three (methyl) acrylate etc..
Furthermore it is also possible to enumerate the reactant of unsaturated carboxylic acid and polybasic carboxylic acid and polyol, example Condensation substance, (methyl) acrylic acid and the maleic acid formed such as (methyl) acrylic acid and phthalic acid and ethylene glycol The contracting that the condensation substance, (methyl) acrylic acid and the p-phthalic acid that are formed with diethylene glycol and tetramethylolmethane are formed The condensation substance etc. that compound, (methyl) acrylic acid and adipic acid and butanediol and glycerol are formed.
The polyurethane formed with polyisocyanate compound as (C2) hydroxyl (methyl) acrylate compounds (methyl) esters of acrylic acid, can enumerate such as: hydroxyl (methyl) acrylate compounds is many with aliphatic Isocyanates, ester ring type polyisocyanates, aromatic polyisocyanate or hetero ring type polyisocyanates etc. are many The reactant etc. of isocyanate compound.
Specifically, such as, as hydroxyl (methyl) acrylate compounds, (methyl) propylene can be enumerated Acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate, tetra methylol ethane three (methyl) acrylate etc.. It addition, polyisocyanate compound can be enumerated: hexamethylene diisocyanate, 1,8-diisocyanate The aliphatic polyisocyantes such as base-4-isocyanatomethyl octane；Cyclohexane diisocyanate, dimethyl Cyclohexane diisocyanate, 4,4-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), isophorone diisocyanate, The ester ring type polyisocyanates such as norbornane triisocyanate；4,4-methyl diphenylene diisocyanate, three The hetero ring types such as aromatic polyisocyanate and chlorinated isocyanurates such as (isocyanatophenyl) thiophosphate are many Isocyanates etc..
Polyurethane (the first formed with polyisocyanate compound as hydroxyl (methyl) acrylate compounds Base) commercially available product of esters of acrylic acid, can enumerate such as: KCC of Xin Zhong village manufactures " U-4HA ", " UA-306A ", " UA-MC340H ", " UA-MC340H " and " U6LPA " etc..
Polyurethane (the first formed with polyisocyanate compound as hydroxyl (methyl) acrylate compounds Base) esters of acrylic acid, in order to substantially ensure that the resistance to chemical reagents etc. of solidfied material, preferably there are more than 4 ammonia Carbamate key [-NH-CO-O-] and the compound of more than 4 (methyl) acryloxies.Such chemical combination Thing can be by such as making the compound with more than 4 hydroxyls react with diisocyanate cpd, make The compound with more than 2 hydroxyls reacts with the compound with more than 3 NCOs, makes tool There is the compound of more than 4 NCOs and there are more than 1 hydroxyl and more than 2 (methyl) propylene The methods such as the compound reaction of acyloxy and obtain.
Specifically can enumerate such as following compound etc..That is, as by the change with more than 4 hydroxyls The compound that compound reacts with diisocyanate cpd and obtains, can enumerate and make tetramethylolmethane, poly-sweet Oil etc. has compound and hexamethylene diisocyanate, the tri-methyl hexamethylene two of more than 4 hydroxyls The diisocyanate cpds such as isocyanates, isophorone diisocyanate, tolylene diisocyanate are anti- The compound etc. answered and obtain.
Anti-with the compound with more than 3 NCOs as the compound with more than 2 hydroxyls The compound answered and obtain, can enumerate compound and the rising sun making ethylene glycol etc. have more than 2 hydroxyls Become " DURANATE (registered trade mark) 24A-100 ", " DURANATE (note that KCC manufactures Volume trade mark) 22A-75PX ", " DURANATE (registered trade mark) 21S-75E ", " DURANATE (registration Trade mark) 18H-70B " etc. biuret type and " DURANATE (registered trade mark) P-301-75E ", " DURANATE (registered trade mark) E-402-90T ", " DURANATE (registered trade mark) E-405-80T " etc. Adduct type etc. has a compound reaction of more than 3 NCOs and the compound etc. that obtains.
As there is the compound of more than 4 NCOs and there is more than 1 hydroxyl and more than 2 The compound that the compound of (methyl) acryloxy reacts and obtains, can enumerate and make NCO second The polymerizations such as base (methyl) acrylate or copolymerization and the compound etc. that obtains have more than 4, preferably have " the DURANATE that the compound of more than 6 NCOs etc. manufacture with Asahi Chemical Corp (registered trade mark) ME20-100 ", tetramethylolmethane two (methyl) acrylate, dipentaerythritol three (methyl) third Olefin(e) acid ester, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc. have The compound having more than 1 hydroxyl and more than 2, preferably more than 3 (methyl) acryloxies reacts And the compound etc. obtained.
As (C3) (methyl) acrylic acid or hydroxyl (methyl) acrylate compounds and polyepoxides shape Epoxy (methyl) esters of acrylic acid become, can enumerate such as: (methyl) acrylic acid or above-mentioned hydroxyl (first Base) acrylate compounds and aliphatic polyepoxide, aromatic polyepoxide compound, hetero ring type The compound etc. that the polyepoxidess such as polyepoxides react and obtain.
Specifically can enumerate such as: (methyl) acrylic acid or above-mentioned hydroxyl (methyl) acrylate compounds Gather with (gathering) ethylene glycol polyglycidyl ether, (gathering) propylene glycol polyglycidyl ether, (gathering) tetramethylene glycol Glycidyl ether, (gathering) pentamethylene glycol polyglycidyl ether, (gathering) neopentyl glycol polyglycidyl ether, (gathering) hexamethylene glycol polyglycidyl ether, (gathering) trimethylolpropane polyglycidyl ether, (gathering) the third three The aliphatic polyepoxide such as alcohol polyglycidyl ether, (gathering) Sorbitol polyglycidyl ether；Phenol Novolaks polyepoxides, bromophenol novolaks polyepoxides, (o-, m-, p-) Cresol novolak polyepoxides, polymer with bis phenol A epoxide, Bisphenol F polyepoxides Deng aromatic polyepoxide compound；Sorbitan polyglycidyl ether, triglycidyl group isocyanuric acid The polycyclics such as hetero ring type polyepoxides such as ester, triglycidyl group three (2-hydroxyethyl) chlorinated isocyanurates The compound etc. that oxygen compound reacts and obtains.
As the compound containing ethylenically unsaturated group beyond (C1)～(C3), can enumerate such as: sub- (methyl) allyl esters such as acrylic amide, dially phthalate such as double (methyl) acrylamides of ethyl Class, phthalic acid divinyl ester etc. have the compounds of vinyl, utilize Phosphoric sulfide etc. to have The ehter bond of the alefinically unsaturated compounds of ehter bond vulcanizes and becomes the compound with thioether bond of thioether bond Class etc..
These compounds containing ethylenically unsaturated group can be used alone one, it is also possible to combines 2 kinds Used above, from the standpoint of guaranteeing high electric reliability and resistance to chemical reagents, (C1) is preferably used unsaturated The esters that carboxylic acid is formed with polyol, particularly preferred dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate etc. has the compound of more than 5 ethylenic unsaturated bonds.
It should be noted that such as, pattern making compositions of thermosetting resin also have photo-curable In the case of rear use, in order to make it develop with alkaline developer, it is possible to use imported carboxyl, hydroxyl The compound containing ethylenically unsaturated group of base, but owing to sufficient working life sometimes cannot be guaranteed, also The Polyethylene Glycol of long-chain, the chemical combination containing ethylenically unsaturated group containing polypropylene glycol moieties can be used Thing guarantees the adaptability that develops.
[(D) radical polymerization initiator]
(D) radical polymerization initiator used in compositions of thermosetting resin for the present invention and Speech, as long as can heat, light homenergic effect under make the compound that polymerizable monomer is polymerized, Known radical polymerization initiator can be used, such as hot radical polymerization can be enumerated and cause Agent, optical free radical polymerization initiator, preferably (D) radical polymerization initiator comprise hot radical polymerization and draw Send out agent and/or optical free radical polymerization initiator.It is believed that the compositions of thermosetting resin of the present invention is by containing There is (D) radical polymerization initiator can improve resistance to chemical reagents further.
As hot radical polymerization initiator, such as organic peroxide, azo-compound etc. can be enumerated.
As the object lesson of organic peroxide, can enumerate: the ketone mistakes such as methyl-ethyl-ketone peroxide Oxide, 1,1-bis-(tertiary hexyl peroxide)-3,3,5-trimethyl-cyclohexane, 1,1-bis-(tertiary hexyl peroxide) hexamethylene, Peroxy ketal, 1,1,3,3-tetramethyl butyl hydroperoxide, the isopropyls such as 1,1-bis-(t-butyl peroxy) hexamethylene Benzene hydrogen peroxide, rightHydroperoxides, diisopropylbenzyl peroxide, the two tertiary fourths such as alkane hydrogen peroxide The diacyls such as the dialkyl peroxides such as base peroxide, dilauroyl peroxide, dibenzoyl peroxide Peroxide, two (4-tert-butylcyclohexyl) peroxydicarbonate, two (2-ethylhexyl) peroxydicarbonate Deng peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, tertiary hexyl peroxy isopropyl base monocarbonate, The peroxy esters etc. such as t-butyl peroxybenzoate, 1,1,3,3-tetramethyl butyl peroxide-2-ethylhexanoate.
As the object lesson of azo-compound, can enumerate: 2,2 '-azodiisobutyronitrile, 2,2 '-azo Double (2-methylbutyronitriles), 2,2 '-azo double (2,4-methyl pentane nitrile), 1,1 '-azo double (hexamethylene-1-formonitrile HCN), 1-[(1-cyano group-1-Methylethyl) azo] Methanamide, dimethyl-2,2 '-azobisisobutylonitrile acid esters, 4,4 '-even Double (2-amidine propane) dihydrochloride of nitrogen double (4-cyanopentanoic acid), 2,2 '-azo, double [the 2-methyl of 2,2 '-azo -N-(2-hydroxyethyl) propionic acid amide .], 2,2 '-azo double [N-(2-acrylic)-2-methyl propanamide], 2,2 '-even Nitrogen double (N-butyl-2-methyl propanamide) etc..
Preferably 10 hours half life temperatures of hot radical polymerization initiator are more than 70 DEG C, are more preferably More than 80 DEG C, particularly preferably more than 90 DEG C, additionally, it is preferred that be less than 140 DEG C, more preferably 130 DEG C Below, particularly preferably less than 120 DEG C.In the case of less than above-mentioned lower limit, sometimes it is difficult to ensure that Storage stability, it addition, in the case of exceeding above-mentioned higher limit, be sometimes difficult to ensure that sufficient low temperature Curable.
From the viewpoint of 10 hours half life temperatures and safety, (D) radical polymerization initiator is preferred Comprising azo-compound, more preferably comprising 10 hours half life temperatures is the azo-compound of 70～140 DEG C, Particularly preferably comprise 2,2 '-azo double (N-butyl-2-methyl propanamide).
As optical free radical polymerization initiator, can enumerate such as: Japanese Laid-Open Patent Publication 59-152396 public affairs The metallocene chemical combination comprising cyclopentadiene titanium compound described in report, No. 61-151197 each publication of Japanese Laid-Open Patent Publication Thing；Six aryl di-imdazole derivatives described in Japanese Unexamined Patent Publication 2000-56118 publication；Japan is special Open the halomethylation described in flat 10-39503 publicationOxadiazole derivative, halomethyl s-triazine are derivative The N-such as thing, N-phenylglycine aryl-alpha-amido acids, N-aryl-a-amino acid salt, N-aryl-α- The free radical activity agent such as amino acid esters, alpha-aminoalkyl benzophenone derivatives；Japanese Unexamined Patent Publication 2000-80068 Oxime ester derivative etc. number described in publication, Japanese Unexamined Patent Publication 2006-36750 publication etc..Wherein, (D) Radical polymerization initiator preferably comprises oxime ester derivative class and alpha-aminoalkyl benzophenone derivatives apoplexy due to endogenous wind At least one.
Specifically, such as, as cyclopentadienyl titanium derivative class, can enumerate: dicyclopentadienyl dichloride Titanium, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl two (2,3,4,5,6-phenyl-pentafluoride-1-base) titanium, two Cyclopentadienyl group two (2,3,5,6-phenyl tetrafluoride-1-base) titanium, dicyclopentadienyl two (2,4,6-trifluoro-benzene-1-base) Titanium, dicyclopentadienyl two (2,6-difluorobenzene-1-base) titanium, dicyclopentadienyl two (2,4 difluorobenzene-1-base) Titanium, two (methyl cyclopentadienyl) two (2,3,4,5,6-phenyl-pentafluoride-1-base) titanium, two (methyl cyclopentadienyls) Two (2,6-difluorobenzene-1-base) titanium, dicyclopentadienyl [the fluoro-3-of 2,6-bis-(acrylate-1-yl)-benzene-1-base] titanium etc..
It addition, as di-imidazole derivatives species, can enumerate: 2-(2 '-chlorphenyl)-4,5-diphenyl miaow Azoles 2 aggressiveness, 2-(2 '-chlorphenyl)-4,5-two (3 '-methoxyphenyl) imidazoles 2 aggressiveness, 2-(2 '-fluorophenyl)-4,5- Diphenyl-imidazole 2 aggressiveness, 2-(2 '-methoxyphenyl)-4,5-diphenyl-imidazole 2 aggressiveness, (4 '-methoxybenzene Base)-4,5-diphenyl-imidazole 2 aggressiveness etc..
It addition, as halomethylationOxadiazole derivative class, can enumerate: 2-trichloromethyl-5-(2 '-benzene And furyl)-1,3,4-Diazole, 2-trichloromethyl-5-[β-(2 '-benzofuranyl) vinyl]-1,3,4-Two Azoles, 2-trichloromethyl-5-[β-(2 '-(6 "-benzofuranyl) vinyl)]-1,3,4-Diazole, 2-trichloromethyl -5-furyl-1,3,4-Diazole etc..
It addition, as halomethyl Striazine derivative class, can enumerate: 2-(4-methoxyphenyl)-4,6- Double (trichloromethyl) s-triazine, 2-(4-methoxyl group naphthyl)-4,6-double (trichloromethyl) s-triazine, 2-(4-ethoxy Base naphthyl)-4,6-pair of (trichloromethyl) s-triazine, double (trichloromethyl) equal three of 2-(4-carbethoxyl group naphthyl)-4,6- Piperazine etc..
It addition, as alpha-aminoalkyl benzophenone derivatives class, can enumerate: 2-methyl isophthalic acid-[4-(methyl mercapto) Phenyl]-2-morpholinopropane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 4-dimethyl aminoethyl benzoic acid Ester, 4-dimethylamino isoamyl benzene formic acid esters, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino benzene Double (the 4-diethylamino benzal) ring of acetone, 2-ethylhexyl-1,4-dimethylaminobenzoic acid ester, 2,5- Hexanone, 7-diethylamino-3-(4-diethylamino benzoyl) coumarin, 4-(diethylamino) look into ear Ketone etc..
Further, it is also possible to enumerate such as Japanese Unexamined Patent Publication 2000-80068 publication, Japanese Unexamined Patent Publication Oxime described in 2006-36750 publication and ketoxime ester compound.
Further, it is also possible to enumerate: benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, The benzoin alkyl ethers such as benzoin isopropyl ether；2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tert-butyl anthracene The anthraquinone-derivative species such as quinone, 1-chloroanthraquinone；Benzophenone, Michler's keton, 2 methyl benzophenone, 3-first Base benzophenone, 4-methyl benzophenone, 2-chlorobenzophenone, 4-bromine benzophenone, 2-carboxyl hexichol The benzophenone derivates classes such as ketone；2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxybenzene second Ketone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-methylpropiophenone, 1-hydroxyl-1-Methylethyl are (to different Propyl group phenyl) ketone, 1-hydroxyl-1-(to dodecylphenyl) ketone, 2-methyl-(4 '-methyl mercapto phenyl)-2-morpholine The generation acetophenone derivs class such as-1-acetone, 1,1,1-trichloromethyl (to butyl phenyl) ketone；Thiaxanthone, 2- Ethyl thiaxanthone, ITX, CTX, 2,4-dimethyl thioxanthone, 2,4-diethyl The thioxanthone species such as thiaxanthone, 2,4-diisopropylthioxanthone；To (dimethylamino) benzoic acid second Ester, to benzoate derivatives classes such as (diethylamino) ethyl benzoate；9-phenylacridine, 9-are (to first Phenyl) the acridine derivatives class such as acridine；The phenazene derivative classes such as 9,10-dimethylbiphenyl azophenlyene；Benzene And the anthracyclinone derivatives class etc. such as anthrone.
In these optical free radical polymerization initiators, from the standpoint of sensitivity, particularly preferred oxime ester derivative Class, it addition, in the case of the thin film forming below 1 μm, preferably alpha-aminoalkyl benzophenone derivatives Class, because its surface cure is more excellent.
Use optical free radical polymerization initiator as (D) free radical of the compositions of thermosetting resin of the present invention In the case of polymerization initiator, owing to also having photo-curable in addition to there is Thermocurable, therefore deposit In the tendency that can give patternability based on lithoprinting (photolitho).On the other hand, The photo-curable of optical free radical polymerization initiator can not also be used and merely with Thermocurable.
(D) radical polymerization initiator may be used alone, can also be used in combination of two or more kinds.
For being applied in combination combination during two or more (D) radical polymerization initiator, it is not particularly limited, From the viewpoint of the thermostability obtaining excellence, preferably azo-compound and oxime ester derivative class combination or Azo-compound and the combination of alpha-aminoalkyl benzophenone derivatives class.
[epoxide beyond (E) (A) ethylenic copolymer]
The compositions of thermosetting resin of the present invention can also be containing (A) ethylenic copolymer as (E) composition Epoxide (hereinafter sometimes referred to simply as " (E) epoxide ") in addition.The thermosetting tree of the present invention Oil/fat composition, in the case of comprising (E) epoxide, has the tendency that can improve resistance to chemical reagents.
As (E) epoxide, can enumerate such as: bisphenol-type epoxy resin, phenolic varnish type ring Epoxy resins, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, Glycidyl amine, hetero ring type epoxy resin, chemical combination that two sense phenol glycidyl ethers are obtained Thing, the compound that two functional alcohol glycidyl ethers are obtained, polyhydric phenols glycidyl ether is obtained The compound arrived and the hydride etc. of these compounds.
As the object lesson of bisphenol-type epoxy resin, can enumerate: bisphenol A type epoxy resin, bis-phenol F type epoxy resin, bisphenol-s epoxy resin etc.；As the object lesson of phenolic resin varnish type epoxy resin, Can enumerate: phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol-A Phenolic resin varnish type epoxy resin, dicyclopentadiene novolac type epoxy resin and their hydride Deng；As the object lesson of alicyclic epoxy resin, can enumerate: 3,4-epoxy-6-methylcyclohexyl first Base-3,4-epoxy-6-cyclohexanecarboxylic acid ester, 3,4-epoxycyclohexyl-methyl-3,4-7-oxa-bicyclo[4.1.0 formic acid Ester, 1-epoxy ethyl-3,4-7-oxa-bicyclo[4.1.0 etc.；As the object lesson of glycidyl ester type epoxy resin, Can enumerate: phthalic acid 2-glycidyl ester, four hydrogen phthalate 2-glycidyl esters, dimeric dibasic acid contract Water glyceride etc.；As the object lesson of glycidyl amine, can enumerate: four glycidyl group two Aminodiphenylmethane, triglycidyl group para-aminophenol, N, N-diglycidylaniline etc.；Make For the object lesson of hetero ring type epoxy resin, can enumerate: 1,3-diglycidyl-5,5-dimethyl second Interior uride, triglycidyl group chlorinated isocyanurates etc..In the middle of these, from the viewpoint of the film quality formed, Preferably bisphenol-type epoxy resin or phenolic resin varnish type epoxy resin, never unsaturated group, not easy coloring side Face considers, more preferably their hydride.
The epoxide equivalent of these (E) epoxides is preferably more than 100g/eq, more preferably 150g/eq Above, and preferably below 1000g/eq, more preferably below 700g/eq.By for above-mentioned lower limit More than value, have shorten hardening time, can the tendency of low temperature further, it addition, by for above-mentioned Below higher limit, there is the tendency that can reduce cure shrinkage.
Additionally, it is preferred that by GPC measure the molecular weight that obtains be more than 150, more preferably 200 with On, and preferably 2, less than 000, more preferably 1, less than 500.More than for above-mentioned lower limit, There is the tendency being able to ensure that enough curable, it addition, by below for above-mentioned higher limit, there is energy Enough guarantee the deliquescent tendency to solvent.
It should be noted that in these (E) epoxides, based on the reason on manufacturing, usually contain Chlora matter, owing to the compositions of thermosetting resin of the present invention requires high electricity reliability, therefore, (E) epoxy Whole chlorine contained in compound are preferably 2, below 000 mass ppm, and more preferably 1,500 mass Below ppm, below particularly preferably 500 mass ppm.From the same viewpoint, as hydrolysis Property chlorine, below preferably 1,200 mass ppm, below more preferably 800 mass ppm, the most excellent Elect below 200 mass ppm as.It addition, from the same viewpoint, as sponifiable chlorine, preferably It is below 200 mass ppm, below more preferably 100 mass ppm, particularly preferably 20 mass Below ppm.
Above-mentioned (E) epoxide can be used alone one, or is applied in combination two or more.
[(F) organic solvent]
The compositions of thermosetting resin of the present invention preferably with (F) organic solvent diluting so that all solids composition Concentration uses after reaching given range.Particularly, (F) organic solvent boiling point under 1013.25hPa is excellent Elect 80～200 DEG C as, more preferably 100～180 DEG C, more preferably 120～160 DEG C.
Use in the case of (F) organic solvent, preferably make the containing ratio of all solids composition be 3 mass % with More than upper, more preferably 5 mass %, and below preferably 40 mass %, more preferably 30 mass Below %.More than for above-mentioned lower limit, there is the tendency that can be easily controlled thickness, it addition, logical Cross as below above-mentioned higher limit, there is the inclining of working life that can easily keep photosensitive polymer combination To.It should be noted that so-called all solids composition, refer to the total of composition beyond organic solvent.
As it has been described above, the preferred boiling point of (F) organic solvent used in the present invention is the molten of 80～200 DEG C of scopes Agent, can enumerate such as: glycol monoalkyl ethers；Glycol dialkyl ether class；Glycol diacetate class； Alkyl acetate class；Ethers；Ketone；1 yuan of alcohol or polyalcohols；Fat hydrocarbon；Ester ring type hydro carbons； Arene；Chain or ring-type esters；Alkoxyl carboxylic acids；Halogenated hydrocarbon；Ether ketone；Nitrile etc., Specifically can enumerate: isopropanol (boiling point 82 DEG C), glycol dimethyl ether (85 DEG C), Propylene Glycol Dimethyl Ether (97 DEG C), 1,4-bis-Alkane (101 DEG C), methyl iso-butyl ketone (MIBK) (118 DEG C), propylene glycol monomethyl ether (120 DEG C), Glycol monoethyl ether (124 DEG C), ethylene glycol monomethyl ether acetate (145 DEG C), propylene glycol methyl ether acetate (146 DEG C), methyl lactate (145 DEG C), dimethylformamide (153 DEG C), ethyl lactate (155 DEG C), hexamethylene Ketone (156 DEG C), diethylene glycol dimethyl ether (162 DEG C), diisobutyl ketone (168 DEG C), DAA (168 DEG C), 3-ethoxy-c acid esters (170 DEG C), dimethyl ether (171 DEG C), butyl cellosolve (171 DEG C), 3- Methoxyl-3-methyl-1-butanol (174 DEG C), diethylene glycol ethyl methyl ether (176 DEG C), diethylene glycol isopropyl Ylmethyl ether (179 DEG C), dipropylene glycol monomethyl ether (188 DEG C), diethylene glycol diethyl ether (189 DEG C), diethyl Glycol monomethyl ether (194 DEG C) etc..
Composition in above-mentioned organic solvent, compositions good from the balance of coating, surface tension etc. From the standpoint of the dissolubility of composition is higher, the glycol alkyl ether second such as propylene glycol methyl ether acetate is preferably used Esters of gallic acid.
It should be noted that these (F) organic solvents can be used alone, it is also possible to combine two or more Use.Furthermore it is also possible to add other organic solvent beyond (F) composition.
Each composition is at all solids composition of the compositions of thermosetting resin of the present invention (beyond organic solvent All compositions) in preferred content as described below.
In all solids composition, the containing ratio of (A) ethylenic copolymer is preferably more than 5 mass %, more It is preferably more than 15 mass %, more preferably more than 30 mass %, is further preferably 35 More than quality %, more than particularly preferably 40 mass %, and below preferably 95 mass %, more excellent Elect below below 94 mass %, more preferably 93 mass %, further preferably 80 mass as Below below %, particularly preferably 70 mass %, below most preferably 60 mass %.By for above-mentioned More than lower limit, such as in the case of the thin film formed being used as protecting film, have and prevent film from becoming For being impregnated with membrane stage, the tendency easily functional layer etc. of lower floor being protected by.On the other hand, by for Below above-mentioned higher limit, have it is easy to ensure that enough curable, resistance to chemical reagents become sufficiently tendency.
In all solids composition, the containing ratio of (B) non-latency imidazoles system epoxy hardener is preferably 1 More than quality %, more than more preferably 2 mass %, more preferably more than 3 mass %, the most excellent Elect as below below more than 5 mass %, and preferably 15 mass %, more preferably 12 mass %, More preferably below 10 mass %.More than for above-mentioned lower limit, have it is easy to ensure that thermosetting The tendency of enough curable of property resin combination, it addition, by below for above-mentioned higher limit, have The tendency easily deteriorated the working life of suppression compositions of thermosetting resin thus use with one pack system.
In all solids composition, the containing ratio of (C) compound containing ethylenically unsaturated group is preferably 1 More than quality %, more than more preferably 5 mass %, more preferably more than 8 mass %, more enter one Step is preferably more than more than 10 mass %, particularly preferably 15 mass %, and preferably 50 mass % Below, it is more preferably below below 40 mass %, more preferably 30 mass %.By for above-mentioned More than lower limit, have it is easy to ensure that the tendency of enough resistance to chemical reagents, below for above-mentioned higher limit, It is easy to ensure that the tendency of enough electric reliabilities when there is the temperature-curable below 200 DEG C.
In all solids composition, the containing ratio of (D) radical polymerization initiator be preferably 0.5 mass % with Above, it is more preferably more than more than 1 mass %, more preferably 2 mass %, and preferably 10 Below quality %, it is more preferably below below 7 mass %, more preferably 5 mass %.By for More than above-mentioned lower limit, have it is easy to ensure that the tendency of enough resistance to chemical reagents, on the other hand, by for Below above-mentioned higher limit, have and be difficult to electricity reliability is brought dysgenic tendency.
For (B) imidazoles system epoxy hardener in the compositions of thermosetting resin of the present invention and (D) radical polymerization For closing the content ratio of initiator, in terms of the mass ratio in all solids composition, (B)/(D) is preferably Less than 20, more preferably less than 10, it addition, its content ratio is preferably more than 0.5, more preferably More than 1.Below for above-mentioned higher limit, there is deterioration and the tendency of coloring easily suppressing working life, On the other hand, more than for above-mentioned lower limit, there is the tendency being difficult to make electricity reliability deteriorate.
More than 3 mass % that when containing (E) epoxide, its containing ratio is preferably in all solids composition, More than more preferably 5 mass %, and below preferably 30 mass %, more preferably 25 mass % with Under.More than for above-mentioned lower limit, have it is easy to ensure that the tendency of enough resistance to chemical reagents, by for Below above-mentioned higher limit, such as, in the case of the thin film formed being used as protecting film, have and prevent Film becomes the tendency being impregnated with membrane stage, being easily protected by the functional layer etc. of lower floor.
[other composition]
As long as the most significantly hindering the excellent effect of the present invention, in the compositions of thermosetting resin of the present invention Use after can mixing other composition as required.As other composition, can enumerate such as: without ring Amino-compound, the fluorine-containing system surface activitys such as the adhesive resin of epoxide, sensitizer, melmac Development modifying agent, the silicon such as levelling agent, nonionic surfactant and the acid such as agent and silicon system surfactant The adaptation improving agent such as alkane couplant, there is the fluorine-containing of the crosslinked group such as ethylenically unsaturated group, epoxy radicals Toner, silicon dioxide, aluminium oxide, titanium oxide, the oxidations such as liquidproof agent, dyestuff, pigment such as compound The inorganic fillers etc. such as zirconium.
[preparation of compositions of thermosetting resin]
The preparation method of the compositions of thermosetting resin of the present invention is not particularly limited, such as, can make as follows Standby: above-mentioned each composition is mixed together with organic solvent, and make it by stirring or applying ultrasound wave Dissolve or dispersion.It should be noted that when preparing compositions, (C) is containing ethylenically unsaturated group In the case of compound, (E) epoxide are liquid, it can also replace organic solvent.
When being prepared, each composition can be added mixing simultaneously, it is also possible to the most successively Add and mix.Order during for adding successively is not particularly limited.Such as can be obtained as below: first First non-to (B) latency imidazoles system epoxy hardener, (D) radical polymerization initiator and (F) organic solvent are mixed Close and obtain mixture 1, in this mixture 1, then add (C) chemical combination containing ethylenically unsaturated group Thing also mixes, and obtains mixture 2, then adds (A) ethylenic copolymer, (E) in this mixture 2 Epoxide also mixes.Alternatively, it is also possible to make (B) imidazoles system epoxy hardener be dissolved in part (F) In organic solvent, and lysate dissolving obtained adds in the mixture of other composition and obtains.
It addition, the compositions of thermosetting resin of the present invention preferably by above-mentioned each composition together with organic solvent After mixing, removing insoluble matter, resin etc. may generate when synthesis by using filter to carry out filtering Gel component, dust, trace meter etc..As filter, it is possible to use such as: Entegris optimize (trade name, Entegris company manufactures), CUNO Nanosheld (trade name, 3M company manufactures), Zeta Plus EC (trade name, 3M company manufacture) etc..It should be noted that insoluble matter, gel component, ash Dirt, trace meter etc. can become the former of the defects such as brushing difficulty (Crawling) in the case of forming thin film Cause, can become the reason of electric leakage (current leakage) as dielectric film when being used by compositions of thermosetting resin, Therefore the filter that preferably mesh is thin.
The chemical constitution of each composition contained by the compositions of thermosetting resin of the present invention can be passed through NMR, GPC, IR etc. are analyzed and confirm.
[formation of solidification component]
By being solidified by the compositions of thermosetting resin of the present invention, can form solidification component, its method does not has It is particularly limited to, such as can be by the compositions of thermosetting resin of the present invention on substrate etc. after wet type film forming Formed by crosslinking.Specifically, the prime coat of substrate etc. is coated with the thermosetting resin of the present invention Compositions is also dried, and then toasts and is formed.
It addition, as the method forming protective coating, such as the thermosetting resin of the present invention can be combined Thing is formed by crosslinking after wet type film forming on anisotropy pigmented film.Specifically, can each to It is coated with the protective coating resin combination of the present invention on opposite sex pigmented film and is dried, then drying Bake and formed.
It should be noted that in the case of also making it have photo-curable and patterning, can dry Exposure, the lithoprinting operation of development is added before roasting.
Furthermore it is also possible to the compositions of thermosetting resin of the present invention is being printed onto on the prime coat of substrate etc. Patterned by baking afterwards.When printing, it is possible to do not use lithoprinting operation and Form pattern, from this point of view, there is the advantage that can simplify manufacturing process.
As coating process, can enumerate such as: spin-coating method, bar (Wire bar) method, flow coat method, mould Coating, scraper plate rubbing method, stick coating method, rolling method, spraying process, ink-jet method, electrospray sedimentation etc.. Wherein, when using die coating method, it is possible to be coated with on a small quantity, and mist (mist) is adhered to compared with the method such as spin-coating method Danger little, be not likely to produce foreign body, the most preferably.
As printing process, can enumerate: hectographic printing, intaglio printing, aniline printing, screen painting, Silk screen printing, ink jet printing, nozzle print, impressing (micro-contact printing) etc..
In the case of the compositions of thermosetting resin of the present invention comprises organic solvent, it is being coated with or is being printed onto base After on plate, it is generally made to be dried.It is dried and can purify baking oven, hot plate, infrared ray, halogen by using The element heating machine such as heater, microwave irradiation heating is carried out.Wherein, to film entirety the most equably From the point of view of Jia Re, preferably purify baking oven and hot plate.Drying condition is according to the kind of organic solvent, drying means Deng suitably selecting.Carry out fully being readily available stable curable after drying, consider from this point, excellent Choosing is dried the most for a long time, but then, short from dry required time, productivity is excellent, no From the standpoint of substrate and other layer easily bring the impact of heating, the short time is dried the most at low temperatures.Cause This, baking temperature is usually more than 40 DEG C, is preferably more than 50 DEG C, on the other hand, usually 120 DEG C Below, it is preferably less than 100 DEG C.It addition, be preferably more than 15 seconds drying time, be more preferably More than 30 seconds, on the other hand, preferably less than 5 minutes, more preferably less than 3 minutes.It addition, It is dried and can be carried out by hypobaric drying method, it is also possible to heating and hypobaric drying method are applied in combination.
Baking temperature (solidification temperature) for making the compositions of thermosetting resin of the present invention solidify is preferably More than 100 DEG C, more preferably more than 120 DEG C, additionally, it is preferred that be less than 200 DEG C, more preferably 180 DEG C Below.In the case of the temperature less than above-mentioned lower limit, there is the time growth required for solidification, life The tendency that producing property is deteriorated, it addition, in the event of high temperatures, having generation cannot tackle plastic base, The tendency damaging such problem is brought in the case of lower floor has functional layer or to this functional layer.It addition, The time short person being used for toasting is preferred in terms of efficiency, but from guaranteeing that this point of sufficient curable comes Seeing, 3 minutes～2 hours is suitable, and particularly 10 minutes～1 hour most suitable.
It should be noted that photo-curable based on exposure can also be combined during solidification.
For the compositions of thermosetting resin of the present invention, preferably by it at 180 DEG C, the bar of 15 minutes Be solidified to form the thin film of thickness 500nm under part, by this thin film at 25 DEG C in N-Methyl pyrrolidone The middle dipping thickness after 15 minutes that stands meets following formula (i),
95≤(thickness before thickness/dipping after dipping) × 100≤105 (i)
In the case of meeting above-mentioned formula (i), having when carrying out lamination to adequately protect is present in lower floor The tendency of layer.In formula (i), lower limit is preferably more than 97, more preferably more than 98, it addition, on Limit value is preferably less than 103, more preferably less than 102.
The solidification component using the compositions of thermosetting resin of the present invention to be formed can be preferred for the such as the 1st And the 2nd purification layer, gate insulating film, interlayer dielectric, various protective coating (protective layer), planarization Layer, column spacer, bank (bank), rib (rib), color filter, resin black matrix etc..
[protective coating]
As it has been described above, the compositions of thermosetting resin of the present invention may be used for forming protective coating.Such as, May be used for forming protective coating, this protective coating is formed at the anisotropy pigment formed by coating On film.
Never from the standpoint of the optical characteristics of infringement anisotropy pigmented film, the protective coating of the present invention is preferred When thickness 500nm, the light transmittance to 550nm is more than 80%, more preferably more than 85%, Particularly preferably more than 90%.Its upper limit is not particularly limited, preferably the higher person.
For the thickness of the protective coating of the present invention, with dried film thickness gauge, it is often preferred that More than 20nm, more preferably more than 50nm, and preferably below 2000nm, more preferably 1000nm Below.
(substrate)
The substrate used when forming anisotropy pigmented film is not particularly limited, and preferably has good table Face character, contact angle characteristic and the substrate of water absorption character.As the base material of the such substrate of formation, permissible Enumerate such as: the inorganic material such as glass；Triacetate resinoid, acrylic resin, polyester resin, Polycarbonate resin, polyethylene terephthalate resinoid, triacetyl cellulose resinoid, fall The macromolecular materials such as bornylene resinoid, cyclic polyolefin hydrocarbon resins or polyurethane based resin；Etc.. They can be used alone one, or is applied in combination two or more.Particularly, substrate preferably comprises and contains There is the substrate of the polymer base material of macromolecular material.
As the water absorption rate of substrate, usually less than 5%, preferably less than 3%, more preferably 1% with Under.By making water absorption rate be above-mentioned scope, there is following tendency: forming anisotropy color by coating During element film, substrate moisture absorption, substrate will not occur warpage, can suppress coating defects.It addition, have energy Enough suppression are to form anisotropy pigmented film metacoxal plate swelling and produce the tendency of optical defect.
It should be noted that " water absorption rate " in present embodiment refers to, use the examination of ASTM D570 Proved recipe method impregnate 4 hours in the water of 23 DEG C after gravimetry rate of change and the value that obtains.
(anisotropy pigmented film)
The anisotropy pigmented film of the present invention refers to from the thickness direction of film and the most vertical face The electromagnetism in any 2 directions selected in 3 directions of total in the three-dimensional coordinate system in interior 2 directions Character has anisotropic blooming.As electromagnetic property, the optics such as absorption, refraction can be enumerated The electrical properties etc. such as character, resistance, capacity.As having the optically anisotropic film of absorption, refraction etc., Including such as linear polarizing layer, rotatory polarization layer, phase retardation film, electric anisotropy film etc..This embodiment party Anisotropy pigmented film in formula is in addition to polarizing layer, it is also possible to be suitable as phase retardation film, conduction respectively Anisotropy film.
For the thickness of the anisotropy pigmented film of the present invention, in terms of dry film thickness, preferably 10nm Above, it is more preferably more than 50nm, on the other hand, below preferably 30 μm, is more preferably 1 μm Below.It is suitable scope by making the thickness of anisotropy pigmented film, has and can obtain pigment in film Be uniformly directed and the tendency of homogeneous film thickness.
In the case of the anisotropy pigmented film of the present invention is used as polarization element, anisotropy pigmented film Orientation characteristic uses dichroic ratio to represent.If dichroic ratio is more than 8, then plays as polarization element and make With, preferably more than 25, more preferably more than 30.It addition, dichroic ratio is the highest more preferred, it does not has The upper limit.By making dichroic ratio be more than particular value, as following optical element, particularly polarization element It is useful.
So-called dichroic ratio (D) in the present invention, in the case of anisotropy pigment is orientated equally, in order to Under formula represent.
D=Az/Ay
Wherein, Az is polarization direction and the anisotropy pigment of the light being incident to anisotropy pigmented film The absorbance observed when differently-oriented directivity is parallel, Ay is its polarization direction and the taking of anisotropy pigment The absorbance observed time vertical to direction.As long as respective absorbance uses phase co-wavelength the most especially Limit, arbitrary wavelength can be selected according to purpose, but represent the degree of orientation of anisotropy pigmented film In the case of, the value maximum absorption wavelength of anisotropy pigmented film under is preferably used.
It addition, the anisotropy pigmented film of the present invention is preferably 25% in the absorbance of visible wavelength region Above, more preferably more than 35%, particularly preferably more than 40%.It addition, for the upper limit of absorbance For, as long as be adapted to the upper limit of purposes.Such as, in the case of improving degree of polarization, preferably It is less than 50%.By making absorbance be particular range, it is useful as following polarization element, special It not to be useful as the liquid crystal display polarization element shown for colour.
The degree of polarization (PE) of the anisotropy pigmented film of the present invention uses following formula subrepresentation, it typically is 95% Above, preferably more than 98%, more preferably more than 99%.It addition, degree of polarization is the highest more preferred, its Maximum is 100%.
As long as respective absorbance uses phase co-wavelength to be just not particularly limited, can select to appoint according to purpose The wavelength of meaning, but in the case of the degree of orientation representing anisotropy pigmented film, it is preferably used each to different Property pigmented film maximum absorption wavelength under value, or, special at the polarisation paid attention under whole visibility region Property and be multiplied by the value of calculation that luminosity coefficient calculates.
Degree of polarization (PE) [%]={ (Ty-Tz)/(Ty+Tz) }1/2×100
Tz: the anisotropy pigmented film absorbance to absorbing axial polarisation
The absorbance of Ty: anisotropy pigmented film polarisation axial to polarisation
The contrast of the anisotropy pigmented film of the present invention defines with Tz/Ty.The value of contrast is preferably More than 20, more preferably more than 100, it addition, its upper limit does not limit, the highest more preferred.
(manufacture method of anisotropy pigmented film)
The anisotropy pigmented film of the present invention is obtained by coating anisotropy pigment film composition.Make For coating process, it is not particularly limited, can enumerate such as: write " coating engineering (U former rugged brave time テ ィ Application グ engineering) " (towards storehouse bookstore, on March 20th, 1971 issues in Co., Ltd.) page 253～page 277 Described in method, the grand chief editor of state of village of city " initiative of molecule coordinating material with application (molecular material と with) " (Co., Ltd. C MC publish, on March 3rd, 1998 distribution) page 118～page 149 Described in method, on the substrate (orientation process can be implemented in advance) have difference of height structure by thin Sheet shape of the mouth as one speaks coating process, spin-coating method, spraying process, stick coating method, rolling method, scraper plate rubbing method, curtain flow coat cloth Method, the method being coated for slurry (fountain) method, infusion process etc..Wherein, the coating of the thin slice shape of the mouth as one speaks is used During method, the anisotropy pigmented film that uniformity is high can be obtained, therefore preferably.
During coating anisotropy pigment film composition, the supplying party of anisotropy pigment film composition Method, supply interval are not particularly limited.Numerous and diverse, coating fluid is become owing to there is the supply operation of coating fluid When coating starts and produce the situation of the variation of coating film thickness when stopping, therefore, at anisotropy pigmented film Thickness relatively thin time, it is therefore highly desirable that continuously feed anisotropy pigment film composition and carry out Coating.
As the speed of coating anisotropy pigment film composition, usually more than the 1mm/ second, preferably More than the 5mm/ second, and usually below the 1000mm/ second, be preferably the 800mm/ second below.Pass through Making coating speed is above-mentioned scope, exist can even spread, the anisotropy of anisotropy pigmented film becomes High tendency.
It should be noted that as the coating temperature of anisotropy pigment film composition, usually 0 DEG C Above, and usually less than 80 DEG C, be preferably less than 40 DEG C.It addition, anisotropy pigmented film is used The compositions humidity when coating is preferably more than 10%RH, more preferably more than 30%RH, and It is preferably below 80%RH.
(anisotropy pigment film composition)
As long as the anisotropy pigment film composition used in the anisotropy pigmented film of the present invention Show above-mentioned anisotropic material, be not particularly limited.It addition, from passing through painting on substrate From the point of view of cloth makes anisotropy pigmented film, preferably comprise the compositions of anisotropy pigment and solvent (below, Sometimes referred to simply as anisotropy pigment film composition).As the form of said composition, can be solution Shape, it is also possible to be gel, it is also possible to be the state that is scattered in solvent such as anisotropy pigment.It addition, Than that described above, it is also possible to contain adhesive resin, monomer, firming agent and additive etc. as required.
In the present invention, for anisotropy pigment film composition, formed after solvent evaporation is inclined From the viewpoint of photosphere is formed as high-orientation, it is the state of liquid crystalline phase preferably as compositions.Need Bright, in the present embodiment, the state of liquid crystalline phase refers to, " basis of liquid crystal and application (liquid crystal Base と with) " state described in (this most positive one, good work in Jiao Tian city of pine, 1991) page 1～16. The particularly preferably nematic phase described in page 3.
(anisotropy pigment)
The anisotropy pigment of the present invention preferably has the pigment of liquid crystalline phase to control orientation.Here, it is so-called The pigment with liquid crystalline phase refers to, shows the pigment of lyotropic liquid crystalline in a solvent.
As the anisotropy pigment of the lyotropic liquid crystalline used in the present invention, in order to be formed by coating Anisotropy pigmented film, is preferably soluble in water, organic solvent, particularly preferred water miscible anisotropy color Element.Anisotropy pigment more preferably be " organic conceptional diagram-basis and application " (first Tian Shansheng writes, Three publish altogether, 1984) defined in inorganic value less than the compound of organic value.It addition, do not taking Under the free state of salt form, its molecular weight is preferably more than 200, particularly preferably more than 300, and And preferably less than 1,500, particularly preferably less than 1,200.It should be noted that water solublity refers to, At room temperature compound generally dissolves more than 0.1 mass % in water, preferably dissolves more than 1 mass % Character.
As anisotropy pigment, specifically can enumerate: azo pigment, class pigment, the peaceful class of match Pigment, phthalocyanines pigment, fused polycycle class pigment (perylene kinds,Piperazine class) etc..In these pigments, Preferably can obtain the azo pigment of high molecules align in anisotropy pigmented film.Azo pigment Refer to the pigment with at least one azo group.From the viewpoint of tone and manufacture view, one divides The number of the azo group in son is preferably more than 2, and preferably less than 6, more preferably less than 4.
The anisotropy pigment used in the present invention is not particularly limited, it is possible to use known pigment.
As anisotropy pigment, such as Japanese Unexamined Patent Publication 2006-079030 publication, Japan can be enumerated JP 2010-168570 publication, Japanese Unexamined Patent Publication 2007-302807 publication, Japanese Unexamined Patent Publication 2008-081700 publication, Japanese Unexamined Patent Publication 09-230142 publication, Japanese Unexamined Patent Publication 2007-272211 Number publication, Japanese Unexamined Patent Publication 2007-186428 publication, Japanese Unexamined Patent Publication 2008-69300 publication, Japan JP 2009-169341 publication, Japanese Unexamined Patent Publication 2009-161722 publication, Japanese Unexamined Patent Publication 2009-173849 publication, Japanese Unexamined Patent Publication 2010-039154 publication, Japanese Unexamined Patent Publication 2010-180314 Number publication, Japanese Unexamined Patent Publication 2010-266769 publication, Japanese Unexamined Patent Publication 2010-031268 publication, day This JP 2011-012152 publication, 2011-No. 016922 publication of Japanese Unexamined Patent Publication, Japanese Unexamined Patent Publication 2010-100059 publication, Japanese Unexamined Patent Publication 2011-141331 publication, Japanese Unexamined Patent Publication 2011-190313 Number publication, Japanese Kohyo 08-511109 publication, Japanese Unexamined Patent Application Publication 2001-504238 publication, day This JP 2006-48078 publication, Japanese Unexamined Patent Publication 2006-98927 publication, Japanese Unexamined Patent Publication 2006-193722 publication, Japanese Unexamined Patent Publication 2006-206878 publication, Japanese Unexamined Patent Publication 2005-255846 Number publication, Japanese Unexamined Patent Publication 2007-145995 publication, Japanese Unexamined Patent Publication 2007-126628 publication, day This JP 2008-102417, Japanese Unexamined Patent Publication 2012-194357 publication, Japanese Unexamined Patent Publication 2012-194297 Number publication, Japanese Unexamined Patent Publication 2011-034061 publication, Japanese Unexamined Patent Publication 2009-110902 publication, day This JP 2011-100059 publication, Japanese Unexamined Patent Publication 2012-194365 publication, Japanese Unexamined Patent Publication Pigment described in 2011-016920 publication etc..
Anisotropy pigment in present embodiment directly can use with the form of free acid, it is also possible to is Part acid groups takes salt form.Furthermore it is also possible to be anisotropy pigment and the free acid of salt form The anisotropy pigment of form is mixed.It addition, in the case of obtaining with salt form during fabrication, can Directly to use, it is also possible to be converted into desired salt form.As the exchange method of salt form, permissible Arbitrarily use known method, such as, can enumerate following method.
1) in the aqueous solution of the anisotropy pigment obtained with salt form, add the strong acid such as hydrochloric acid, make each to After opposite sex pigment goes out with the form acid out of free acid, apparatus has the aqueous slkali (example of desired counter ion counterionsl gegenions Such as lithium hydroxide aqueous solution) anisotropy pigment acidic-group is neutralized, thus carry out salt exchange Method.
2) in the aqueous solution of the anisotropy pigment obtained with salt form, interpolation has desired contending with The neutral salt (such as lithium chloride) of a large amount of excess of ion, carries out the side of salt exchange with the form of filter cake of saltouing Method.
3) the aqueous solution storng-acid cation exchange resin of anisotropy pigment that will obtain with salt form Processing, after making anisotropy pigment go out with the form acid out of free acid, apparatus has desired contending with Pigment acidic-group is neutralized by the aqueous slkali (such as lithium hydroxide aqueous solution) of ion, thus carries out salt The method of exchange.
4) aqueous solution making the anisotropy pigment with the acquisition of salt form has desired anti-with apparatus in advance The storng-acid cation exchange resin that the aqueous slkali (such as lithium hydroxide aqueous solution) of weighing apparatus ion is processed Effect, thus the method carrying out salt exchange.
It addition, the acidic-group that the anisotropy pigment in present embodiment is had becomes free acid form also It is to become salt form to depend on the pKa of pigment and the pH of pigment aqueous solution.
As the example of above-mentioned salt form, the alkali-metal salt such as Na, Li, K, optionally quilt can be enumerated Alkyl or the substituted ammonium salt of hydroxy alkyl or the salt of organic amine.As the example of organic amine, can enumerate: The low-grade alkylamine of carbon number 1～6, the low-grade alkylamine of the substituted carbon number of hydroxyl 1～6, carboxyl The low-grade alkylamine etc. of substituted carbon number 1～6.In the case of above-mentioned salt form, its kind does not limits In one, it is also possible to multiple be mixed.
It addition, in the present invention, anisotropy pigment can be used alone, it is also possible to they are combined 2 Plant used above, furthermore it is also possible to coordinate beyond the pigment of above-mentioned example not reduce the degree of orientation Pigment uses.Thus, it is possible to manufacture the anisotropy pigmented film with various form and aspect.
As the example of cooperation pigment during other pigment of cooperation, can enumerate: C.I. directly yellow (Direct Yellow) 12, C.I. directly yellow 34, C.I. directly yellow 86, C.I. directly yellow 142, C.I. directly yellow 132, C.I. Indian yellow (Acid Yellow) 25, C.I. direct orange (Direct Orange) 39, C.I. direct orange 72, C.I. The reddest (the Direct Red) 39 of direct orange 79, C.I. acid orange 28, C.I., C.I. are the reddest 79, C.I. is straight Connect that red 81, C.I. is the reddest 83, C.I. is the reddest 89, C.I. Xylene Red (Acid Red) 37, C.I. are the most purple (Direct Violet) 9, C.I. directly purple 35, C.I. directly purple 48, C.I. directly purple 57, C.I. sun blue (Direct Blue) 1, C.I. sun blue 67, C.I. sun blue 83, C.I. sun blue 90, C.I. direct green (Direct Green) 42, C.I. direct green 51, C.I. direct green 59 etc..
(solvent of anisotropy pigment film composition)
As solvent, water, there is the blended organic solvent of water or their mixture is suitable. As the object lesson of organic solvent, alcohols, the second such as methanol, ethanol, isopropanol, glycerol can be enumerated Independent the one of the cellosolve classes etc. such as the glycols such as glycol, diethylene glycol, methyl cellosolve, ethyl cellosolve Kind or their mixed solvent of more than two kinds.
(anisotropy pigment concentration in anisotropy pigment film composition)
As anisotropy pigment concentration in anisotropy pigment film composition, according to membrance casting condition And different, but more than preferably 0.01 mass %, more than more preferably 0.1 mass %, and be preferably Below 50 mass %, below more preferably 30 mass %.If anisotropy pigment concentration is too low, then Obtained anisotropy pigmented film cannot obtain the anisotropy of enough dichroic ratios etc., if each to different Property pigment concentration is too high, then exist viscosity uprise and be difficult to uniform film coated or each to The situation that in opposite sex pigment film composition, anisotropy pigment separates out.
(additive of anisotropy pigment film composition)
In anisotropy pigmented film compositions, can further matching surface activating agent, stream as required The additives such as flat agent, coupling agent, pH adjusting agent.By additive, wettability, painting sometimes can be made Cloth etc. improve.
As surfactant, it is possible to use the arbitrary table of anionic, cationic and nonionic Face activating agent.It adds concentration and is not particularly limited, as obtaining sufficient additive effect and will not hinder Hinder the amount of molecularly oriented, with its densitometer in anisotropy pigment film composition, it is usually preferred to More than 0.05 mass % and below 0.5 mass %.
It addition, in order to suppress anisotropy pigment to become salt and cohesion in anisotropy pigment film composition Deng unstability etc., it is also possible to before and after the mixing of the constituent of anisotropy pigment film composition Or any period in Hun He adds the pH adjusting agents etc. such as known acid/base.It should be noted that make For additive other than the above, it is also possible to use " Additive for Coating ", Edited by Known additive described in J.Bieleman, Willey-VCH (2000).
(anisotropy pigmented film insoluble)
In the present invention, can the anisotropy pigmented film being formed on substrate by coating be carried out insoluble Change.In the present invention, what is called is insoluble refers to, by making the anisotropy color in anisotropy pigmented film The dissolubility of element reduces and suppresses this anisotropy pigment dissolution from film, thus improve the stability of film Treatment process.Specifically, can enumerate such as by ion exchange little for valence mumber be valence mumber than its big from The process of son (such as be multivalent ion by 1 valency ion exchange).
(insoluble liquid)
The insoluble liquid used in the present invention is not particularly limited.Such as Japanese Unexamined Patent Publication can be used 2007-241267 publication, Japanese Unexamined Patent Publication 2009-199075 publication, Japanese Unexamined Patent Publication 2010-44130 Number publication, Japanese Unexamined Patent Publication 2010-197760 publication, Japanese Unexamined Patent Publication 2011-257489 publication, day Insoluble liquid etc. described in this JP 2012-058427 publication etc..
In the middle of these, insoluble liquid viscosity at 25 DEG C is preferably more than 25mPa s, is more preferably More than 40mPa s, particularly preferably more than 50mPa s, on the other hand, preferably 1000mPa s with Under, more preferably below 500mPa s.By using the suitable insoluble liquid of viscosity, ion exchange is filled Divide ground to carry out, therefore can keep the optical characteristics of anisotropic membrane, and can be fast after insoluble Clean fastly.
The temperature of insoluble liquid is not particularly limited, preferably less than 30 DEG C, more preferably less than 25 DEG C, And it is preferably more than-10 DEG C.By making the temperature of insoluble liquid in above-mentioned scope, there is holding insoluble Change performance, and polarized light property deteriorate the tendency that the defect such as little, crackle is few.
The pH of insoluble liquid is not particularly limited, but from cation exchange principle consider, contribute to from The cation concn of son exchange is necessary for more than a certain constant density.Accordingly, it sometimes is necessary to be based on material The pH of a certain specific pH more oxytropism side.It addition, the tone of insoluble liquid it is not also specifically limited, But preferably substantially degree of polarization will not be brought the colourless, light of impact.
The insoluble liquid used in the present invention is not particularly limited, and preferably comprises insoluble compound and molten Agent.Insoluble compound and solvent can use one, it is possible to use multiple.
As insoluble compound, preferably have and form salt with sulfo group, carboxyl, phosphoryl and phosphonate group The compound of multivalent ion.Specifically can enumerate: the inorganic salt of Mg, Ca etc., polyamine compounds, The polymer with cationic groups and the mixing of the compound forming metal ion in insoluble liquid Thing etc..Wherein, in order to reduce the crackle of insoluble rear polarizing layer, preferably polyamine compounds.
Polyamine compounds refers to, its intramolecular has the compound of more than 2 amino.It addition, conduct The number of the amino that a part polyamine compounds is had, usually more than 2, it addition, its upper limit Usually less than 20, preferably less than 10.It is suitable scope by the number making amino, tool There is polyamine compounds anisotropy pigmented film can be made insoluble at anisotropy pigmented film internal diffusion Tendency.
As polyamine compounds, aliphatic polyamine compounds and aromatic polyamine class can be enumerated Compound.Wherein, preferred aliphat polyamine compounds.
As the object lesson of aliphatic polyamine compounds, can enumerate: diamino hexane, diaminourea The Diaminoalkane compounds such as decane；The diamino-cyclohexane such as 1,4-cyclohexane diamine；4,4 '-di-2-ethylhexylphosphine oxide The diaminourea cyclanes compounds such as cyclo-hexylamine；Diethylenetriamines, penten, double (six Asias Methyl) the poly-ethylene compound such as triamine；Etc..Wherein, the most poly-ethylene compound, The most double (hexa-methylene) triamines.
As the object lesson of aromatic polyamine compounds, can enumerate: diaminobenzene, xyxylene Diamidogen etc..Wherein, preferred diaminobenzene.
As the solvent of insoluble liquid, preferably dissolve the polar solvent of ion.Specifically can enumerate water, from Sub-liquid etc..Wherein, from the viewpoint of economy, safety, preferably water.
For insoluble compound amount in insoluble liquid, just do not have as long as having ion-exchange capacity There is especially restriction, can be according to insoluble compound and the kind of solvent, insoluble liquid at 25 DEG C Viscosity etc. suitably adjust.It is preferably more than the 10% of saturated concentration, is more preferably the 20% of saturated concentration Above, additionally, it is preferred that be saturated concentration (=100%) below, more preferably saturated concentration less than 90%. By for this scope, there is the unnecessary insoluble compound of suppression and separate out and can carry out not rapidly Dissolve the tendency of reaction.
(additive of insoluble liquid)
The insoluble liquid used in the present invention can also contain thickening agent, wetting agent, surfactant etc. and add Add agent.It addition, the amount that additive is in insoluble liquid can be according to additive, insoluble compound and molten The kind of agent, insoluble liquid viscosity at 25 DEG C etc. suitably adjust.
(thickening agent)
In order to adjust the viscosity of insoluble liquid, thickening agent can be added.Specifically can enumerate: cellulose family, Cellulose derivative, protein-based, alginic acid, agar, starch, polysaccharide, hargil class etc. are natural Based compound or vinyl-based, ethenylidene class, polyesters, polyamide-based, polyethers, poly-two Alcohols, polyvinyl alcohol, polyoxyalkylene hydro carbons, polyacrylic, acrylic emulsions, polyurethanes, Synthesis compound and the combinations thereof etc. such as polyureas, it addition, these materials can be with various ions Form salt.
As thickening agent, more than the 0.1% of the most insoluble liquid gross mass, more preferably more than 1%, Additionally, it is preferred that be less than 80%, more preferably less than 60%.By being this scope, there is holding Insoluble performance and being capable of is suitable to the tendency of the viscosity having version to print.
(wetting agent)
For the anisotropy pigmented film after suppressing dry, the suppression of insoluble liquid to contact with insoluble liquid Crackle or rupture, can add wetting agent.Specifically can enumerate: aminoacid, carboxylic acid, ketopyrrolidine carboxylic Acid, lactic acid or the mucopolysaccharide such as hyaluronic acid, chondroitin sulfate, glycerol, propylene glycol, 1,4-butanediol, The protein hydrolysates such as the polyalcohols such as Sorbitol, soluble collagen, elasticin, keratin, And intacellin, mucin, chitin/chitosan, intersection Metabolite of lactobacillus, culture propagation The natural goods such as metabolite, yeast extract, these materials can form salt with various ions.
As wetting agent, more than the 0.1% of the most insoluble liquid gross mass, more preferably more than 1%, Additionally, it is preferred that be less than 80%, more preferably less than 60%.By being this scope, there is holding Insoluble performance and prevent the tendency being dried.
(surfactant)
In order to disperse, control cohesion, froth breaking, improving wettability, control viscosity, control flatness etc., Surfactant can be added.Specifically can enumerate: anionic, cationic, amphoteric, non-from The various surfactants of subtype.
As surfactant, more than the 0.01% of the most insoluble liquid gross mass, more preferably 0.03% Above, additionally, it is preferred that be less than 5%, more preferably less than 1%.By being this scope, have Improve dispersibility and meet the tendency of wettability, flatness.
The preparation method of the insoluble liquid of the present invention is not particularly limited.For example, it is possible to by above-mentioned insoluble Compound and solvent are mixed to above-mentioned concentration range, are stirred etc. further according to needs and make it dissolve In solvent.Alternatively, it is also possible to the above-mentioned additive used as required is mixed in solvent also respectively Become above-mentioned concentration range.It should be noted that the period of mixing, order etc. are also arbitrary.
(insoluble method)
Thawless for anisotropy pigmented film method is not particularly limited, can enumerate: dipping；With stream Water supplies the method for insoluble liquid on anisotropy pigmented film；Spraying；Curtain flow coat cloth, roller coat, dip-coating, The coatings such as flow coat and blowout coating；Etc..The anisotropy pigment arranged by coating of the present invention Film is the thinnest, has when contacting the tendency being easily peeling etc. with object.It is therefore preferable that use energy The method enough suppressing the defect such as the polarizing properties decline of anisotropy pigmented film and the stripping of film.
Defect, the process speed such as the stripping from the polarizing properties decline and film suppressing above-mentioned anisotropy pigmented film From the viewpoint of degree and installation cost, dipping and coating are preferably used.
(alignment films)
For the polarization element of the present invention, in order to make the orientation of anisotropy pigmented film improve, can With before being formed on substrate by anisotropy pigmented film, substrate arranges alignment films.The most permissible Use " liquid crystal brief guide " Wan Shan Co., Ltd., distribution on 12 years (2000) October 30 of Heisei, 226 Page is to the known method described in page 239 grades.
Embodiment
Hereinafter, by embodiment, the present invention will be described in more detail.But the present invention is not limited to following Embodiment, can implement after the scope without departing from its purport arbitrarily changes.
It should be noted that in below example, comparative example, " part " refers to " mass parts ".
[assay method of absorbance, degree of polarization and contrast]
Absorbance, degree of polarization and contrast use the spectrophotometer possessing Glan Thompson polarizer (big electronics (strain) system, goods name " RETS-100 ") and try to achieve.To anisotropy pigmented film incident straight The mensuration light of polarisation, absorbance wavelength dependency based on 400nm～800nm obtained by mensuration (Ty (λ), Tz (λ), Tm (λ)), according to calculating formula shown below calculate measure element monomer transmission Rate (Tm) [%], degree of polarization (PE) [%], contrast (CR).
Tm [%]=Σ V (λ) D65(λ)Tm(λ)/ΣV(λ)D65(λ)×100
Ty [%]=Σ V (λ) D65(λ)Ty(λ)/ΣV(λ)D65(λ)×100
Tz [%]=Σ V (λ) D65(λ)Tz(λ)/ΣV(λ)D65(λ)×100
CR=Ty/Tz
PE={ (Ty-Tz)/(Ty+Tz) }1/2×100
Tm (λ): anisotropy pigmented film monomer absorbance under each wavelength
Tz (λ): anisotropy pigmented film under each wavelength to absorb axial polarisation absorbance
Ty (λ): anisotropy pigmented film is the absorbance of polarisation axial to polarisation under each wavelength
D65(λ): the mensuration intensity of light source (reference light of CIE, ISO of the object color under each wavelength Intensity)
V (λ): the luminosity coefficient wavelength dependence specified by International Commission on Illumination, Conference Generale des Poid et measures Property
[embodiment 1～25, comparative example 1～11]
Embodiment 1～25 and each compositions of comparative example 1～11 all can be obtained as below: each composition is mixed, Stirring, after fully dissolving, uses politef (PTFE) filter of aperture 0.02 μm to filter. The details of each composition is as described below.The containing ratio of each composition and evaluation result are shown in table 1～table 4.
＜ ethylenic copolymer-1 ＞
Possessing reflux condenser, blender, nitrogen are blown in the flask of pipe addition and have tristane bone (methacrylic acid bicyclo-pentyl ester, Hitachi Chemical Co., Ltd. manufactures the monomethacrylates of frame " FA-513M ") 47 mass parts, glycidyl methacrylate 61 mass parts, propylene glycol monomethyl ether Acetas 400 mass parts, dimethyl 2, double (2 Methylpropionic acid ester) 8.0 mass parts of 2 '-azo, nitrogen is replaced After, make liquid temperature rise to 80 DEG C while stirring, react 6 hours at 80 DEG C, enter at 100 DEG C 1 hour dimethyl 2 of row, the resolution process of 2 '-azo double (2 Methylpropionic acid ester), then the decompression of 80 DEG C Lower distillation propylene glycol methyl ether acetate, is concentrated to, about solid component concentration 50 mass %, obtain Ethylenic copolymer-1.The weight average molecular weight (Mw) of this resin is about 11,000.
It should be noted that weight average molecular weight uses the " gel infiltration that Shimadzu Scisakusho Ltd manufactures Chromatographic system LS Solution " and use " the post GPC-804 " that Shimadzu Scisakusho Ltd manufactures Measure.
The structure of the repetitive contained by ethylenic copolymer-1 is as described below.
It should be noted that ethylenic copolymer-1 derives from the unsaturated compound containing epoxy radicals The content ratio of the repeat unit structure of (glycidyl methacrylate) is 67 moles of %, derives from and contains Have the unsaturated compound (methacrylic acid bicyclo-pentyl ester) of cyclic alkyl repeat unit structure containing than Example is 33 moles of %.
It addition, the epoxide equivalent of ethylenic copolymer-1 is 252g/eq, the (+)-2,3-Epoxy-1-propanol in a molecule The number of ether is 43.Epoxide equivalent is calculated by feeding quantity, and the number of glycidyl ether is also led to Cross feeding quantity to calculate.
[chemical formula 3]
＜ ethylenic copolymer-2 ＞
There is ethylenic copolymer (epoxide number: 1.4meq/g, the Weight-average molecular of following repeat unit structure Amount: 2900)
The structure of the repetitive contained by ethylenic copolymer-2 is as described below.
It should be noted that derive from the unsaturated compound containing epoxy radicals, (Glycidyl methacrylate is sweet Grease) the content ratio of repeat unit structure be 17 moles of %, derive from the insatiable hunger containing chain-like alkyl It is 83 moles of % with the content ratio of the repeat unit structure of compound (butyl acrylate).
[chemical formula 4]
＜ contains homopolymer-1 ＞ of epoxy radicals
Poly (glycidyl methacrylate) (homopolymer of glycidyl methacrylate, and the pure medicine of light Industrial Co., Ltd's system, weight average molecular weight: 25,000)
＜ ethylenic copolymer-1 ＞ without epoxy radicals
Styrene/α-methyl styrene/acrylic acid copolymer (mol ratio: 70/10/20, weight average molecular weight: 4,600)
＜ contains condensation polymer-1 ＞ of epoxy radicals
NC-2000L (Nippon Kayaku K. K's system, it has by the chemical constitution of following formula subrepresentation, In formula, n is the integer of more than 1, and its material containing n=1 is the thing of more than 2 as main constituent, n Matter is as accessory ingredient.)
[chemical formula 5]
＜ non-latency imidazoles system epoxy hardener-1 ＞
2-ethyl-4-methylimidazole (Tokyo HuaCheng Industry Co., Ltd's system, reaction beginning temperature province: About 90～110 DEG C)
＜ non-latency imidazoles system epoxy hardener-2 ＞
(Mitsubishi chemical Co., Ltd's system, 1-isobutyl-2-methyl imidazole, reaction start humidity province to IBMI12 Territory: about 80～100 DEG C)
＜ non-latency imidazoles system epoxy hardener-3 ＞
2-phenylimidazole (Tokyo HuaCheng Industry Co., Ltd's system, reaction beginning temperature province: 95～110 DEG C of left sides Right)
＜ latency imidazoles system epoxy hardener-1 ＞
(bisphenol A type epoxy resin adds mould assembly, Mitsubishi chemical Co., Ltd's system to P200, and it has by following The chemical constitution that formula represents, in formula, Ph be phenyl, Me be methyl.)
[chemical formula 6]
＜ contains compound-1 ＞ of ethylenically unsaturated group
Dipentaerythritol acrylate (Nippon Kayaku K. K's system)
＜ contains compound-2 ＞ of ethylenically unsaturated group
LIGHT ESTER NB (Kyoeisha Chemical Co., Ltd.'s system, n-BMA)
＜ radical polymerization initiator-1 ＞
VAm-110 (Wako Pure Chemical Industries, Ltd.'s system): 10 hours half life temperatures are the idol of 110 DEG C Nitrogen compound (hot radical polymerization initiator), it is represented by following chemical formula.
[chemical formula 7]
＜ radical polymerization initiator-2 ＞
Irgacure (registered trade mark) 907 (Ciba Specialty chemicals company manufacture): alpha-aminoalkyl Benzophenone compound (optical free radical polymerization initiator), it is represented by following chemical formula.
[chemical formula 8]
＜ radical polymerization initiator-3 ＞
Ketoxime ester compound I-8: the oxime esters of [embodiment 3] of International Publication the 2009/131189th Compound (optical free radical polymerization initiator), it is represented by following chemical formula.
[chemical formula 9]
＜ radical polymerization initiator-4 ＞
The compound of embodiment B-9 of Japanese Unexamined Patent Publication 2008-179611 publication, it is by following chemical formula Represent.
[chemical formula 10]
＜ radical polymerization initiator-5 ＞
The compound of embodiment B-2 of Japanese Unexamined Patent Publication 2008-179611 publication, it is by following chemical formula Represent.
[chemical formula 11]
＜ radical polymerization initiator-6 ＞
The radical polymerization initiator that following chemical formula represents, it is according to Japanese Unexamined Patent Publication 2008-179611 The record synthesis of publication.
[chemical formula 12]
＜ radical polymerization initiator-7 ＞
Irgacure (registered trade mark) OXE01 (Ciba Specialty chemicals company manufacture), its by under State chemical formula to represent.
[chemical formula 13]
＜ epoxide-1 ＞
YX8034 (Mitsubishi chemical Co., Ltd's system): epoxide equivalent 295g/eq, obtain based on GPC mensuration Molecular weight 570, below total chlorine 1,500 mass ppm, sponifiable chlorine 70 mass ppm
＜ epoxide-2 ＞
JER157S70 (Mitsubishi chemical Co., Ltd's system): epoxide equivalent 210g/eq, water-disintegrable chlorine 800 matter Amount below ppm
＜ epoxide-3 ＞
JER834 (Mitsubishi chemical Co., Ltd's system): epoxide equivalent 250g/eq, obtain based on GPC mensuration Molecular weight 470, total chlorine 1,700 mass ppm, water-disintegrable chlorine 1,000 mass ppm
＜ epoxide-4 ＞
JER806 (Mitsubishi chemical Co., Ltd's system): epoxide equivalent 165g/eq, obtain based on GPC mensuration Molecular weight 320
＜ epoxide-5 ＞
Celoxide (registered trade mark) 2021P (Co., Ltd.'s Daicel manufactures): epoxide equivalent 137g/eq, base The molecular weight 252 obtained is measured in GPC
＜ epoxide-6 ＞
YX8000 (Mitsubishi chemical Co., Ltd's system): epoxide equivalent 205g/eq, obtain based on GPC mensuration Molecular weight 390, total chlorine 1,500 mass ppm, water-disintegrable chlorine 700 mass ppm, sponifiable chlorine 100 Quality ppm
＜ epoxide-7 ＞
YL980 (Mitsubishi chemical Co., Ltd's system): epoxide equivalent 185g/eq, obtain based on GPC mensuration Molecular weight 360, total chlorine 300 mass ppm, water-disintegrable chlorine 150 mass ppm, sponifiable chlorine 10 Quality ppm
＜ epoxide-8 ＞
YL983U (Mitsubishi chemical Co., Ltd's system): epoxide equivalent 170g/eq, obtain based on GPC mensuration Molecular weight 330, total chlorine 300 mass ppm, water-disintegrable chlorine 150 mass ppm, sponifiable chlorine 10 Quality ppm
＜ oxetane compound-1 ＞
OXT-121 (Toagosei Co., Ltd's system)
＜ cationic polymerization initiators-1 ＞
SI-B3A (three new KCC systems)
＜ cationic polymerization initiators-2 ＞
SI-B3 (three new KCC systems)
＜ levelling agent-1 ＞
Polyether-modified polydimethylsiloxane BYK-330 (BYK-Chemie Japan manufacture)
＜ organic solvent-1 ＞
Propylene glycol methyl ether acetate (boiling point under 1013.25hPa: 146 DEG C)
The evaluation ＞ of ＜ film apparent condition
Utilize spin coater in alkali-free glass substrate (Asahi Glass strain formula meeting square for the 5cm through over cleaning Society's system " AN100 ") each compositions of thermosetting resin 1 minute of upper coating table 1～table 4, by the heat of 90 DEG C Plate is dried 90 seconds so that dried thickness is 500nm.It is toasted in the baking oven of 180 DEG C 15 minutes, obtain defining the substrate of thin film on whole.To the film surface state after being formed Observe, observe by the naked eye and there is no crawling and during with the observation by light microscope of multiplying power 5 times In the visual field, the defect below 10 μm is less than 1, does not also have person to set more than the defect 1 of 10 μm For " well ".On the other hand, observe by the naked eye it can be seen that crawling or the light by multiplying power 5 times Learn when microscope is observed defect below 10 μm in the visual field to be more than 2 or can confirm that and be more than The defect of 10 μm, then be set as " there is crawling ".It addition, when prepared by heat-curable composition There is dissolvent residual or precipitation and cannot be carried out filtration treatment, do not carry out filtration treatment and masking is it can be seen that many More than individual 100 μm irregular piece, this situation is evaluated as " can not ".Result is recorded in table 1～4 In.
The evaluation ＞ of ＜ resistance to chemical reagents
Formed in a part for the thin film of the substrate made in the evaluation ＞ of above-mentioned ＜ film apparent condition and pass through Through the damage of glass baseplate surface, measure the difference in height of this part with contact pin type section difference meter, thus measure The thickness of thin film.
Then, this is impregnated 15 minutes in the N-Methyl pyrrolidone of 25 DEG C with the substrate of thin film, It is dried after washing, before again measuring, determines the thickness of the part of difference in height.With (N-crassitude Thickness after ketone dipping) form of/(N-Methyl pyrrolidone dipping before thickness) × 100=thickness conservation rate It is recorded in table 1～table 4.
The evaluation ＞ of ＜ voltage retention (VHR)
Prepare in alkali-free glass substrate (Asahi Glass Co., Ltd's manufacture square for the 2.5cm through over cleaning " AN100 ") whole of one side on be formed with the substrate A of ito film and square at 2.5cm The one side central part of glass substrate same as described above is formed with the substrate B of ito film square for 1cm, The ito film that this 1cm is square connects and has taking-up electrode wide for 2mm.
Spin coater is utilized to be formed with each of coating table 1 on the surface of ito film～table 4 at substrate A Compositions of thermosetting resin solution, is dried 90 seconds at 90 DEG C with hot plate, by the swab stick containing acetone Wipe the compositions of thermosetting resin of contact portion, then toast 15 minutes at 180 DEG C with baking oven, Obtain film forming on whole and have the substrate A of compositions of thermosetting resin.
Then, use allotter to be coated with on the periphery on the surface being formed with ito film of substrate B to contain The UV curing type sealant of the silica beads of diameter 5 μm, then defines thermosetting by substrate A Property resin combination film face with its according to outer edge deviation 3mm mode be oppositely disposed, after pressure viscosity shine Penetrate ultraviolet.
Liquid crystal (Merck Ltd., Japan system, MLC-6846-000) is injected in the sylphon so obtained, Periphery UV curing type sealant is packaged, completes voltage retention mensuration liquid crystal cells.
Carry out above-mentioned liquid crystal cells making annealing treatment (heating 2.5 hours in recirculation furnace) in 105 DEG C After, under conditions of voltage 5V, application time 16.67msec, interval 500msec, apply 60Hz's Pulse voltage, " VHR-1 " that manufacture with TOYO Corporation determines voltage retention, is tied Fruit is shown in table 1～table 4.
[embodiment 26～29]
For the compositions of thermosetting resin of embodiment 4, only change as shown in table 5 like that film forming/be dried After the condition (temperature and time) of baking, other similarly carries out evaluating and VHR of resistance to chemical reagents Measure, the results are shown in table 5 together with embodiment 4.
Table 5
By the embodiment of table 1～table 4 with the comparison of comparative example it can be said that there is epoxy radicals by comprising The special ethylene base co-polymer of side chain use solidification that non-latency imidazoles system epoxy hardener carries out and The combination of the solidification that the employing radical polymerization initiator of the compound containing ethylenically unsaturated group is carried out, VHR is improved greatly, it is achieved that high electricity reliability.In addition understand, by combination (E) epoxide, On the basis of maintaining high electricity reliability, additionally it is possible to guarantee sufficient resistance to chemical reagents.
It is believed that comparative example 1～6 is by employing cationic polymerization initiators, produce during curing reaction Acid, makes electricity reliability deteriorate.
In addition we know, for the resin with epoxy radicals, it is difficult to when not meeting (A) be formed uniformly Thin film, and then, in the case of imidazoles system epoxy hardener is latency, dissolubility is poor, be difficult to preparation all Even compositions, the solid constituent in compositions liquid left behind in film as former state, the most impossible Form thin film.Specifically, comparative example 8 by employing the imidazoles system epoxy hardener of latency, its The most also will not uniform dissolution, it is in the film, film surface left behind with the form of foreign body. Additionally it can be said that comparative example 10 is by using the condensation substance containing epoxy radicals, skeleton has upright and outspoken virtue Fragrant race group, thus in the drying process when thin film is formed, shape is easily varied, and the film obtained becomes not Uniformly.In addition it can be said that comparative example 11 is owing to employing the homopolymer of same repetitive, due to it Upright and outspoken structure, cannot relax the impact of solvent flow, obtain in the drying process when thin film is formed Film becomes uneven.
It addition, as shown in Table 5, the compositions of thermosetting resin of the present invention toasts 15 points at 150 DEG C Clock or when toasting 30 minutes at 120 DEG C, has obtained equal for 15 minutes with baking at 180 DEG C Sufficiently electricity reliability and the resistance to chemical reagents of level.In addition understand, compared with embodiment 16,19,20, Although these embodiments do not carry out light irradiation, but optical free radical polymerization initiator (oxime ester derivative) is with heat certainly Radical polymerization effect is similarly improve by base polymerization initiator.
[embodiment 30]
Obtain for making as the sample made in the evaluation ＞ of the ＜ resistance to chemical reagents of embodiment 4 Sample (membrane substrate), use the spectrophotometric determination absorbance of wavelength 250～850nm. Its spectrogram (chart) is shown in Fig. 1.It follows that use the compositions of thermosetting resin of the present invention to make Thin film is substantially transparent in the 380～780nm of visible region, is suitable to the display of the requirement transparency Device purposes.
[embodiment 31]
Make the pigment shown in the lithium salts 20 parts of the pigment shown in following formula (I), following formula (II) 1 part 79 Stirring and dissolving in part water, is prepared for anisotropy pigment film composition 1.
[chemical formula 14]
As substrate, prepare to form alignment films on glass substrate (10 × 10cm, thick 0.7mm) (poly- Acid imide film, thickness about 60nm) and the substrate of grinding process is implemented in the direction with end face level. With die coating device (wet coating thickness 2 μm, die head speed 15mm/s) coating anisotropy pigmented film in this alignment films By compositions 1, and make its natural drying, thus form the anisotropy pigmented film of thickness about 0.4 μm. It should be noted that environmental condition during coating is 23 DEG C, 50RH%.
With pure water, the end of the anisotropy pigmented film on obtained glass substrate is carried out wiping process, Make the shape of square (7 × 7cm).Carry out coating protective coating thermosetting resin in this condition Polarization optical before compositions-1 measures.
Then, prepare compositions of thermosetting resin similarly to Example 4, be made for protective coating heat Thermosetting resin compositions-1.
With spin coater (Mikasa Corporation (1H-DX2): 1500rpm, 10 seconds) each to It is coated with protective coating compositions of thermosetting resin-1 on opposite sex pigment coated substrates, then enters at 80 DEG C The prebake conditions gone 90 seconds processes.And then, carry out in 150 DEG C in temperature chamber (ESPEC company system) The heat cure of 15 minutes processes, and has obtained the polarization element of the protective coating being formed with thickness 500nm. The polarization optical having carried out polarization element in this condition measures.
The result that optical characteristics is table 6 before and after protective coating formation, before and after protective coating is formed, not There is the deterioration of polarization element polarized light property, obtain good result.
Table 6
[embodiment 32]
Use and the identical material of embodiment 31, method, carry out the sample after having made protective coating The heat-resistance test of product, the results are shown in table 7.Heat resistant test uses ESPEC company system (STH-120) Carrying out, experimental condition is as described below.
Combustor (chamber) temperature: 150 DEG C, 170 DEG C, 200 DEG C, 230 DEG C
Test period: 0 minute, 20 minutes, 60 minutes, 120 minutes
Wherein, in the experiment of the same temperature of table 7, mensuration is the same position of same sample.
Table 7
As shown in Table 7, under the treatment temperature below 200 DEG C, there is no optical characteristics Deterioration, show good characteristic.On the other hand, when 230 DEG C, along with the increase of the time of process, Absorbance and degree of polarization decline, and optical characteristics substantially deteriorates.It addition, for identical with sample 2-1～2-4 Condition make 150 DEG C～230 DEG C processed 0 minute, 20 minutes, 60 minutes, 120 minutes appoint For meaning sample, sample drips NMP (N-Methyl pyrrolidone) and has stood 5 minutes afterwards, by aobvious Micro mirror is observed and be can confirm that, the polarizing layer of protective coating and lower floor is not the most by solvent attack.More than by Result understand, the protective coating of the present embodiment the low temperature process less than 200 DEG C has have both optics spy Property and the excellent performance of solvent tolerance.
[embodiment 33]
It is changed to non-except the non-latency imidazoles system epoxy hardener-1 that replaces using in embodiment 32 Beyond latency imidazoles system epoxy hardener-3, according to material identical with embodiment 32, method Carry out heat-resistance test, show the result in table 8.
Table 8
As shown in Table 8, under the treatment temperature below 200 DEG C, there is no optical characteristics Deterioration, show good characteristic.On the other hand, when 230 DEG C, along with the increase of the time of process, Absorbance and degree of polarization decline, and optical characteristics substantially deteriorates.It addition, for identical with sample 3-1～3-3 Condition make 150 DEG C～230 DEG C processed 0 minute, 20 minutes, 60 minutes, 120 minutes appoint For meaning sample, having stood 5 minute after dripping NMP on sample, being observed by microscope can be true Recognizing, the polarizing layer of protective coating and lower floor is not the most by solvent attack.From result above, with reality Executing example 32 same, the protective coating of the present embodiment has in the low temperature process below 200 DEG C and has both light Learn the excellent performance of characteristic and solvent tolerance.
[embodiment 34]
Except not using radical polymerization initiator-1 used in embodiment 32, by radical polymerization Agent-2 increases to beyond 5 parts, carries out thermostability according to material identical with embodiment 32, method Test, shows the result in table 9.
Table 9
As shown in Table 9, under the treatment temperature below 200 DEG C, there is no optical characteristics Deterioration, show good characteristic.On the other hand, when 230 DEG C, along with the increase of the time of process, Absorbance and degree of polarization decline, and optical characteristics substantially deteriorates.It addition, for identical with sample 4-1～4-4 Condition make 150 DEG C～230 DEG C processed 0 minute, 20 minutes, 60 minutes, 120 minutes appoint For meaning sample, having stood 5 minute after dripping NMP on sample, being observed by microscope can be true Recognizing, the polarizing layer of protective coating and lower floor is not the most by solvent attack.From result above, with reality Execute example 32, embodiment 33 equally, in the protective coating of the present embodiment low temperature process below 200 DEG C There is the excellent performance having both optical characteristics and solvent tolerance.
[embodiment 35]
The PET film (Mitsubishi Plastics Inc T680E, thick 100 μm) of 7 × 7cm size will be cut into Corner be fixed on glass base with KAPTON Kapton Tape (Dupont Toray Co., Ltd. system) On plate (10 × 10cm, thick 0.7mm).Use the thermosetting tree that spin coater will use in embodiment 4 Oil/fat composition is coated on the PET film being fixed on glass substrate, and make baking after thickness be 600nm.Then, it is placed on the hot plate of 90 DEG C together with glass substrate, carries out 90 seconds being dried, Toast 30 points with the purification baking oven of 120 DEG C again, obtain the PET film of band cured film (planarization layer).? To the bending that the PET film of band cured film does not finds because shrinking, thermally-induced damage is brought or contraction Deng.
Use Vertscan (Ryoka Systems Inc. system) for obtained band cured film PET film with PET film without cured film determines surface roughness.Its result, the table of the PET film of band cured film Surface roughness (Ra) is 0.018 μm, is that the surface roughness (Ra) with the PET film without cured film is The result that 0.017 μm is equal.
And then, the PET film of band planarization layer is rolled up at pencil (Mitsubishi Pencil K. K uni) upper (bent Rate radius about 4mm), after this operation is repeated 10 times, observe the situation of cured film, now, complete Entirely do not observe crackle and stripping.
Be can confirm that by the result of embodiment 35, the compositions of thermosetting resin of the present invention also is able to for resistance to The PET film that hot temperature is low etc., the planarization of the flexible base board that to can also be used to roughness big, it is known that its Can also be suitable to the projection of substrate become the various TFT of electric leakage (leak) reason, organic EL flexibility this The purposes of sample.In addition we know, it also has soft without compromising on the flexibility of flexible base board, cured film itself Property patience.
With reference to specific embodiment, the present invention is illustrated in detail, but those skilled in the art should This is clear and definite, can add various change or correction without departing from the spirit and scope of the present invention. Japanese patent application (the Japanese Patent Application that the application filed an application based on January 10th, 2014 2014-003372) and the Japanese patent application (Japanese Patent Application filed an application on April 17th, 2014 2014-085762), its content is introduced in this as reference.
Industrial applicibility
The compositions of thermosetting resin of the present invention can be suitable as forming requirement high electricity reliability Protecting film used in liquid crystal indicator, organic EL display, organic semiconductor device etc., The material of the component such as dielectric film, planarization film.The compositions of thermosetting resin of the application of the invention, can Obtain having curability at low temperatures and the electricity cured film of reliability, component concurrently, and then it is excellent to form surface texture Different thin film, is the most industrially useful.

Claims (22)

1. a compositions of thermosetting resin, it contains:
(A) comprising the 1st side chain and the ethylenic copolymer of the 2nd side chain, described 1st side chain has epoxy Base, described 2nd side chain has alkyl or aromatic ring group, described alkyl or aromatic ring group and optionally has replacement Base；
(B) non-latency imidazoles system epoxy hardener；
(C) compound containing ethylenically unsaturated group；And
(D) radical polymerization initiator.
Compositions of thermosetting resin the most according to claim 1, wherein, in described 2nd side chain Alkyl be cyclic alkyl.
Compositions of thermosetting resin the most according to claim 1 and 2, wherein, (A) vinyl is common Polymers has more than 7 glycidyl ethers, and weight average molecular weight is 1, more than 000.
4. according to the compositions of thermosetting resin according to any one of claims 1 to 3, wherein, (A) Ethylenic copolymer is the unsaturated compound containing epoxy radicals and the chemical combination containing ethylenically unsaturated group Thing copolymerization and obtain, the described compound containing ethylenically unsaturated group has alkyl or aromatic ring group, Described alkyl or aromatic ring group optionally have substituent group.
5. according to the compositions of thermosetting resin according to any one of Claims 1 to 4, wherein, (A) Ethylenic copolymer content ratio in all solids composition is 30～95 mass %.
6. according to the compositions of thermosetting resin according to any one of Claims 1 to 5, wherein, (B) Non-latency imidazoles system epoxy hardener content ratio in all solids composition is 1～15 mass %.
7. according to the compositions of thermosetting resin according to any one of claim 1～6, wherein, (C) Compound containing ethylenically unsaturated group has more than 2 ethylenically unsaturated groups.
8. according to the compositions of thermosetting resin according to any one of claim 1～7, wherein, (D) It is the azo-compound of 70～140 DEG C that radical polymerization initiator comprises 10 hours half life temperatures.
9. according to the compositions of thermosetting resin according to any one of claim 1～8, wherein, (D) Radical polymerization initiator comprises oxime ester derivative class and alpha-aminoalkyl benzophenone derivatives apoplexy due to endogenous wind at least One.
10., according to the compositions of thermosetting resin according to any one of claim 1～9, it is possibly together with (A) Epoxide beyond ethylenic copolymer is as (E) composition.
11. according to the compositions of thermosetting resin according to any one of claim 1～10, its possibly together with Under 1013.25hPa, boiling point is that the organic solvent of 80～200 DEG C is as (F) composition.
12. compositions of thermosetting resin according to claim 11, wherein, all solids composition Content ratio in compositions of thermosetting resin is 3～20 mass %.
13. according to the compositions of thermosetting resin according to any one of claim 1～12, wherein, and will This compositions of thermosetting resin 180 DEG C, under conditions of 15 minutes solidification and obtain thickness 500nm's Thin film, stands dipping thickness after 15 minutes full at 25 DEG C in N-Methyl pyrrolidone by this thin film Foot following formula (i),
95≤(thickness before thickness/dipping after dipping) × 100≤105 (i).
14. according to the compositions of thermosetting resin according to any one of claim 1～13, and it is used for protecting Protect coating.
15. compositions of thermosetting resin according to claim 14, it is used for protective coating, institute State protective coating to be formed on the anisotropy pigmented film formed by coating.
16. 1 kinds of solidification components, it is to use the thermosetting tree according to any one of claim 1～15 Oil/fat composition and formed.
17. solidification components according to claim 16, it is the solidification temperature below 200 DEG C Lower formation.
18. 1 kinds of cured film, it includes the solidification component described in claim 16 or 17.
19. use compositions of thermosetting resin according to any one of claim 1～13 and the guarantor that formed Protecting coating, it is formed on the anisotropy pigmented film formed by coating.
20. 1 kinds of polarization elements, it has the protective coating described in claim 19 and by being coated with Cloth and the anisotropy pigmented film that formed.
21. 1 kinds of image display devices, it possesses the polarization element described in claim 20.
22. 1 kinds of image display devices, it possesses the solidification component described in claim 16 or 17.
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