CN103576457A - Solid resin compound and purpose thereof - Google Patents

Solid resin compound and purpose thereof Download PDF

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Publication number
CN103576457A
CN103576457A CN201310348018.6A CN201310348018A CN103576457A CN 103576457 A CN103576457 A CN 103576457A CN 201310348018 A CN201310348018 A CN 201310348018A CN 103576457 A CN103576457 A CN 103576457A
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methyl
mentioned
resin composition
monomer
acid
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CN103576457B (en
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山口稔
前田顺启
田村亮太
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Filters (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Materials For Photolithography (AREA)

Abstract

The invention provides a solid resin compound and a purpose thereof. The solid resin compound can be used to develop various physical properties such as solidification, the solvent resistance performance after the solidification, the adaptation performance of the substrate (base material), the heat resistance performance, and the transparency, and the storage stability is excellent, and the compound is useful for the color filter. The solid condensate provided with the solidification resin, the color filter of the condensate, and the display device are also provided. The solid resin compound contains the (methyl) acrylate system polymer, a polymerized compound, the photopolymerization initiator, and wherein the acrylate system polymer is the polymer provided with a structural unit containing the tertiary carbon (methyl) acrylate monomer. The solid resin compound further comprises the polymer provided with hydroxyl, and/or the (methyl) acrylate system polymer is further provided with the hydroxyl.

Description

Hardening resin composition and uses thereof
[technical field]
The present invention relates to hardening resin composition and uses thereof.Useful hardening resin composition, its solidfied material in the various uses such as the various opticses such as the color filter that in more detail, the present invention relates in liquid crystal indicator or solid state image sensor etc. to use, ink, galley, printed circuit board (PCB), semiconductor element, photoresist or motor electronics, use color filter and the display device of solidfied material.
[background technology]
For having studied the application towards various uses by the hardening resin composition of heat or active energy line curing, for example, the purposes such as the various opticses such as the color filter using in liquid crystal indicator or solid state image sensor etc., ink, galley, printed circuit board (PCB), semiconductor element, photoresist or motor electronics, have developed the hardening resin composition of desired excellent in each purposes.Among these purposes; so-called color filter is for forming the critical piece of liquid crystal indicator or solid state image sensor etc.; conventionally by the pixel of substrate, at least 3 primary colors (red (R) green (G) blue (B)) and by (BM) and the formations such as diaphragm in addition at the bottom of their separated resin black; this diaphragm carries out coating protection at the bottom of to pixel and resin black, and arranges in order to make these concavo-convex planarizations.
Conventionally, in the situation that the pixel of using hardening resin composition to carry out color filter forms, for each color pixel, carry out following operation: (1) is at the painting process of whole coating hardening resin composition of substrate; (2) exposure process carries out pattern exposure exposure portion is solidified on the resist film being formed by painting process across photomask, make afterwards solidified portion insoluble; (3) develop and to fire (baking) treatment process, utilize after developer solution removes unexposed portion, by firing (baking), exposure portion is further solidified; Employing is to method of repeatedly carrying out the operation identical with it of all kinds.If consider the application in such color filter purposes etc., require that hardening resin composition has curability, the various physical property such as solvent resistance, the adaptation with substrate (base material), thermotolerance and the transparency after solidifying.In addition, in recent years, the miniaturization slimming of having carried out optics, motor electronics etc. economizes and can quantize, and accompanies with it, and the parts such as color filter that urgent hope is used have high-grade performance.
About existing hardening resin composition, as the composition that is suitable for color filter purposes, for example, following composition is disclosed: the photosensitive composition (referring to patent documentation 1) that contains resin glue (this resin glue contains the structural unit of being derived by the monomer with aliphatics polycycle epoxy radicals and is the structural unit that monomer is derived by unsaturated carboxylic acid), colorant, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent; The photosensitive composition (referring to patent documentation 2) that contains multipolymer (this multipolymer contains following structural unit: have being thermal decomposited property of carboxyl/phenolic hydroxyl group group and protect the structural unit of the residue forming, the structural unit that has the structural unit of epoxy radicals/oxetanyl and have carboxyl/phenolic hydroxyl group), radioactivity-sensitive radical polymerization initiator, ethylenically unsaturated compounds and colorant.
[prior art document]
[patent documentation]
Patent documentation 1: TOHKEMY 2007-333847 communique
Patent documentation 2: TOHKEMY 2012-22048 communique
[summary of the invention]
[inventing problem to be solved]
As mentioned above, for hardening resin composition, require that it has curability, the various physical property such as solvent resistance, the adaptation with substrate (also referred to as base material), thermotolerance and the transparency after solidifying.On the other hand, the aspect from processing, also requires hardening resin composition itself to have storage stability (also referred to as storage stability), and solidfied material can play consistently out the transparency, solvent resistance, adaptation, thermotolerance etc.And, in recent years, along with the progress of the technology such as display device, for each used parts, also strongly expect to have higher performance, for example, in color filter purposes, require to there is high transparent after solidifying.But in existing resin combination, present situation is fully to tackle these an urgent demands.For example, in the resin combination described in patent documentation 1,2, because curability is insufficient, cannot obtain the solidfied material that the transparency is high; And storage stability is also insufficient, thereby is further improving the curability of resin combination, can stablize the leeway that aspects such as having given play to high transparent also has improvement.And improve resin combination storage stability aspect also have the leeway of improvement.
The present invention carries out in view of above-mentioned present situation, its object is to provide a kind of hardening resin composition, this hardening resin composition can stablize given play to curability, the various physical property such as solvent resistance, the adaptation with substrate (base material), thermotolerance and the transparency after solidifying, excellent storage stability is useful in the various uses such as color filter.The present invention also aims to provide the solidfied material forming with such hardening resin composition and color filter and the display device of having used this solidfied material.
[solving the means of problem]
The inventor has carried out various research for hardening resin composition useful in the various uses such as color filter, be conceived to following content:, the resin combination that contains (methyl) acrylic ester polymer, polymerizable compound and Photoepolymerizationinitiater initiater if make, can become the composition with curability.Also find, if making this hardening resin composition is following proposal (form), the excellent storage stability of hardening resin composition, in addition curability and solidify after solvent resistance improve tremendously, can obtain stably showing the solidfied material of the various physical property such as high transparent, the adaptation with substrate (base material), thermotolerance, high rigidity; Described scheme is come the structural unit of (methyl) acrylic ester monomer of self-contained tertiary carbon and the scheme that this hardening resin composition further contains the polymkeric substance with hydroxyl for (methyl) acrylic ester polymer has; And/or this (methyl) acrylic ester polymer further has the scheme of hydroxyl.Such hardening resin composition is useful especially in color filter purposes, as being used to form color filter, with the resin combination of diaphragm or dielectric film etc., is wherein suitable.Therefore find, the solidfied material being formed by such hardening resin composition, color filter and display device can fully be tackled an urgent demand of high performance in recent years, in optical field, motor electronic field, be extremely useful, expect thus ideally solving above-mentioned problem, thereby completed the present invention.
Herein, contained (methyl) acrylic ester polymer of hardening resin composition of the present invention has the structural unit of (methyl) acrylic ester monomer of self-contained tertiary carbon, the easy decomposes of this structural unit.Specifically, and the O-C key between the oxygen atom of (methyl) acryloyl group adjacency and the tertiary carbon atom that is adjacent is easily cut off, thereby is decomposed into (methyl) acrylic acid and the stable compound becoming at tertiary carbon atom adnation.Therefore, for example, in situation about hardening resin composition of the present invention being formed for the pixel of color filter, by the heating process after developing (also referred to as ablating work procedure or after cure operation), the structural unit of (methyl) acrylic ester monomer of above-mentioned next self-contained tertiary carbon decomposes, the stable compound that generates (methyl) acrylic acid and produce in tertiary carbon atom side.And think, between the hydroxyl that hydroxyl in the polymkeric substance with hydroxyl that hardening resin composition can further contain and/or (methyl) acrylic ester polymer can further have and (methyl) acrylic acid generating, produce ester cross-linked structure, due to this reason, the curability of resin combination and solidify after solvent resistance be improved tremendously.
In addition, above-mentioned (methyl) acrylic ester polymer, there is hydroxyl polymkeric substance preferably as described later for there is the polymkeric substance of the two keys of polymerism at side chain.Thus, can further improve curability, compare with only using the situation that has a polymkeric substance of the two keys of polymerism at side chain, the present invention can improve the curability of hardening resin composition, also can improve storage stability simultaneously.This be due to, in the present invention, as described above, between (methyl) acrylic acid producing in thermal decomposition and hydroxyl, can expect the curing reaction based on ester cross-linked structure, in this case, even if the content of the two keys of the polymerism in minimizing polymkeric substance, also can show sufficient curability, the two keys of polymerism that can further be reduced in side chain in preservation react and produce the possibility of gelation.
; the present invention relates to a kind of hardening resin composition; it is hardening resin composition of containing (methyl) acrylic ester polymer, polymerizable compound and Photoepolymerizationinitiater initiater, and this hardening resin composition is characterised in that: should (methyl) acrylic ester polymer be the polymkeric substance of structural unit come with (methyl) acrylic ester monomer of self-contained tertiary carbon; This hardening resin composition is at least one mode of selecting in the group that free following manner forms, and described mode is: this hardening resin composition further contains the mode of the polymkeric substance with hydroxyl; And this (methyl) acrylic ester polymer further has the mode of hydroxyl.
The invention still further relates to a kind of solidfied material, it solidifies above-mentioned hardening resin composition to form.
The invention further relates to color filter, it has above-mentioned solidfied material on substrate.
And, the invention still further relates to display device, it uses above-mentioned color filter to form.
The present invention is below described in detail in detail.It should be noted that, the mode that each optimal way of the present invention of 2 kinds or 3 kinds above following records is combined is also optimal way of the present invention.
It should be added that:
The technical scheme of claim 1 comprise following a)～c) three kinds of modes.
A) at least comprise (methyl) acrylic ester polymer ※ 1, polymerizable compound, Photoepolymerizationinitiater initiater and the hardening resin composition with these 4 kinds of compositions of polymkeric substance of hydroxyl.
※ 1:(methyl) acrylic ester polymer has the structural unit of (methyl) acrylic ester monomer of self-contained tertiary carbon, and this polymkeric substance can also further have hydroxyl.
B) at least comprise (methyl) acrylic ester polymer ※ 2, polymerizable compound and these 3 kinds of compositions of Photoepolymerizationinitiater initiater hardening resin composition.
※ 2:(methyl) acrylic ester polymer be have self-contained tertiary carbon (methyl) acrylic ester monomer structural unit and there is the polymkeric substance of hydroxyl.
C) at least comprise (methyl) acrylic ester polymer ※ 3, polymerizable compound, Photoepolymerizationinitiater initiater and the hardening resin composition with these 4 kinds of compositions of polymkeric substance of hydroxyl.
※ 3:(methyl) acrylic ester polymer be have self-contained tertiary carbon (methyl) acrylic ester monomer structural unit and there is the polymkeric substance of hydroxyl.
[hardening resin composition]
Hardening resin composition of the present invention contains (methyl) acrylic ester polymer, polymerizable compound and Photoepolymerizationinitiater initiater, and these contain composition and can use respectively one kind or two or more.In addition, can further contain as required other one kind or two or more composition.
< (methyl) acrylic ester polymer >
In above-mentioned hardening resin composition, (methyl) acrylic ester polymer has the structural unit of (methyl) acrylic ester monomer of self-contained tertiary carbon.Come the structural unit of (methyl) acrylic ester monomer of self-contained tertiary carbon to mean that the polymerism carbon-to-carbon double bond (C=C) in this monomer becomes the structural unit of singly-bound (C-C); the structure that suitable is this monomer has oxygen atom and tertiary carbon atom bonding forms, and this oxygen atom is the oxygen atom with (methyl) acryloyl group adjacency.That is, above-mentioned (methyl) acrylic ester monomer containing tertiary carbon has and is adjacent to the oxygen atom of (methyl) acryloyl group and structure that tertiary carbon atom bonding forms is applicable to.It should be noted that, so-called tertiary carbon atom means that other carbon atom with this carbon atom bonding is the carbon atom of 3.
As above-mentioned (methyl) acrylic ester monomer containing tertiary carbon, suitable is has the compound of 1 polymerism carbon-to-carbon double bond in molecule, in molecule, have 1 (methyl) acryloyl group (CH 2=C (R)-C (=O)-) compound, be for example preferably the represented compound of following general formula (1):
CH 2=C(R)-C(=O)-O-A (1)
(R represents hydrogen atom or methyl.A represents to be included in any monovalent organic radical group that oxygen atom side has the structure of tertiary carbon atom.)。
In above-mentioned general formula (1), the represented organic group of A can be with for example-C (R 1) (R 2) (R 3) represent.In this case, R 1, R 2and R 3alkyl identical or different and carbon number 1～30 is suitable, and this alkyl can be saturated hydrocarbyl, can be also unsaturated alkyl.And, can there is ring texture, also can be further with substituting group.In addition, R 1, R 2and R 3the distal portion formation ring texture that can interconnect.
It should be noted that; in the present invention; as described later; from O-C key, (this O-C key is the O-C key between oxygen atom and tertiary carbon atom; this oxygen atom is the oxygen atom with (methyl) acryloyl group adjacency; this tertiary carbon atom is the tertiary carbon atom being adjacent in the A of this oxygen atom) be cut off and the noval chemical compound that generates holds volatile aspect and considers, the carbon number of the organic group that A is represented is preferably below 12.Wherein, the represented organic group of A is preferably the group from (methyl) tert-butyl acrylate and/or (methyl) acrylic acid tert-pentyl ester.And the represented organic group of A can have branched structure.
Herein, above-mentioned containing in (methyl) acrylic ester monomer of tertiary carbon, about being bonded in the tertiary carbon atom on the oxygen atom with (methyl) acryloyl group adjacency, with in the carbon atom of this tertiary carbon atom adjacency at least 1 be suitable with hydrogen atom bonding.For example, at (methyl) acrylic ester monomer containing tertiary carbon, be that the represented compound of above-mentioned general formula (1), A are-C (R 1) (R 2) (R 3) in the situation of represented group, R 1, R 2and R 3in at least 1 there is 1 above hydrogen atom, this is preferred.In such mode; by heating; (this O-C key is the O-C key between oxygen atom and tertiary carbon atom to O-C key; this oxygen atom is the oxygen atom with (methyl) acryloyl group adjacency; this tertiary carbon atom is the tertiary carbon atom that is adjacent to this oxygen atom) be cut off and generate (methyl) acrylic acid; simultaneously between this tertiary carbon atom and the carbon atom that is adjacent, form two keys (C=C), more stably generate new compound.
The noval chemical compound generating is as mentioned above preferably volatile.In this case, this noval chemical compound is waved loose from solidfied material, and thus, the thickness of solidfied material (cured film) reduces, and in the situation that for example above-mentioned hardening resin composition further contains colorant, colorant concentration increases after heating simultaneously.Therefore, further filming, while can be realized and the high shading rate of high color purity and black matrix layer can be further sought.If consider this aspect, above-mentioned R 1, R 2and R 3identical or different and be that carbon number is that 1～15 saturated hydrocarbyl is for preferred.More preferably the saturated hydrocarbyl that carbon number is 1～10, the saturated hydrocarbyl that further preferably carbon number is 1～5, the saturated hydrocarbyl that particularly preferably carbon number is 1～3.
From the aspect of developability, preferably above-mentioned (methyl) acrylic ester polymer is for demonstrating alkali-soluble polymkeric substance, and the polymkeric substance in molecule with acidic group is suitable.
As above-mentioned acidic group, can enumerate the functional group with buck generation neutralization reaction such as carboxyl, phenolic hydroxyl group, acid anhydride, phosphate, sulfonic group etc., can only there is wherein a kind, also can there is two or more.Wherein preferably carboxyl, acid anhydride, more preferably carboxyl.
Above-mentioned (methyl) acrylic ester polymer is in the situation that have the polymkeric substance of acidic group in molecule, as the acid number (AV) of this polymkeric substance, be not particularly limited, and for example, 20mgKOH/g is above, be less than 300mgKOH/g is suitable.Thus, more sufficient alkali solubility can be shown, the solidfied material that developability is more excellent can be accessed.As the lower limit of acid number more preferably 30mgKOH/g above, more preferably more than 40mgKOH/g.In addition more preferably 200mgKOH/g following, more preferably below 150mgKOH/g.
The acid number of polymkeric substance for example can be obtained as mentioned below.
Above-mentioned (methyl) acrylic ester polymer can also be for having the polymkeric substance of hydroxyl in molecule.That is, above-mentioned (methyl) acrylic ester polymer can be for further having the polymkeric substance of hydroxyl, and such mode is also one of suitable method of the present invention.Thus, can further improve the curability of hardening resin composition, the further solidfied material of excellence of the transparency can be provided.
Above-mentioned (methyl) acrylic ester polymer for example can be by carrying out polymerization and obtain comprising monomer component containing (methyl) acrylic ester monomer of tertiary carbon.Preferably this monomer component further contains the monomer with acidic group and the two keys of polymerism.In addition, above-mentioned (methyl) acrylic ester polymer has in the situation of hydroxyl, and it is suitable that above-mentioned monomer component further contains the monomer with the two keys of hydroxyl and polymerism.
It should be noted that, each monomer using can be used respectively one kind or two or more.
Above-mentioned (methyl) acrylic ester polymer can be to carry out by the monomer component to such the polymkeric substance (also referred to as base polymer (base polymer)) that polymerization obtains, also can be to make as mentioned below to have the polymkeric substance (have the polymkeric substance of the two keys of polymerism or contain pendant double bonds polymkeric substance also referred to as side chain) that can react with this base polymer with the functional group of acidic group bonding and the compound of the two keys of polymerism and obtain, it be suitable.More preferably, containing pendant double bonds polymkeric substance, curability can be further improved thus, the more excellent solidfied materials such as the transparency, adaptation can be obtained.It should be noted that, the two keys of polymerism of side chain are that free-radical polymerised two keys are suitable.
In above-mentioned monomer component, containing (methyl) acrylic ester monomer of tertiary carbon as mentioned above, with respect to the total amount 100 quality % of above-mentioned monomer component, this monomer containing proportional be suitably 5 quality % more than.Thus, can further show effect of the present invention, effect of the present invention comes the structural unit of self-contained tertiary carbon (methyl) acrylic ester monomer to produce.Should be above containing proportional more preferably 15 quality %, be particularly preferably 20 quality % more than.And, above-mentionedly containing the proportional upper limit, consider that the ratio that contains of other monomer take the circumstances into consideration to set, for example, for color filter purposes in the situation that, from the viewpoint of further raising pattern properties, developability, be suitably below 90 quality %.More preferably 75 quality % following, more preferably below 60 quality %.
As the above-mentioned monomer with the two keys of acidic group and polymerism, can enumerate such as unsaturated monocarboxylic classes such as (methyl) acrylic acid, butenoic acid, cinnamic acid, vinyl benzoic acids; The unsaturated polybasic carboxylic acid classes such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; Between the unsaturated groups such as succinic acid list-2-(2-acryloxy) hydroxyl ethanol, succinic acid list-2-(2-methacryloxy) hydroxyl ethanol and carboxyl, there is the unsaturated monocarboxylic class of chain extension; The unsaturated acid anhydride such as maleic anhydride, itaconic anhydride class; The unsaturated compound of the phosphorous acidic groups such as light ester P-1M (common prosperity society chemistry is manufactured); Etc..Among these, from versatility, the aspect such as acquired, being suitable for using carboxylic acid is monomer (unsaturated monocarboxylic class, unsaturated polybasic carboxylic acid class, unsaturated acid anhydride class).More preferably, from the viewpoint of reactivity, alkali solubility etc., preferably use unsaturated monocarboxylic class, further preferably (methyl) acrylic acid, wherein methacrylic acid particularly preferably.
It should be noted that, (methyl) acrylic acid means acrylic acid and/or methacrylic acid.
The ratio that contains of the above-mentioned monomer with the two keys of acidic group and polymerism takes the circumstances into consideration to be set in that to make the acid number of (methyl) acrylic ester polymer be in above-mentioned preferable range.For example, with respect to the total amount 100 quality % of above-mentioned monomer component, have the two keys of acidic group and polymerism monomer containing proportional be preferably 5 quality % above, more preferably 10 quality % above, more preferably more than 20 quality %.And be preferably 85 quality % following, more preferably 60 quality % following, more preferably below 50 quality %.
In addition, as mentioned above, above-mentioned monomer component comprises that the monomer with the two keys of hydroxyl and polymerism is also suitable.Such monomer is preferably the monomer that side chain has hydroxyl, and, from reactive aspect, be suitably the monomer with hydroxyl and (methyl) acryloyl group.Preferably for example can enumerate (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-3-hydroxy propyl ester, (methyl) acrylic acid-2-hydroxyl butyl ester, (methyl) acrylic acid-3-hydroxyl butyl ester, (methyl) acrylic acid-4-hydroxyl butyl ester, (methyl) acrylic acid-2, (methyl) acrylic acid hydroxy alkyl esters such as 3-hydroxy propyl ester.
It should be noted that, so-called (methyl) acryloyl group means methacryl and/or acryloyl group.
Above-mentioned monomer component comprises in the situation of the monomer with the two keys of hydroxyl and polymerism, with respect to the total amount 100 quality % of above-mentioned monomer component, this monomer containing proportional be for example suitably 1 quality % more than.Should be containing more than proportional more preferably 5 quality %, more preferably more than 10 quality %.In addition, if consider (methyl) acrylic ester monomer containing tertiary carbon, have acidic group and the two keys of polymerism monomer containing proportional, be preferably 70 quality % following, more preferably below 50 quality %.
Contained (methyl) acrylic ester polymer of hardening resin composition of the present invention is the polymkeric substance of structural unit come with (methyl) acrylic ester monomer of self-contained tertiary carbon, and more preferably main chain has ring structure.As ring structure, can enumerate imide ring, amylene oxide ring, tetrahydrofuran ring, lactonic ring etc.In order to have these ring structures, above-mentioned monomer component also contains the monomer (also referred to as other monomer) that other can copolymerization except above-mentioned monomer.
As above-mentioned other monomer, for example preferably using above-mentioned monomer N substituted maleimide amine is in addition monomer, dialkyl group-2, and 2 '-(oxygen base dimethylene) diacrylate is monomer, α-(unsaturated alkoxyalkyl) acrylic ester monomer (preferred alkyl-(α-allyloxy methyl) acrylic ester monomer) etc.Thus, above-mentioned monomer component further contains that to select free N substituted maleimide amine be monomer, dialkyl group-2, and 2 '-(oxygen base dimethylene) diacrylate is that the mode of at least one monomer in the group of monomer and α-(unsaturated alkoxyalkyl) acrylic ester monomer composition is also one of suitable way of the present invention.In addition,, according to desired physical property, can suitably use one kind or two or more in (methyl) acrylic ester monomer and aromatic vinyl base system monomer etc.
Herein, using for example N substituted maleimide amine, be monomer and/or dialkyl group-2, when 2 '-(oxygen base dimethylene) diacrylate is monomer and/or alkyl-(α-allyloxy methyl) acrylic ester monomer, can access the solidfied material that thermotolerance, hardness, colorant dispersiveness etc. are further enhanced.Particularly, using dialkyl group-2, when 2 '-(oxygen base dimethylene) diacrylate is monomer and/or alkyl-(α-allyloxy methyl) acrylic ester monomer, can obtain more excellent solidfied material aspect heat-resisting coloring.
It should be noted that, in the total amount 100 quality % of above-mentioned monomer component, above-mentioned other monomer containing proportional be preferably 60 quality % following, be preferably below 50 quality %.Particularly containing N substituted maleimide amine is monomer, dialkyl group-2,2 '-(oxygen base dimethylene) diacrylate is in the situation of monomer and/or α-(unsaturated alkoxyalkyl) acrylic ester monomer, from aspects such as thermotolerance, hardness, colorant dispersiveness, developing powder, the transparencys, it is containing proportional 2 quality %～60 quality %, more preferably 2 quality %～50 quality %, the 3 quality %～40 quality % more preferably of being preferably.
As above-mentioned N substituted maleimide amine, it is monomer, such as N-N-cyclohexylmaleimide, N-phenylmaleimide, N-methyl maleimide, NEM, N-isopropyl maleimide, N-tert-butyl group maleimide, N-dodecyl maleimide, N-benzyl maleimide, N-naphthyl maleimide etc. can be enumerated, one kind or two or more in them can be used.Wherein, from transparent aspect, preferably N-phenylmaleimide, N-benzyl maleimide, be suitably N-benzyl maleimide especially.
As above-mentioned N-benzyl maleimide, for example can enumerate: benzyl maleimide; To methyl-benzyl maleimide, to alkyl substituted benzyl base maleimides such as butyl benzyl maleimides; To phenolic hydroxyl group substituted benzyl maleimides such as hydroxybenzyl maleimides; O-chlorobenzyl maleimide, adjacent dichloro benzyl maleimide, to halogen substituted benzyl maleimides such as dichloro benzyl maleimides; Etc..
As above-mentioned dialkyl group-2,2 '-(oxygen base dimethylene) diacrylate is monomer, for example can enumerate 2,2 '-[oxo two (methylene)] two acrylic acid, dialkyl group-2,2 '-[oxo two (methylene)] two 2-acrylate, dialkyl group-2, at least 1 in the esteratic sites such as 2 '-[oxo two (methylene)] two 2-acrylate contains tertiary carbon compound etc.Among these, from the transparency, dispersed, the industrial aspects such as easiness that obtain, be suitable for using for example dimethyl-2,2 '-[oxo two (methylene)] two 2-acrylate etc.
As above-mentioned α-(unsaturated alkoxyalkyl) acrylic ester monomer, can enumerate for example α-allyloxy methacrylic acid, α-allyloxy methyl methacrylate, α-allyloxy β-dimethyl-aminoethylmethacrylate, α-allyloxy n propyl methacrylate, α-allyloxy isopropyl methacrylate, α-allyloxy n-BMA, the secondary butyl ester of α-allyloxy methacrylic acid, α-allyloxy Tert-butyl Methacrylate, α-allyloxy methacrylic acid n-pentyl ester, the secondary pentyl ester of α-allyloxy methacrylic acid, α-allyloxy methacrylic acid tert-pentyl ester, α-allyloxy methacrylic acid peopentyl ester etc.Wherein be suitably alkyl-(α-allyloxy methyl) acrylic ester monomer.As alkyl-(α-allyloxy methyl) acrylic ester monomer, from the transparency, the aspects such as easiness that dispersed, industry obtains, be suitable for using such as methyl-(α-allyloxy methyl) acrylate etc.
Above-mentioned α-(unsaturated alkoxyalkyl) acrylate for example can be manufactured by disclosed manufacture method in No. 2010/114077 pamphlet of International Publication.
As above-mentioned (methyl) acrylic ester monomer, for example, if consider skin hardness of solidfied material etc., preferably there is the monomer of alicyclic ring skeleton.Specifically, can enumerate for example (methyl) cyclohexyl acrylate, (methyl) acrylic acid (cyclohexyl) methyl esters, (methyl) isobornyl acrylate, (methyl) acrylic acid-1-diamantane ester, (methyl) acrylic acid (3, 4-epoxycyclohexyl) methyl esters, (methyl) acrylic acid two cyclopentene esters, two cyclopentene oxygen base (methyl) ethyl acrylates, methacrylic acid three ring [last of the ten Heavenly stems ester, dihydroxymethyl-tristane two (methyl) acrylate, pentacyclopentadecandimethanol dimethanol two (methyl) acrylate, cyclohexanedimethanol two (methyl) acrylate, norcamphane dimethanol two (methyl) acrylate, terpane-1, 8-glycol two (methyl) acrylate, terpane-2, 8-glycol two (methyl) acrylate, terpane-3, 8-glycol two (methyl) acrylate, dicyclo [2.2.2]-octane-1-methyl-4-isopropyl-5, 6-dihydroxymethyl two (methyl) acrylate etc.Among these, from versatility, the aspect such as acquired, be suitable for using (methyl) cyclohexyl acrylate, (methyl) acrylic acid (cyclohexyl) methyl esters, (methyl) isobornyl acrylate, methacrylic acid three ring esters in the last of the ten Heavenly stems.In addition, be also suitable for using the alicyclic epoxy compounds such as (methyl) glycidyl acrylate, (methyl) acrylic acid methyl ethylene oxidic ester, (methyl) acrylic acid ethyl ethylene oxidic ester.
Above-mentioned (methyl) acrylic ester monomer for example can also be enumerated: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) acrylic acid n-pentyl ester, the secondary pentyl ester of (methyl) acrylic acid, the just own ester of (methyl) acrylic acid, (methyl) acrylic acid-2-ethyl caproite, (methyl) isodecyl acrylate, (methyl) tridecyl acrylate, (methyl) acryllic acid monooctyl ester, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid-2-methoxyl ethyl ester, (methyl) acrylic acid-2-ethoxy ethyl ester, (methyl) acrylic acid phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid N, N-dimethylaminoethyl, Alpha-hydroxy methyl methacrylate, Alpha-hydroxy β-dimethyl-aminoethylmethacrylate, Alpha-hydroxy Tert-butyl Methacrylate, Alpha-hydroxy methacrylic acid tert-pentyl ester etc., and Isosorbide-5-Nitrae-dioxo spiro [4,5] decane-2-ylmethyl acrylic acid, (methyl) acryloyl morpholine, tetrahydrofurfuryl acrylate, 4-(methyl) acryloyl-oxy ylmethyl-2-methyl-2-ethyl-DOX, 4-(methyl) acryloyl-oxy ylmethyl-2-methyl-2-isobutyl-DOX, 4-(methyl) acryloyl-oxy ylmethyl-2-methyl-2-cyclohexyl-DOX, 4-(methyl) acryloyl-oxy ylmethyl-2,2-dimethyl-DOX etc.Wherein, from the viewpoint of easily obtaining, thermotolerance, colorant are dispersed, solvent deliquescent balance again, and (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) benzyl acrylate are suitable.
As above-mentioned aromatic vinyl base system monomer, for example can enumerate styrene, vinyltoluene, α-methyl styrene, methoxy styrene etc.Wherein, from the viewpoint of the heat-resisting coloring of resin, heat-resisting decomposability, styrene and/or vinyltoluene are suitable.
As above-mentioned other monomer, can be for such as in following compound etc. one kind or two or more.
N, (methyl) acrylic amides such as N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide; Polystyrene, poly-(methyl) methyl acrylate, polyoxyethylene, PPOX, polysiloxane, polycaprolactone, polycaprolactam etc. have the large monomer class of (methyl) acryloyl group at an end of polymer molecular chain; 1,3-butadiene, isoprene, chlorbutadiene equiconjugate dienes; The vinyl esters such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate; The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl group vinyl ether, methoxyethoxyethyl vinyl ether, methoxy poly (ethylene glycol) vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; The N-vinyl compound classes such as NVP, N-caprolactam, N-vinyl imidazole, N-vinyl morpholine, N-vinyl acetamide; (methyl) acrylic acid isocyanates root closes the unsaturated isocyanate classes such as ethyl ester, allyl isocyanates; Etc..
As by the method for above-mentioned monomer component polymerization, can use the normally used methods such as bulk polymerization, solution polymerization, emulsion polymerization, can be according to object, the suitable selection of purposes.Wherein, in industrial favourable, the reason that is also easy to carry out the structural adjustments such as molecular weight, solution polymerization is suitable.In addition the polymerization of the polymerization mechanism that can use above-mentioned monomer component based on mechanism such as free radical polymerization, anionic polymerisation, cationic polymerization, coordination polymerizations, the polymerization based on radical polymerization mechanism industrial be also favourable, thereby preferably.
As long as can supplying with polymerization to monomer component by heat, electromagnetic wave (such as infrared ray, ultraviolet ray, X ray etc.), electron ray isoreactivity energy source, the polymerization initiating method in above-mentioned polyreaction causes required energy, if further share polymerization initiator, can greatly reduce polymerization and cause needed energy, and make to react easy control, because of but suitable.
In addition, above-mentioned monomer component is carried out to polymerization and the molecular weight of the polymkeric substance that obtains can be controlled by adjusting the kind of the amount of polymerization initiator or kind, polymerization temperature, chain-transferring agent or amount etc.
In the situation that utilizing solution polymerization process to carry out polymerization to above-mentioned monomer component, as the solvent using in polymerization, as long as be being just not particularly limited of inertia in polyreaction.For example, can take the circumstances into consideration to set according to polymerizing conditions such as the kind of polymerization mechanism, the monomer used or amount, polymerization temperature, polymerization concentration, thereafter when making hardening resin composition, in the situation that using solvent as thinning agent etc., solution polymerization by the solvent that contains this solvent for monomer component, this is efficient and is preferred.
As above-mentioned solvent, such as can suitably enumerating following compound etc., can use one kind or two or more in them.
The single methanol classes such as methyl alcohol, ethanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol; The glycols such as ethylene glycol, propylene glycol; The ring-type such as tetrahydrofuran, dioxane ethers; The glycol monoethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, 3-methoxybutanol; The glycol ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl methyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether; The ester class of the glycol monoethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, DPE acetic acid esters, dipropylene glycol monobutyl ether acetic acid esters, 3-methoxy butyl acetate; The alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, methyl acetoacetate, ethyl acetoacetate; The ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; Benzene,toluene,xylene, ethylbenzene etc. are aromatic hydrocarbon based; The aliphatic hydrocarbons such as hexane, cyclohexane, octane; The amide-types such as dimethyl formamide, dimethyl acetamide, 1-METHYLPYRROLIDONE; Etc..
Among these solvents, from the dissolubility of resulting polymkeric substance, form surface smoothness while filming, on the impact of human body and environment less, the aspect of the easiness that obtains of industry, be more suitable for using propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diglycol ethyl methyl ether, ethyl lactate.
As the consumption of above-mentioned solvent, with respect to above-mentioned monomer component 100 mass parts, it is suitably 50 mass parts～1000 mass parts.100 mass parts～500 mass parts more preferably.
In the situation that utilizing radical polymerization mechanism to carry out polymerization to above-mentioned monomer component, use the polymerization initiator that produces free radical based on heat industrial favourable, be preferred.As such polymerization initiator, as long as produce free radical by heat supply and be just not particularly limited, can carry out suitable selection according to polymerization temperature or solvent, the polymerizing conditions such as kind that carry out the monomer of polymerization.In addition, also can share the reductive agents such as transition metal salt, amine together with polymerization initiator.
As above-mentioned polymerization initiator, can enumerate for example cumene hydroperoxide, di-isopropylbenzene hydroperoxide, di-tert-butyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butylperoxy isopropyl carbonate, peroxidating (2 ethyl hexanoic acid) tert-butyl ester, azoisobutyronitrile, 1, 1 '-azo two (cyclohexane formonitrile HCN), 2, 2 '-azo two (2, 4-methyl pentane nitrile), dimethyl 2, 2 '-azo two (2 Methylpropionic acid ester), hydrogen peroxide, the superoxide that persulfate etc. are used usually used as polymerization initiator, azo-compound etc., they can use separately, also can share two or more.
The consumption of above-mentioned polymerization initiator can take the circumstances into consideration to set according to molecular weight of the polymerizing conditions such as the kind of used monomer or amount, polymerization temperature, polymerization concentration, subject polymer etc., is not particularly limited.For example, in order to obtain weight-average molecular weight, be thousands of～tens thousand of polymkeric substance, with respect to above-mentioned monomer component 100 mass parts, this polymerization initiator is that 0.1 mass parts～20 mass parts is suitable.0.5 mass parts～15 mass parts more preferably.
In above-mentioned polymerization, also can use as required chain-transferring agent used conventionally.Preferably polymerization initiator and chain-transferring agent are share.It should be noted that, if use chain-transferring agent when polymerization, have the increase that can Inhibitory molecules amount distributes and the tendency of gelation.
As above-mentioned chain-transferring agent, can enumerate such as mercaptan carboxylic acid's classes such as mercaptoacetic acid, 3-mercaptopropionic acids; The mercapto-carboxylic ester classes such as methyl thioglycolate, 3-mercapto-propionate, 3-mercaptopropionic acid-2-Octyl Nitrite, 3-mercaptopropionic acid n-octyl, 3-mercaptopropionic acid methoxyl butyl ester, 3-mercaptopropionic acid stearyl ester, trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester); Ethanethio, tert-butyl mercaptan, n-dodecyl mercaptan, 1, the alkyl mercapto alcohols such as 2-dimercaptoethane; The sulfydryl alcohols such as 2 mercapto ethanol, 4-sulfydryl-n-butyl alcohol; Benzenethiol, a toluenethiol, to aromatic mercaptans classes such as toluenethiol, 2-naphthyl mercaptans; The sulfydryl isocyanuric acid ester classes such as three [(3-sulfydryl propionyloxy)-ethyl] isocyanuric acid ester (ト リ ス ((3-メ Le カ プ ト プ ロ ピ オ ニ ロ キ シ)-エ チ Le) イ ソ シ ア ヌ レ ー ト); The disulfides such as 2-hydroxyethyl disulfide, Thiuram disulfide; The dithiocarbamates such as benzyl DDC; The monomer dipolymer classes such as α-methylstyrenedimer; The alkyl halide base class such as carbon tetrabromide etc.They can use separately, also can share two or more.
Among these, from the viewpoint of acquired, anti-crosslinked ability, polymerization speed, reduce degree little etc., the compound that use mercaptan carboxylic acid class, mercapto-carboxylic ester class, alkyl thiol alcohols, sulfydryl alcohols, aromatic mercaptans class, sulfydryl isocyanuric acid ester class etc. have sulfydryl is suitable.More preferably alkyl thiol alcohols, mercaptan carboxylic acid's class, mercapto-carboxylic ester class, more preferably n-dodecyl mercaptan, mercaptopropionic acid.
The consumption of above-mentioned chain-transferring agent takes the circumstances into consideration to set according to molecular weight of the polymerizing conditions such as the kind of used monomer or amount, polymerization temperature, polymerization concentration, subject polymer etc., is not particularly limited.For example, in order to obtain weight-average molecular weight, be thousands of～tens thousand of polymkeric substance, with respect to above-mentioned monomer component 100 mass parts, the consumption of this chain-transferring agent is that 0.1 mass parts～20 mass parts is suitable.0.5 mass parts～15 quality % more preferably.
About above-mentioned polymerizing condition, as polymerization temperature, according to the kind of the kind of used monomer or amount, polymerization initiator or amount etc., take the circumstances into consideration to set, be for example preferably 50 ℃～150 ℃, more preferably 70 ℃～120 ℃.And, also can be similarly to polymerization time, take the circumstances into consideration to set, be for example preferably 1 hour～6 hours, more preferably 2 hours～5 hours.
Above-mentioned (methyl) acrylic ester polymer is to make to have to react in the situation of the polymkeric substance (also referred to as containing pendant double bonds polymkeric substance) that obtains with the functional group of acidic group bonding and the compound of the two keys of polymerism and base polymer (this base polymer obtains above-mentioned monomer component polymerization), as have can with the compound of the functional group of acidic group bonding and the two keys of polymerism, can use one kind or two or more.In such compound, as the two keys of polymerism, can enumerate such as (methyl) acryloyl group, vinyl, allyl, methylallyl etc., as this compound, there is one kind or two or more for suitable in the two keys of these polymerisms.Wherein, from the viewpoint of reactive, preferred (methyl) acryloyl group.In addition, as can with the functional group of acidic group bonding, can enumerate such as hydroxyl, epoxy radicals, oxetanyl, isocyanate group etc.; As this compound, there is one kind or two or more for suitable in these functional groups.Wherein, from the viewpoint of the speed of modification reaction, thermotolerance, dispersed, preferred epoxy radicals (comprising glycidyl).
As have can with the compound of the functional group of above-mentioned acidic group bonding and the two keys of polymerism, can enumerate for example (methyl) glycidyl acrylate, (methyl) senecioate-methyl ethylene oxidic ester, (methyl) senecioate-ethyl ethylene oxidic ester, vinyl benzyl glycidol ether, allyl glycidyl ether, (methyl) acrylic acid (3,4-epoxycyclohexyl) methyl esters, vinyl epoxy cyclohexane etc., can be used one kind or two or more in them.Wherein, be suitable for using the compound (monomer) with epoxy radicals and (methyl) acryloyl group.
As obtaining the above-mentioned method containing pendant double bonds polymkeric substance, can enumerate example as described below: make above-mentioned base polymer and having can react with the compound of the functional group of acidic group bonding and the two keys of polymerism time, acidic group (preferably carboxyl) amount that makes this base polymer than this have can with the method for the amount surplus of the functional group of acidic group bonding and the compound of polymerism pair keys; After making above-mentioned base polymer and having and can react with the compound of the functional group of acidic group bonding and the two keys of polymerism, further make to have the method that the compound of multi-anhydride base reacts; Etc..
Above-mentioned, make base polymer (preferably thering is carboxyl as the polymkeric substance of acidic group) and have in the operation that can react with the functional group of acidic group bonding and the compound of the two keys of polymerism, in order to ensure good reaction velocity and prevent gelation, preferably the temperature range of 50 ℃～160 ℃, carry out this operation.More preferably 70 ℃～140 ℃, more preferably 90 ℃～130 ℃ of this temperature.In addition, in order to improve reaction velocity, as catalyzer, can use normally used esterification or base catalyst, acidic catalyst for transesterification.Wherein, the reason reducing for subsidiary reaction, is preferably used base catalyst.
As above-mentioned base catalyst, can enumerate such as tertiary amines such as dimethyl benzyl amine, triethylamine, three n-octylamine, tetramethylethylenediamines; The quaternary ammonium salts such as tetramethyl ammonium chloride, 4 bromide, tetrabutyl ammonium bromide, dodecyl trimethyl ammonium chloride; The carbamide compounds such as tetramethylurea; The alkyl guanidines such as tetramethyl guanidine; The amide compound such as dimethyl formamide, dimethyl acetamide; The tertiary phosphine such as triphenylphosphine, tributylphosphine; The quaternary alkylphosphonium salts such as 4-phenyl phosphonium bromide, benzyl triphenyl phosphonium bromide; Etc., can use one kind or two or more in them.Wherein, from the viewpoint of reactivity, treatability, halogen-free etc., preferably dimethyl benzyl amine, triethylamine, tetramethylurea, triphenylphosphine.
With respect to above-mentioned monomer component with have can with total amount 100 mass parts of the compound of the functional group of acidic group bonding (such as epoxy radicals etc.) and polymerism pair keys, the consumption of above-mentioned catalyzer is preferably 0.01 mass parts～5.0 mass parts.0.1 mass parts～3.0 mass parts more preferably.
Above-mentionedly make base polymer and have in the operation that can react with the compound of the functional group of acidic group bonding and the two keys of polymerism, in order to prevent gelation, preferably add polymerization inhibitor and under the existence of the gas that contains molecularity oxygen, carry out this operation.As the gas that contains molecularity oxygen, conventionally use the air or oxygen after the inert gas dilutions such as nitrogen, be blown in reaction vessel.
As above-mentioned polymerization inhibitor, can use free radical polymerization monomer polymerization inhibitor used conventionally, for example can enumerate: quinhydrones, methylnaphthohydroquinone, trimethylhydroquinone, tertiary butylated hydroquinone, MEHQ, the 6-tert-butyl group-2,4-xylenols, 2,6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-4-metoxyphenol, 2, the phenol such as 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol) are polymerization inhibitor; Organic acid mantoquita, phenothiazine etc., can be used one kind or two or more in them.Wherein, from the viewpoint of less colored, ability that prevent polymerization etc., preferably phenol is polymerization inhibitor; For the easy reason of acquired, economy, more preferably 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), MEHQ, the 6-tert-butyl group-2,4-xylenols, 2,6-DI-tert-butylphenol compounds.
Consumption as above-mentioned polymerization inhibitor, the aspects such as curability when guaranteeing prevent fully the effect of polymerization and make hardening resin composition, with respect to above-mentioned monomer component with have can with total amount 100 mass parts of the compound of the functional group of acidic group bonding and the two keys of polymerism, the consumption of this polymerization inhibitor is preferably 0.001 mass parts～1.0 mass parts.0.01 mass parts～0.5 mass parts more preferably.
As the above-mentioned compound with multi-anhydride base, for example can enumerate, succinic anhydride, dodecenyl succinic succinic acid, 15 carbon alkenyl succinic acids, vaccenic acid base succinic acid, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, Nadic anhydride, methyl Nadic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic acid dianhydride etc., can use one kind or two or more in them.
The weight-average molecular weight of above-mentioned (methyl) acrylic ester polymer is 2000～250000th, suitable.Due to the scope in such, can give play to more good developability.This weight-average molecular weight more preferably 3000～100000, more preferably 4000～50000.It should be noted that, above-mentioned (methyl) acrylic ester polymer is for example, in the situation of high molecular (being 10000～50000), has and obtains the more tendency of the solidfied material of high rigidity; By control, be high acid value (more than being preferably 150mgKOH/g, below 200mgKOH/g), there is the tendency of easily developing.
The weight-average molecular weight of polymkeric substance for example can be tried to achieve as described later.
Above-mentioned (methyl) acrylic ester polymer is that two key equivalents are preferably 200～10000 in the situation that side chain has the polymkeric substance (containing pendant double bonds polymkeric substance) of two keys.Due to the scope in such, can make the storage stability of polymkeric substance more good.This pair of key equivalent more preferably 200～5000, more preferably 250～4000, be particularly preferably 300～4000.
So-called two key equivalent is the quality with respect to the solid constituent of the polymer solution (also referred to as resin solution) of the two keys of every 1mol polymkeric substance.The quality of constituent that the quality of the solid constituent of said polymer solution is above-mentioned monomer component herein and the total quality of the quality of polymerization inhibitor.By the two key amounts divided by polymkeric substance by the quality of the solid constituent of polymer solution, can try to achieve this pair of key equivalent.Two key amounts of polymkeric substance can by input acidic group with have can bonding functional group and the amount of the compound of the two keys of polymerism try to achieve.
In addition, hardening resin composition of the present invention for choosing freely this hardening resin composition further contain the mode of the polymkeric substance with hydroxyl and should (methyl) acrylic ester polymer further there is at least one mode in the group that the mode of hydroxyl forms.So by there is hydroxyl in system, by the above-mentioned structural unit that carrys out (methyl) acrylic ester monomer of self-contained tertiary carbon, decompose and produce (methyl) acrylic acid, between produced (methyl) acrylic acid, generate ester cross-linked structure, based on this reason, curability is especially high, can access the solidfied material that the transparency is excellent especially.It should be noted that, when above-mentioned hardening resin composition further contains the polymkeric substance with hydroxyl, above-mentioned (methyl) acrylic ester polymer also can further have hydroxyl.
The mode further as above-mentioned (methyl) acrylic ester polymer with hydroxyl, as mentioned above, can preferably enumerate: base polymer, this base polymer makes monomer component carry out polymerization and obtains, and this monomer component contains containing (methyl) acrylic ester monomer of tertiary carbon and has hydroxyl and the monomer of the two keys of polymerism, preferably further contain the monomer with acidic group and the two keys of polymerism; Containing pendant double bonds polymkeric substance, should make this base polymer and have and can react and obtain with the functional group of acidic group bonding and the compound of the two keys of polymerism containing pendant double bonds polymkeric substance.Wherein preferably the latter containing pendant double bonds polymkeric substance.
< has the polymkeric substance > of hydroxyl
Above-mentioned hardening resin composition above-mentioned except containing (methyl) acrylic ester polymer, also further contain in the situation of the polymkeric substance with hydroxyl, as this, there is the polymkeric substance of hydroxyl, as long as there is hydroxyl in molecule, be just not particularly limited.Wherein, from the viewpoint of further raising developability, be preferably and demonstrate alkali-soluble polymkeric substance, be suitably the polymkeric substance in molecule with acidic group.About acidic group, as in above-mentioned (methyl) acrylic ester polymer as mentioned above; About the above-mentioned acid number with the polymkeric substance of hydroxyl, be also preferably in the above-mentioned optimum range in above-mentioned (methyl) acrylic ester polymer.
As the above-mentioned polymkeric substance with hydroxyl, preferably for example can enumerate: base polymer, this base polymer makes the monomer that contains hydroxyl and the two keys of polymerism, the preferred monomer component that further contains the monomer with acidic group and the two keys of polymerism carry out polymerization and obtain; Containing pendant double bonds polymkeric substance, should make this base polymer and have and can react and obtain with the functional group of acidic group bonding and the compound of the two keys of polymerism containing pendant double bonds polymkeric substance.Wherein preferably the latter containing pendant double bonds polymkeric substance.
So, above-mentioned (methyl) acrylic ester polymer and/or the polymkeric substance with hydroxyl are included in suitable way of the present invention for have the mode of the polymkeric substance of the two keys of polymerism at side chain.
In above-mentioned formation, have in the monomer component of polymkeric substance of hydroxyl, there is the monomer of the two keys of hydroxyl and polymerism and there is acidic group and the optimal way of the monomer of the two keys of polymerism, concrete example etc. as mentioned above, each monomer can be used respectively one kind or two or more.
For the above-mentioned monomer with the two keys of hydroxyl and polymerism containing proportional, for example, with respect to above-mentioned formation, there are the total amount 100 quality % of monomer component of the polymkeric substance of hydroxyl, should containing proportional be preferably 1 quality % more than.More preferably 5 quality % above, more preferably more than 10 quality %.And be preferably 90 quality % following, more preferably 50 quality % following, more preferably below 25 quality %.
The above-mentioned monomer with the two keys of acidic group and polymerism containing proportional, be suitablely set as making acid number in above-mentioned preferred scope, for example, the total amount 100 quality % of monomer component with respect to above-mentioned formation with the polymkeric substance of hydroxyl, have the two keys of acidic group and polymerism monomer containing proportional be preferably 5 quality % more than.More preferably 10 quality % above, more preferably more than 20 quality %.And be preferably 99 quality % following, more preferably 85 quality % following, more preferably 60 quality % following, be particularly preferably below 50 quality %.
Form in the monomer component of the above-mentioned polymkeric substance with hydroxyl, except above-mentioned monomer, can also contain the monomer that other can copolymerization.As other monomer, the suitable use for example N substituted maleimide amine except above-mentioned monomer is monomer, dialkyl group-2, and 2 '-(oxygen base dimethylene) diacrylate is one kind or two or more in monomer, alkyl-(α-allyloxy methyl) acrylic ester monomer, (methyl) acrylic ester monomer, aromatic vinyl base system monomer etc.Their suitable way and concrete example are like above-mentioned.
It should be noted that, in the total amount 100 quality % of monomer component that form the above-mentioned polymkeric substance with hydroxyl, other monomer containing proportional be preferably 60 quality % following, be preferably below 50 quality %.Particularly in the situation that containing N substituted maleimide amine and being monomer, from aspects such as thermotolerance, hardness, colorant dispersiveness, developing powder, the transparencys, it is containing proportional 2 quality %～60 quality %, more preferably 2 quality %～50 quality %, the 3 quality %～40 quality % more preferably of being preferably.
About the polymerization of above-mentioned monomer component, make to have the method that can react with the base polymer that the functional group of acidic group bonding and the compound of the two keys of polymerism obtain with above-mentioned monomer component is carried out to polymerization as above-mentioned.
In above-mentioned hardening resin composition, (methyl) acrylic ester polymer and have hydroxyl polymkeric substance containing proportional, can take the circumstances into consideration to set according to the mixing of purposes or other composition etc., for example, solid constituent total amount 100 quality % with respect to hardening resin composition, their total solid component content (in the situation that do not contain the polymkeric substance with hydroxyl, only means the solid component content of (methyl) acrylic ester polymer.) be preferably 5 quality % more than.And be suitably below 80 quality %.By the scope in such, can give play to more significantly effect of the present invention.This content is 7 quality %～70 quality %, 10 quality %～60 quality % more preferably more preferably.
It should be noted that, so-called " solid constituent total amount " refers to the total amount of the composition (except the solvent volatilizing during the formation of solidfied material etc.) that forms solidfied material.
Herein, in the situation that contain above-mentioned (methyl) acrylic ester polymer with have hydroxyl polymkeric substance the two, about their mixing ratio, as long as produce hydroxyl in (methyl) acrylic acid and system according to the thermal decomposition of the structural unit of (methyl) acrylic ester monomer of the self-contained tertiary carbon of origin, easily there is the crosslinked mode of ester its mixing ratio is set, be not particularly limited.For example, their mass ratio ((methyl) acrylic ester polymer/have the polymkeric substance of hydroxyl)=1～99/99～1 is for suitable.More preferably 10～90/90～10.
< polymerizable compound >
Above-mentioned hardening resin composition also contains polymerizable compound.So-called polymerizable compound is also referred to as polymerizable monomer, be can be by free radical, electromagnetic wave (such as infrared ray, ultraviolet ray, X ray etc.), electron ray isoreactivity energy line irradiation etc. there is low molecular compound polymerization, that there is polymerism unsaturated link (also referred to as polymerism unsaturated group).For example can enumerate the polyfunctional compound who there is the monofunctional compound of 1 polymerism unsaturated group and there is more than 2 polymerism unsaturated group in molecule.
As above-mentioned simple function polymerizable monomer, for example can enumerate N substituted maleimide amine or (methyl) esters of acrylic acid among the compound exemplifying as other monomer preferably containing in the monomer component of above-mentioned (methyl) acrylic ester polymer; (methyl) acrylic amide; Unsaturated monocarboxylic class; Unsaturated polybasic carboxylic acid class; Between unsaturated group and carboxyl, there is the unsaturated monocarboxylic class of chain extension; Unsaturated acid anhydride class; Aromatic vinyl base class; Conjugated diene; Vinyl ester; Vinyl ethers; N-vinyl compound class; Unsaturated isocyanate class; Etc..
As above-mentioned multifunctional polymerization monomer, can enumerate such as following compound etc.
2 officials' energy (methyl) acrylate compounds such as ethylene glycol bisthioglycolate (methyl) acrylate, diglycol two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, hexanediol two (methyl) acrylate, cyclohexanedimethanol two (methyl) acrylate, bisphenol-A epoxy alkane two (methyl) acrylate, Bisphenol F epoxyalkane two (methyl) acrylate;
Trimethylolpropane tris (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, glycerine three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, ethylene oxide addition trimethylolpropane tris (methyl) acrylate, ethylene oxide addition double trimethylolpropane four (methyl) acrylate, ethylene oxide addition pentaerythrite four (methyl) acrylate, ethylene oxide addition dipentaerythritol six (methyl) acrylate, propylene oxide addition trimethylolpropane tris (methyl) acrylate, propylene oxide addition double trimethylolpropane four (methyl) acrylate, propylene oxide addition pentaerythrite four (methyl) acrylate, propylene oxide addition dipentaerythritol six (methyl) acrylate, 6-caprolactone addition trimethylolpropane tris (methyl) acrylate, 6-caprolactone addition double trimethylolpropane four (methyl) acrylate, 6-caprolactone addition pentaerythrite four (methyl) acrylate, 3 officials such as 6-caprolactone addition dipentaerythritol six (methyl) acrylate can be above multifunctional (methyl) acrylate compounds,
Ethylene glycol bisthioglycolate vinyl ether, diethylene glycol divinyl ether, polyglycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol-A epoxy alkane divinyl ether, Bisphenol F epoxyalkane divinyl ether, trimethylolpropane tris vinyl ether, double trimethylolpropane tetrem alkene ether, glycerine trivinyl ether, pentaerythrite tetrem alkene ether, dipentaerythritol five vinyl ether, dipentaerythritol six vinyl ether, ethylene oxide addition trimethylolpropane tris vinyl ether, ethylene oxide addition double trimethylolpropane tetrem alkene ether, ethylene oxide addition pentaerythrite tetrem alkene ether, the polyfunctional vinyl ethers such as ethylene oxide addition dipentaerythritol six vinyl ether,
(methyl) acrylic acid-2-ethyleneoxy ethyl ester, (methyl) acrylic acid-3-ethyleneoxy propyl ester, (methyl) acrylic acid-1-methyl-2-ethyleneoxy ethyl ester, (methyl) acrylic acid-2-ethyleneoxy propyl ester, (methyl) acrylic acid-4-ethyleneoxy butyl ester, (methyl) acrylic acid-4-ethyleneoxy cyclohexyl, (methyl) acrylic acid-5-ethyleneoxy pentyl ester, the own ester of (methyl) acrylic acid-6-ethyleneoxy, (methyl) acrylic acid-4-ethyleneoxy methylcyclohexyl methyl esters, (methyl) acrylic acid is to ethyleneoxy aminomethyl phenyl methyl esters, (methyl) acrylic acid-2-(ethyleneoxy ethoxy) ethyl ester, (methyl) esters of acrylic acid that (methyl) acrylic acid-2-(ethyleneoxy ethoxy ethoxy ethoxy) ethyl ester etc. contains vinyl ether group,
Ethylene glycol bisthioglycolate allyl ether, diglycol diallyl ether, polyglycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol-A epoxy alkane diallyl ether, Bisphenol F epoxyalkane diallyl ether, trimethylolpropane tris allyl ether, double trimethylolpropane tetraallyl ether, glycerine triallyl ether, pentae-rythritol tetraallyl ether, dipentaerythritol pentaene propyl ether, dipentaerythritol six allyl ethers, ethylene oxide addition trimethylolpropane tris allyl ether, ethylene oxide addition double trimethylolpropane tetraallyl ether, ethylene oxide addition pentae-rythritol tetraallyl ether, the multifunctional allyl ether series such as ethylene oxide addition dipentaerythritol six allyl ethers,
(methyl) allyl acrylate etc. contains allylic (methyl) esters of acrylic acid;
The isocyanuric acid ester class that three (acryloxy ethyl) isocyanuric acid ester, three (methacryloxyethyl) isocyanuric acid esters, epoxyalkane addition three (acryloxy ethyl) isocyanuric acid ester, epoxyalkane addition three (methacryloxyethyl) isocyanuric acid ester etc. contain multifunctional (methyl) acryloyl group;
Cyanacrylates etc. contain multifunctional allylic isocyanuric acid ester class;
(methyl) esters of acrylic acid by the polyfunctional isocyanates such as toluene diisocyanate, isophorone diisocyanate, XDI and the hydroxyls such as (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate react polyfunctional carbamate (methyl) esters of acrylic acid obtaining;
The multifunctional aromatic vinyl base class such as divinylbenzene; Deng.
In above-mentioned polymerizable compound, from the viewpoint of the curability of further raising hardening resin composition of the present invention, be suitable for using multifunctional polymerization compound.As polymerizable compound, use in the situation of multifunctional polymerization compound, as its functional number be preferably more than 3, more preferably more than 4, more preferably more than 5.In addition, from the viewpoint of further inhibition cure shrinkage, functional number is preferably below 10, more preferably below 8.
In addition, as the molecular weight of above-mentioned polymerizable compound, be not particularly limited, the aspect from processing, for example, be suitably below 2000.
As above-mentioned polymerizable compound, use in the situation of multifunctional polymerization compound; in this polymerizable compound; from reactivity, economy, the aspect such as acquired, isocyanurate compound that be suitable for using multifunctional (methyl) acrylate compounds, polyfunctional carbamate (methyl) acrylate compounds, contains (methyl) acryloyl group etc. has the compound of (methyl) acryloyl group.More preferably multifunctional (methyl) acrylate compounds, can make the photonasty of hardening resin composition and curability more excellent thus, can obtain further having the more solidfied material of the high transparent of high rigidity.Further preferably use multifunctional (methyl) acrylate compounds that 3 officials can be above.
Proportional as containing of above-mentioned polymerizable compound, can take the circumstances into consideration to set according to kind and object or the purposes etc. of used polymerizable compound or above-mentioned (methyl) acrylic ester polymer, more excellent from the viewpoint of developability, plate-making property, solid constituent total amount 100 quality % with respect to hardening resin composition, should containing proportional be preferably 2 quality % more than, and be suitably below 80 quality %.As lower limit more preferably 5 quality % above, more preferably 8 quality % above, be particularly preferably 10 quality % more than, as higher limit more preferably 70 quality % following, more preferably 50 quality % following, be particularly preferably 30 quality % following, most preferably be below 20 quality %.
< Photoepolymerizationinitiater initiater >
Above-mentioned hardening resin composition further contains Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, be preferably free-radical polymerised Photoepolymerizationinitiater initiater.The Photoepolymerizationinitiater initiater of liberty base polymerism, for the irradiation by electromagnetic wave or electron ray isoreactivity energy line produces the material that polymerization causes free radical, can be used one kind or two or more material used conventionally.In addition, also can share as required one kind or two or more photosensitizer or optical free radical polymerization accelerant etc.Photosensitizer and/or optical free radical polymerization accelerant can be used together with Photoepolymerizationinitiater initiater, also can not use photosensitizer and/or optical free radical polymerization accelerant.Even if inadequacy photosensitizer and/or optical free radical polymerization accelerant also can give full play of the effect of the present application, in the situation that share, can further improve sensitivity, curability.
As above-mentioned Photoepolymerizationinitiater initiater, specifically, can enumerate routine compound described as follows etc.
2, 2-diethoxy acetophenone, 2, 2-dimethoxy-2-phenyl acetophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl propiono) benzyl] phenyl }-2-methylpropane-1-ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propyl group 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-alkyl phenones the based compounds such as 1-butanone, benzophenone, 4, the benzophenone based compounds such as 4 '-bis-(dimethylamino) benzophenone, 2-carboxyl benzophenone, the benzoin based compounds such as benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, thioxanthones, 2-ethyl thioxanthones, ITX, CTX, 2,4-dimethyl thioxanthones, 2, the thioxanthones based compounds such as 4-diethyl thioxanthone,
2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-ethoxy naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-ethoxy carbonyl naphthyl)-4, the halomethylation triazine based compounds such as two (the trichloromethyl)-s-triazines of 6-; 2-trichloromethyl-5-(2 '-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2 '-benzofuranyl) vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1, the halogen Jia Jiization oxadiazole based compounds such as 3,4-oxadiazole; 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1, the bisglyoxaline based compounds such as 2 '-bisglyoxaline; 1,2-octane diketone, 1-[4-(thiophenyl)-, 2-(O-benzoyl oximes)], ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-, the oxime ester based compounds such as 1-(O-acetyl group oxime); The cyclopentadiene titanium sub-group compounds such as two (η 5-2,4-cyclopentadiene-1-yls)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-yl)-phenyl) titanium; P-(dimethylamino)-benzoic acid, to benzoic ether based compounds such as diethyl amino yl benzoic acids; The acridine based compounds such as 9-phenylacridine etc.
As photosensitizer or the optical free radical polymerization accelerant that can share with above-mentioned Photoepolymerizationinitiater initiater, for example can enumerate: xanthene pigment, cumarin pigment, 3-ketone coumarin series compounds, pyrroles's methine pigment isochrome prime system compound; The dialkyl amido benzene compounds such as 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid-2-Octyl Nitrite; The mercaptan such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole are hydrogen donor etc.
The content of above-mentioned Photoepolymerizationinitiater initiater can take the circumstances into consideration to set according to object, purposes etc., is not particularly limited; With respect to solid constituent total amount 100 mass parts of the hardening resin composition except Photoepolymerizationinitiater initiater, more than this content is suitably 0.1 mass parts.Thus, can obtain the solidfied material that adaptation is more excellent, even also can suppress more fully to peel off after high temperature exposure.In addition, the impact that the analyte of Photoepolymerizationinitiater initiater brings if consider and with the balance of economy etc., this content is preferably below 30 mass parts.As lower limit more preferably 0.5 mass parts above, more preferably 1 mass parts above, be particularly preferably 2 mass parts more than, as higher limit more preferably 25 mass parts following, more preferably below 20 mass parts.
Above-mentioned photosensitizer and optical free radical polymerization accelerant can not used as mentioned above, in the situation that using, the aspect of the impact bringing from curability, analyte and the balance of economy, with respect to the solid constituent total amount 100 quality % of hardening resin composition, this content is preferably 0.001 quality %～20 quality %.More preferably 0.01～15 quality %, 0.05～10 quality % more preferably.
Other composition of < >
-solvent-
In addition, above-mentioned hardening resin composition is suitable for containing solvent.Solvent is as preferably uses such as thinning agents.That is, specifically, dissolving is suitably used for following object: reduce viscosity, improve treatability; By dry formation, film; Become the dispersion medium of colorant; Etc., its be solubilized or disperse each composition contained in hardening resin composition, low viscous organic solvent or water.
As above-mentioned solvent, can use normally used solvent, can, according to object, the suitable selection of purposes, be not particularly limited, such as enumerating following compound etc.These solvents can be used separately, also can share two or more.
The single methanol classes such as methyl alcohol, ethanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol; The glycols such as ethylene glycol, propylene glycol; The ring-type such as tetrahydrofuran, dioxane ethers; The glycol monoethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, 3-methoxybutanol; The glycol ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl methyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether;
The ester class of the glycol monoethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, DPE acetic acid esters, dipropylene glycol monobutyl ether acetic acid esters, 3-methoxy butyl acetate; The alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, methyl acetoacetate, ethyl acetoacetate; The ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; Benzene,toluene,xylene, ethylbenzene etc. are aromatic hydrocarbon based; The aliphatic hydrocarbons such as hexane, cyclohexane, octane; The amide-types such as dimethyl formamide, dimethyl acetamide, 1-METHYLPYRROLIDONE; Water; Etc..
As the consumption of above-mentioned solvent, can take the circumstances into consideration to set according to object, purposes, be not particularly limited, in the total amount 100 quality % of hardening resin composition of the present invention, preferably making its content is 10 quality %～90 quality %.20 quality %～80 quality % more preferably.
In above-mentioned hardening resin composition, according to the desired characteristic of its applied each purposes, can also further contain one kind or two or more in following substances for example: colorant (also referred to as colorant); Spreading agent; Heat-resisting improving agent; Levelling agent; Development promoter; The inorganic particles such as silicon dioxide microparticle; The coupling agents such as silane system, aluminium system, titanium system; The thermoset resins such as filler, epoxy resin, phenol resin, polyvinylphenol; The auxiliary curing agents such as multi-functional thiol's compound; Plastifier; Polymerization inhibitor; Ultraviolet light absorber; Antioxidant; Deluster; Defoamer; Antistatic agent; Antiseize paste; Surface modifier; Thixotropic agent; Thixotroping auxiliary agent; Quinone di-azido compound; Polyhydric phenols; Cationically polymerizable compound; Acid agent; Etc..For example, above-mentioned hardening resin composition, in the situation of color filter purposes, is preferably contained to colorant.So, the mode that above-mentioned hardening resin composition further contains colorant is also one of suitable way of the present invention.Be suitably in addition at least one the mode of selecting in the group that free colorant, spreading agent, heat-resisting improving agent, levelling agent, coupling agent and development promoter form that contains.These being contained to composition below describes.
-colorant-
As above-mentioned colorant, can suitably use for example pigment, dyestuff.They can use separately, also two or more can be used in combination.In addition, can be by pigment and dye combinations.For example, in the situation that form redness, blueness, the green pixel of color filter, be suitable for using the method that Lan Yuzi, the colorant such as green and yellow is combined to have given play to desired chromatic characteristic.In addition, in the situation that forming black matrix layer, also can form with black material.
In above-mentioned pigment and dyestuff, from the viewpoint of for example permanance, pigment (for example organic pigment or inorganic pigment) is excellent; In addition, from the viewpoint of the brightness such as improving panel etc., dyestuff is excellence, thereby can they suitably be selected or be share according to desired characteristic.It should be noted that more preferably organic pigment in pigment.
As above-mentioned pigment, can enumerate such as organic pigments such as azo pigment, phthualocyanine pigment, polycycle pigment (such as quinacridone, perylene system, purple cyclic ketones system, isoindolinone system, isoindoline system, dioxazine system, thioindigo system, anthraquinone system, quinophthalone system, metal complex system, diketopyrrolopyrrolecocrystals system etc.), dyestuff color lake series pigments, white non-opaque pigment (titania for example, zinc paste, zinc sulphide, clay, talcum, barium sulphate, calcium carbonate etc.), color pigment (chrome yellow for example, cadmium system, chrome vermilion, NiTi, chromium titanium, yellow iron oxide, iron oxide red, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, pucherite etc.), black pigment (carbon black for example, bone black, graphite, iron black, titanium is black etc.), light material pigment (pearl pigment for example, aluminium pigment, bronze pigments etc.), fluorescent pigment (zinc sulphide for example, strontium sulfide, strontium aluminate etc.) inorganic pigment such as.In addition,, as the color of spendable pigment, can enumerate yellow, redness, purple, blueness, green, brown, black, white etc.
Above-mentioned pigment also can carry out according to object, purposes the surface treatments such as rosin processing, surfactant processing, the processing of resin system spreading agent, pigment derivative processing, oxide film thereon processing, silica-coating, wax coating.
Following color separation is by color index (C.I.; The Society of Dyers and Colourists distribution) numbering illustrates the concrete example of above-mentioned pigment, but colorant of the present invention is not limited in these.In addition, they can use separately, also can be used in combination of two or more." C.I. " below means that color index, numeral mean color index numbering.
As yellow uitramarine, can enumerate for example C.I. pigment yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 49, 53, 55, 60, 61, 61:1, 62, 62:1, 63, 65, 71, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 123, 124, 126, 127, 127:1, 128, 129, 130, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170.172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 209, 209:1, 212, 213, 214, 215, 219 etc.
As orange pigment, can enumerate such as C.I. pigment orange 1,2,3,4,5,13,15,16,17,19,20,21,22,23,24,31,34,36,38,39,40,43,46,48,49,51,60,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78,79,81 etc.
As violet pigment, can enumerate such as C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,13,14,15,16,17,19,23,25,27,29,31,32,36,37,38,39,42,44,47,49,50 etc.
As red pigment, can enumerate for example C.I. paratonere 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 37, 38, 40, 41, 42, 47, 48, 48:1, 48:2, 48:3, 48:4, 48:5, 49, 49:1, 49:2, 50:1, 52, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 54, 57, 57:1, 57:2, 58, 58:2, 58:4, 60, 60:1, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 89, 90:1, 95, 97, 101, 101:1, 102, 104, 105, 106, 108, 108:1, 109, 112, 113, 114, 122, 123, 136, 144, 146, 147, 149, 150, 151, 164, 166, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 215, 216, 220, 221, 224, 226, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 248, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 279 etc.
As blue pigment, can enumerate such as C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:5,15:6,16,17,17:1,19,24,24:1,25,26,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78,79,80 etc.
As viridine green, can enumerate such as C.I. naphthol green 1,2,4,7,8,10,13,15,17,18,19,26,36,45,48,50,51,54,55,58 etc.
As brown pigments, can enumerate such as C.I. pigment brown 5,6,23,24,25,32,41,42 etc.
As black pigment, can enumerate, C.I. pigment black 1,6,7,9,10,11,12,13,20,31,32,34 black such as nigrosine, carbon black, dim, bone black, iron oxide black, titanium etc.As Chinese white, can enumerate such as C.I. Pigment white 1,2,4,5,6,7,11,12,18,19,21,22,23,26,27,28 etc.
As above-mentioned dyestuff, can use the organic dyestuff of recording in for example TOHKEMY 2010-9033 communique, TOHKEMY 2010-211198 communique, TOHKEMY 2009-51896 communique, TOHKEMY 2008-50599 communique.Wherein preferably azo based dye, anthraquinone based dye, phthalocyanine based dye, quinone imines based dye, quinoline based dye, nitro based dye, carbonyl based dye, methine based dye etc.
Can setting as one sees fit according to object, purposes containing proportional (being the total ratio of pigment and dyestuff) of above-mentioned colorant, with respect to the solid constituent total amount 100 quality % of hardening resin composition, this colorant containing proportional preferable range be 3 quality %～70 quality %.More preferably 5 quality %～60 quality %, 10 quality %～50 quality % more preferably.
-spreading agent-
Above-mentioned spreading agent have with the interactional position of colorant and with the interactional position of dispersion medium (for example solvent or resin glue), there is the effect that makes the decentralized stabilization of colorant in dispersion medium, be conventionally classified as resin type spreading agent (for example macromolecule dispersing agent), surfactant (for example low dispersal agent molecule), pigment derivative.The suitable spreading agent that contains together with colorant of hardening resin composition of the present invention.It should be noted that, as spreading agent (being resin type spreading agent, surfactant and/or pigment derivative), can use normally used spreading agent.In addition, as spreading agent, can be used singly or in combination of two or more.
As above-mentioned resin type spreading agent, can enumerate such as multi-carboxylates such as polyurethane, polyacrylate; Unsaturated polyester acid amides, polybasic carboxylic acid, polybasic carboxylic acid amine salt, polybasic carboxylic acid ammonium salt, polybasic carboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, the multi-carboxylate of containing hydrogen base; By poly-(rudimentary alkyleneimines) with have free carboxy polyester react acid amides or its salt forming; (methyl) acrylic acid-styrol copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyester system, modified polyacrylate, oxirane/polypropyleneoxide addition product etc.
In addition, structure as above-mentioned resin type spreading agent, particularly preferably use the Grafting Structure resin of (if main chain is that to have anchor chain, grafted chain with the interactional position of colorant be the compatibility chain having with the interaction of dispersion medium), or anchor chain and compatibility chain form the resin of block structure.
If enumerate the trade name of above-mentioned resin type spreading agent, for example can enumerate following material.Wherein be not limited to these.
EFKA-46, 47, 48, 745, 1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4540, 4550, 6750, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN470, 472, 480, 482, K-SPERSE131, 1525070, 5207 (being manufactured by EFKA ADDITIVES society above), Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205, Anti-Terra-P, Disperbyk-101,102,103,106,108,109,110,111,112,151,160,161,162,163,164,166,182, P-104, P-104S, P105,220S, 203,204,205,2000,2001,9075,9076,9077 (by Bi Ke chemistry society, being manufactured above), SOLSPERSE3000,5000,9000,12000,13240,13940,17000,20000,22000,24000,24000GR, 26000,28000 (by Japanese Lu Borun society, being manufactured above), Disperlon7301,325,374,234,1220,2100,2200, KS260, KS273N, 152MS (by nanmu, originally changing into society above manufactures), AJISPER PB-711,821,822,880, PN-411, PA-111 (being manufactured by AJINOMOTO FINE TECHNO society above), KP series (manufacture of chemical industry society of SHIN-ETSU HANTOTAI), POLYFLOW series (chemistry society of common prosperity society manufactures), MEGAFACE series (manufacture of DIC society), Dispersion Aid (デ ィ ス パ ー エ イ De) series (manufacture of SAN NOPCO society), etc..
As above-mentioned surfactant, can enumerate such as anionic surface active agent such as polyoxyethylene alkyl ether sulfate salt, neopelex, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, odium stearate, NaLSs; The non-ionics such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl ether, Tween-60, polyethylene glycol monolaurate; Alkyl quaternary ammonium salts or their cationic surfactants such as ethylene oxide adduct; The amphoteric surfactantes such as the alkyl betaines such as alkyl-dimethyl oxyneurine, alkyl imidazoline; Etc..
Above-mentioned pigment derivative, for imported the compound of the structure of functional group in pigment, as functional group, can be enumerated such as sulfonic group, sulfoamido and quaternary salt thereof, dialkyl amido, hydroxyl, carboxyl, amide group, phthalimide-based etc.As the pigment structure that becomes parent, can enumerate such as azo system, anthraquinone system, quinophthalone system, phthalocyanine system, quinacridone, benzimidazolone system, isoindoline system, dioxazine system, indanthrene system, perylene system, diketopyrrolopyrrolecocrystals system etc.
Can setting as one sees fit according to object or purposes containing proportional of above-mentioned spreading agent (being resin type spreading agent, surfactant and/or pigment derivative), aspect from dispersion stabilization, permanance (thermotolerance, photostability, weatherability etc.) and transparent balance, with respect to the solid constituent total amount 100 quality % of hardening resin composition, should be containing the proportional 0.01 quality %～60 quality % that is for example preferably.More preferably 0.1 quality %～50 quality %, 0.3 quality %～40 quality % more preferably.
-heat-resisting improving agent-
Above-mentioned heat-resisting improving agent is used in order to improve thermotolerance or intensity.As heat-resisting improving agent, such as N-(alkoxy methyl) melamine compound, there are 2 above epoxy radicals or the compound of oxetanyl etc. for suitable.Particularly, using above-mentioned hardening resin composition as resist for light spacer, transparent resist, interlayer dielectric are used with resist for diaphragm in the situation that, preferably use them.
-levelling agent-
Above-mentioned levelling agent is preferably used in order to improve levelability.As levelling agent, preferably fluorine system, silicon are surfactant.
-coupling agent-
Above-mentioned coupling agent is preferably used in order to improve adaptation.As coupling agent, preferred silane is coupling agent, and can enumerate for example epoxy system, metha crylic, amino is silane coupling agent.Wherein preferably epoxy is silane coupling agent.
-development promoter-
Above-mentioned development promoter is preferably used in order to improve developability.As development promoter, such as following substances, be suitable: the monocarboxylic acid classes such as (methyl) acrylic acid, acetic acid, propionic acid; The polybasic carboxylic acid classes such as maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid, trimellitic acid; The carboxyanhydrides such as maleic anhydride, succinic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride; Etc..
Manufacture method as above-mentioned hardening resin composition is not particularly limited, for example can be by the above-mentioned composition that contains being mixed and disperses to be prepared with various mixers or dispersion machine.Mix dispersion step and be not particularly limited, utilize usual way.In addition also can further comprise other operation of conventionally carrying out.It should be noted that, in the situation that above-mentioned hardening resin composition contains colorant, the suitable dispersion treatment operation through colorant is manufactured.
Dispersion treatment operation as above-mentioned colorant, can enumerate example as described below: the colorant (preferably organic pigment), spreading agent and the solvent that weigh first respectively specified quantitative, use the dispersion machines such as paint mixing unit (Paint Conditioner), ball mill, edge runner, bowl mill, jet pulverizer, homogenizer, kneader, stirring machine that colorant differential is loose, make liquid colorant dispersion liquid (also referred to as millbase).Preferably utilize edge runner, kneader, stirring machine etc. to carry out mixing dispersion treatment, utilize afterwards the medium grinding machines such as ball mill that are filled with 0.01mm～1mm mill pearl to carry out micro-dispersion treatment.In resulting millbase, add composition (preferably clear liquid) that be uniformly mixed in advance, that contain (methyl) acrylic ester polymer, polymerizable monomer and Photoepolymerizationinitiater initiater and solvent if desired or levelling agent etc. in addition, mix, make uniform dispersion soln, can obtain hardening resin composition.
In addition, resulting hardening resin composition preferably utilizes filtrator etc. to carry out filtration treatment, removes fine dust.
[solidfied material]
As mentioned above, hardening resin composition of the present invention can provide photonasty and the curability solidfied material of the key property excellence such as excellence, developability, solvent resistance, the adaptation with substrate (base material), thermotolerance and the transparency especially.The imaging of such solidfied material and surface smoothness are also excellent, such as there is no the residue of unexposed portion or scum silica frost etc. after development.Like this above-mentioned hardening resin composition is solidified to the solidfied material form is also one of the present invention.
The thickness (thickness) of above-mentioned solidfied material (cured film) is that 0.1 μ m～20 μ m is suitable.Thus, can fully tackle dwarf forms (the low back of the body) requirement of the parts etc., display device etc. that use above-mentioned solidfied material.More preferably 0.5 μ m～10 μ m, 0.5 μ m～8 μ m more preferably.
In the purposes such as various opticses such as the color filter that can use in liquid crystal indicator, solid state image sensor etc., ink, galley, printed circuit board (PCB), semiconductor element, photoresist of above-mentioned solidfied material or motor electronics, preferably use.Wherein be preferred for color filter.Using in this wise the color filter that above-mentioned hardening resin composition forms, the color filter specifically on substrate with above-mentioned solidfied material is also one of the present invention.Further color filter is described below.
< color filter >
Color filter of the present invention consists of the mode on substrate with above-mentioned solidfied material.
In above-mentioned color filter; the suitable especially conduct of the solidfied material being formed by hardening resin composition of the present invention maybe needs to carry out the painted sections (セ グ メ Application ト) of each pixel such as redness, green, blueness, yellow such as black matrix, but control as light spacer, protective seam, orientation, with timber (the hired リ Block of orientation system) etc., not necessarily to need painted sections be also suitable.
As the substrate using in above-mentioned color filter, can enumerate glass substrates such as: blank glass, blue or green glass sheet, alkaline reinforcing glass, the blue or green glass sheet of silica-coating; The sheet material, film material or the substrate that by thermoplastic resins such as the ring-opening polymerization polymer of polyester, polycarbonate, polyolefin, polysulfones, cyclic olefin or its hydride, are formed; The sheet material being formed by thermoset resins such as epoxy resin, unsaturated polyester resins, film material or substrate; The metal substrates such as aluminium sheet, copper coin, nickel plate, corrosion resistant plate; Ceramic substrate; The semiconductor substrate with photo-electric conversion element; The parts that glass substrate (such as LCD color filter) that possesses colorant layer on surface etc. consists of various materials; Etc..Wherein, from the viewpoint of stable on heating, preferred glass substrate, the sheet material being formed by heat-resistant resin, film material or substrate.In addition, aforesaid substrate is suitably transparency carrier.
In addition, on above-mentioned base material, can carry out as required Corona discharge Treatment, ozone treatment, the chemicals processing based on silane coupling agent etc. etc.
The manufacture method > of < color filter
In order to obtain above-mentioned color filter, it is suitable for example adopting following manufacture method,, adopts the method that comprises following operation: the operation (also referred to as arrangement step) that configures above-mentioned hardening resin composition on substrate for each color pixel that is; The operation (also referred to as irradiation operation) of irradiating light for the hardening resin composition being configured on this substrate; Utilize developer solution to carry out the operation (also referred to as developing procedure) of development treatment; And the operation (also referred to as heating process) of carrying out heat treated, to of all kinds, repeatedly carry out the method identical with it.It should be noted that, the formation of each color pixel is sequentially not particularly limited.
-arrangement step (preferably painting process)-
Above-mentioned arrangement step is applicable to by coating.As the method that is coated with above-mentioned hardening resin composition on substrate, can enumerate such as rotary coating, slot coated, roller coat cloth, curtain coating coating etc., either method all can preferably be used.
In addition, in above-mentioned arrangement step, after above-mentioned hardening resin composition is coated on substrate, suitable to dried coating film.Being dried of filming can be used such as heating plate, IR baking oven, convection oven etc. to carry out.Drying condition can be according to next suitable selections such as the performances of the kind of the boiling point of contained solvent composition, cure component, thickness, dryer, and it is suitable conventionally at the temperature of 50 ℃～160 ℃, carrying out 10 seconds～300 seconds.
-irradiation operation-
In above-mentioned irradiation operation, as the light source of used active ray, can use such as lamp source such as xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lights; The lasing light emitters such as Argon ion laser, YAG laser instrument, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser etc.In addition, as the mode of exposure machine, can enumerate the mode that closely connects (プ ロ キ シ ミ テ ィ ー mode), mirror surface projection mode, step-by-step system, preferably use closely connects mode.
It should be noted that, in the irradiation process of active-energy light, also can across specific mask pattern, carry out according to purposes the irradiation of active-energy light.In this case, exposure portion occurs to solidify, and solidified portion is insoluble or indissoluble with respect to developer solution.
-developing procedure-
Above-mentioned developing procedure for utilizing developer solution to carry out the operation that development treatment is removed unexposed portion, formed pattern after above-mentioned irradiation operation.Can obtain the cured film of patterning thus.Development treatment can utilize the methods such as immersion development, spray development, fur brush development, ultrasound wave development to carry out being generally under the development temperature of 10 ℃～50 ℃.
The developer solution using in above-mentioned developing procedure, as long as solubilized hardening resin composition of the present invention is just not particularly limited, conventionally with an organic solvent, aqueous alkali, also can be used their potpourri.It should be noted that, in the situation that using aqueous alkali as developer solution, preferably after development, water cleans.
As the suitable organic solvent of above-mentioned developer solution, can enumerate such as ether series solvent or alcohol series solvent etc.Specifically, can enumerate such as dialkyl ether, ethylene glycol monoalkyl ether class, glycol dialkyl ether class, diglycol dialkyl ether, triethylene glycol dialkyl ether, alkyl phenyl ethers, aralkyl phenyl ethers, two aromatic series ethers, isopropyl alcohol, phenmethylol etc.
In above-mentioned aqueous alkali, except alkaline reagent, also can contain as required surfactant, organic solvent, buffering agent, dyestuff, pigment etc.As organic solvent in this case, can enumerate above-mentioned as suitable organic solvent of developer solution etc.
As above-mentioned alkaline reagent, can enumerate such as inorganic alkaline agents such as sodium silicate, potassium silicate, NaOH, potassium hydroxide, lithium hydroxide, tertiary sodium phosphate, sodium hydrogen phosphate, sodium carbonate, sal tartari, sodium bicarbonates; The amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, they can use separately, also two or more can be combined.
As above-mentioned surfactant, can enumerate such as non-ionics such as polyoxyethylene alkyl ether class, polyxyethylated ester class, sorbitan acid alkyl ester class, single glycerine alkyl esters; The anionic surface active agent such as alkyl benzene sulfonate, alkyl naphthalene sulfonic acid salt, alkylsurfuric acid salt, alkyl sulfonates, sulfosuccinate ester salt class; The amphoteric surfactantes such as alkyl betaine class, amino acids etc., they can use separately, also two or more can be combined.
-heating process-
Above-mentioned heating process for to make exposure portion (solidified portion) that curing operation (also referred to as rear curing process) further occur by firing after above-mentioned developing procedure.Can enumerate such as: use the light sources such as high-pressure sodium lamp, with for example 0.5J/cm 2～5J/cm 2the light quantity operation of carrying out post-exposure; At the temperature such as 60 ℃～260 ℃, carry out the operation etc. of the rear heating of 10 seconds～120 minutes.By carrying out so rear curing process, can make hardness and the adaptation of cured film of patterning more strong.In addition, utilize this heating process, can make a part (this part is carried out a part for (methyl) acrylic ester monomer of self-contained tertiary carbon) for the structural unit of contained (methyl) acrylic ester polymer of above-mentioned hardening resin composition decompose, thereby can improve curability and solvent resistance.
The thickness of the cured film obtaining by above-mentioned heating process (above-mentioned hardening resin composition being carried out to the cured film that heat curing obtains) is suitably 0.1 μ m～20 μ m.The hardening resin composition of the application of the invention, can provide thickness to obtain the cured film fully reducing.This thickness is 0.5 μ m～10 μ m, 0.5 μ m～8 μ m more preferably more preferably.
It should be noted that, when the thickness of filming before establishing heating is 100%, the thickness of film (being cured film) obtaining by above-mentioned heating process is suitably below 90%.More preferably below 80%, more preferably below 70%.
In above-mentioned heating process, heating-up temperature is suitably more than 150 ℃.Thus, can make this part (this part is from a part for above-mentioned (methyl) acrylic ester monomer containing tertiary carbon) more effectively decompose, thereby can further realize the raising of curability and solvent resistance.This heating-up temperature more preferably 160 ℃ above, more preferably 170 ℃ above, be particularly preferably more than 180 ℃.And below being preferably 260 ℃, more preferably below 250 ℃.
Heat time in above-mentioned heating process is not particularly limited, for example, be suitably 5 minutes～60 minutes.In addition, heating means are also not particularly limited, such as carrying out with firing equipments such as heating plate, convection oven, high frequency heating machines.
[display device]
The invention still further relates to display device, it forms with above-mentioned color filter.
It should be noted that, the display device with the solidfied material forming by above-mentioned hardening resin composition is also contained in suitable embodiment of the present invention by parts and display device.The solidfied material forming by above-mentioned hardening resin composition (cured film) is stable; excellent with the adaptation of base material etc.; and be high rigidity; demonstrate in addition high flatness; there is high permeability; thereby be suitable especially as transparent component, and be also useful as the diaphragm in various display device or dielectric film.
As above-mentioned display device, such as being suitably liquid crystal indicator, solid state image sensor, touch-screen type display device etc.
It should be noted that, in situation about using with parts above-mentioned solidfied material (cured film) as display device, these parts can be the membranaceous single or multiple lift parts that consist of above-mentioned cured film, these single or multiple lift parts can be the parts that further other layer of combination forms, and can be for contain the parts of above-mentioned cured film in formation.
[effect of invention]
Hardening resin composition of the present invention is owing to being above-mentioned formation, thereby can stablize given play to curability, the various physical property such as solvent resistance, the adaptation with substrate (base material), thermotolerance and the transparency after solidifying, excellent storage stability is useful in various uses such as color filters.Thereby color filter and the display device with the solidfied material (cured film) forming by such hardening resin composition are very useful in optical field or motor electronic field.
[embodiment]
Enumerate embodiment below and illustrate in greater detail the present invention, but the present invention is not limited in these embodiment.It should be noted that, only otherwise special declaration, " part " means " mass parts ".
In following synthesis example etc., various physical property etc. are measured as follows.
< weight-average molecular weight >
Take polystyrene as standard substance, take tetrahydrofuran as eluent, utilize HLC-8220GPC (Dong Caoshe manufacture), post: TSKgel SuperHZM-M (Dong Caoshe manufacture) measures weight-average molecular weight by GPC (gel permeation chromatography) method.
< solid constituent >
In aluminium cup, measure about 1g polymer solution (also referred to as resin solution or polymer solution), after adding about 3g acetone that it is dissolved, natural drying at normal temperatures.Use thereafter air drier (Espec society manufactures, trade name: PHH-101), in 140 ℃ after dry 1.5 hours, naturally cooling in exsiccator under vacuum, quality measurement.By its quality reduction, calculated the solid constituent (quality %) of polymer solution.
< acid number >
Accurate weighing 3g resin solution, be dissolved in the mixed solvent of acetone 90g and water 10g, use the KOH aqueous solution of 0.1 equivalent as vs, (Ping Zhao industry society manufactures, trade name: COM-555) measure the acid number of polymer solution, obtained the acid number (AV) of every 1g solid constituent by the acid number of solution and the solid constituent of solution to utilize automatic titration device.
The absorbance > of < hardening resin composition
Hardening resin composition is spin-coated on the square glass substrate of 5cm, at 80 ℃, is dried after 3 minutes, utilize high-pressure sodium lamp to expose under 100mJ, at 220 ℃, carry out the thermal treatment of 30 minutes, obtain the film that thickness is 5 μ m., among 1-Methyl-2-Pyrrolidone 20gs 25 ℃ at flood 2 hour, utilize the tone of spectrophotometer UV3100 (manufacture of society of Shimadzu Seisakusho Ltd.) mensuration 1-Methyl-2-Pyrrolidone of stripping in filming, obtain the absorbance of 450nm thereafter.
Synthesis example 1
Synthesizing of resin solution 1 (BzMI-CHMA-t-BMA-MAA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol methyl ether acetate 844.57g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), prepare to be uniformly mixed the mixed liquor that N-benzyl maleimide 50g, cyclohexyl methacrylate 125g, Tert-butyl Methacrylate 225g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " that Japanese grease society manufactures) 10g forms in beaker; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 21g, propylene glycol methyl ether acetate 84g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 7800, acid number is that 129mgKOH/g, resin solid composition are 35.0 quality %.
Synthesis example 2
Synthesizing of resin solution 2 (BzMI-CHMA-HEMA-MAA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol methyl ether acetate 844.57g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), prepare to be uniformly mixed the mixed liquor that N-benzyl maleimide 50g, cyclohexyl methacrylate 250g, methacrylic acid-2-hydroxy methacrylate 100g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " that Japanese grease society manufactures) 10g forms in beaker; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 21g, propylene glycol methyl ether acetate 84g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 7700, acid number is that 129mgKOH/g, resin solid composition are 35.0 quality %.
Synthesis example 3
Resin solution 3 is (containing the multipolymer of pendant double bonds; Synthesizing BzMI-t-BA-AA//GMA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol monomethyl ether 1006.67g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), prepare to be uniformly mixed the mixed liquor that N-benzyl maleimide 20g, tert-butyl acrylate 250g, acrylic acid 230g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " that Japanese grease society manufactures) 10g forms in beaker; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 40g, propylene glycol monomethyl ether 160g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Thereafter, the nitrogen of gas introduction tube is become to oxygen/nitrogen mixture gas (oxygen/nitrogen=5/95vol%), interpolation is as 2 of polymerization inhibitor, (chemistry society of Kawaguchi manufactures 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), " ANTAGE w-400 ") 1.34g, and as the triethylamine 2.68g of catalyzer, after being uniformly mixed, interpolation is as the glycidyl methacrylate 393.74g of additive compound, be warming up to 115 ℃ and carry out addition reaction, after 8 hours, in the remaining GMA amount of analyzing based on GC (gas chromatography), reach 0.5 quality % cessation reaction when following, obtain the polymer solution containing acidic group multipolymer that side chain has free-radical polymerised pair of key.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 6800, acid number is that 58mgKOH/g, resin solid composition are 39.0 quality %.
It should be noted that, the implication of " BzMI-t-BA-AA//GMA copolymer solution " is GMA to be reacted and the copolymer solution that obtains with the base polymer that uses BzMI, t-BA and AA to obtain.
Synthesis example 4
Resin solution 4 is (containing the multipolymer of pendant double bonds; Synthesizing BzMI-CHA-HEA-AA//GMA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol monomethyl ether 1006.67g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), prepare to be uniformly mixed the mixed liquor that N-benzyl maleimide 20g, cyclohexyl acrylate 150g, 2-Hydroxy ethyl acrylate 100g, acrylic acid 230g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " that Japanese grease society manufactures) 10g forms in beaker; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 40g, propylene glycol monomethyl ether 160g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Thereafter, the nitrogen of gas introduction tube is changed to oxygen/nitrogen mixture gas (oxygen/nitrogen=5/95vol%), interpolation is as 2 of polymerization inhibitor, (chemistry society of Kawaguchi manufactures 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), " ANTAGE w-400 ") 1.34g, and as the triethylamine 2.68g of catalyzer, after being uniformly mixed, interpolation is as the glycidyl methacrylate 393.74g of additive compound, be warming up to 115 ℃ and carry out addition reaction, after 8 hours, in the remaining GMA amount of analyzing based on GC (gas chromatography), reach 0.5 quality % cessation reaction when following, obtain the polymer solution containing acidic group multipolymer that side chain has free-radical polymerised pair of key.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 6800, acid number is that 58mgKOH/g, resin solid composition are 39.0 quality %.
It should be noted that, the implication of " BzMI-CHA-HEA-AA//GMA copolymer solution " is GMA to be reacted and the copolymer solution that obtains with the base polymer that uses BzMI, CHA, HEA and AA to obtain.
Synthesis example 5
Synthesizing of resin solution 5 (BzMI-CHMA-t-BMA-HEMA-MAA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol methyl ether acetate 844.57g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), prepare to be uniformly mixed the mixed liquor that N-benzyl maleimide 50g, cyclohexyl methacrylate 125g, Tert-butyl Methacrylate 125g, methacrylic acid-2-hydroxy methacrylate 100g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " that Japanese grease society manufactures) 10g forms in beaker; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 21g, propylene glycol methyl ether acetate 84g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 7700, acid number is that 133mgKOH/g, resin solid composition are 35.0 quality %.
Synthesis example 6
Resin solution 6 is (containing the multipolymer of pendant double bonds; Synthesizing BzMI-t-BA-HEA-AA//GMA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol monomethyl ether 1006.67g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), prepare to be uniformly mixed the mixed liquor that N-benzyl maleimide 20g, tert-butyl acrylate 150g, 2-Hydroxy ethyl acrylate 100g, acrylic acid 230g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " that Japanese grease society manufactures) 10g forms in beaker; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 40g, propylene glycol monomethyl ether 160g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Thereafter, the nitrogen of gas introduction tube is changed to oxygen/nitrogen mixture gas (oxygen/nitrogen=5/95vol%), interpolation is as 2 of polymerization inhibitor, (chemistry society of Kawaguchi manufactures 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), " ANTAGE w-400 ") 1.34g, and as the triethylamine 2.68g of catalyzer, after being uniformly mixed, interpolation is as the glycidyl methacrylate 393.74g of additive compound, be warming up to 115 ℃ and carry out addition reaction, after 8 hours, in the remaining GMA amount of analyzing based on GC (gas chromatography), reach 0.5 quality % cessation reaction when following, obtain the polymer solution containing acidic group multipolymer that side chain has free-radical polymerised pair of key.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 6800, acid number is that 58mgKOH/g, resin solid composition are 39.0 quality %.
It should be noted that, the implication of " BzMI-t-BA-HEA-AA//GMA copolymer solution " is GMA to be reacted and the copolymer solution that obtains with the base polymer that uses BzMI, t-BA, HEA and AA to obtain.
Synthesis example 7
Synthesizing of resin solution 7 (MMA-MAA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol methyl ether acetate 844.57g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), prepare to be uniformly mixed the mixed liquor that methyl methacrylate 400g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" Perbutyl O " that Japanese grease society manufactures) 10g forms in beaker; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 21g, propylene glycol methyl ether acetate 84g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 7700, acid number is that 133mgKOH/g, resin solid composition are 35.0 quality %.
Synthesis example 8
Synthesizing of resin solution 8 (BzMI-t-BMA-HEMA-MAA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol methyl ether acetate 874.57g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), prepare to be uniformly mixed the mixed liquor that N-benzyl maleimide 50g, Tert-butyl Methacrylate 235g, methacrylic acid-2-hydroxy methacrylate 100g, methacrylic acid 115g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " that Japanese grease society manufactures) 10g forms in beaker; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 6g, propylene glycol methyl ether acetate 54g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 15500, acid number is that 150mgKOH/g, resin solid composition are 35.0 quality %.
Synthesis example 9
Synthesizing of resin solution 9 (MD-t-BMA-HEMA-MAA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol methyl ether acetate 844.57g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), preparation is uniformly mixed dimethyl-2 in beaker, the mixed liquor that 2 '-[oxo two (methylene)] two 2-acrylate (MD) 50g, Tert-butyl Methacrylate 250g, methacrylic acid-2-hydroxy methacrylate 100g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " that Japanese grease society manufactures) 10g forms; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 15g, propylene glycol methyl ether acetate 84g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 12000, acid number is that 133mgKOH/g, resin solid composition are 35.0 quality %.
Synthesis example 10
Synthesizing of resin solution 10 (AMA-t-BMA-HEMA-MAA copolymer solution)
In the reactive tank that possesses thermometer, stirring machine, gas introduction tube, cooling tube and dropwise adding tank introducing port, drop into propylene glycol methyl ether acetate 844.57g, carry out being heated to 90 ℃ after nitrogen replacement.On the other hand, as dropwise adding tank (A), prepare to be uniformly mixed the mixed liquor that methyl-(α-allyloxy methyl) acrylate (AMA) 50g, Tert-butyl Methacrylate 250g, methacrylic acid-2-hydroxy methacrylate 100g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " that Japanese grease society manufactures) 10g forms in beaker; In dropwise adding tank (B), prepare to be uniformly mixed the mixed liquor that n-dodecyl mercaptan 15g, propylene glycol methyl ether acetate 84g form.Temperature at reactive tank reaches after 90 ℃, remains at this temperature and is started to drip by dropwise adding tank, carries out polymerization in 3 hours.After dropping finishes, at 90 ℃, keep 30 minutes, be warming up to afterwards 115 ℃, carry out slaking in 90 minutes.
Resulting polymer solution is analyzed, and result weight-average molecular weight is 12300, acid number is that 132mgKOH/g, resin solid composition are 35.2 quality %.
In table 1, show in detail resin solution 1～10.
It should be noted that, about forming the combined amount of the monomer of resin in table 1, what the numerical value of each monomer of formation base polymkeric substance was recorded is the blending ratio (quality %) of each monomer when their total amount is made as to 100 quality %.In addition, in synthesis example 4 and 6, the numerical value of the GMA of addition on this base polymer (have can with the functional group of acidic group bonding and the compound of the two keys of polymerism) be take the form of the GMA ratio of institute's addition on the carboxylic acid composition of the monomer (being AA in this case) with acidic group and the two keys of polymerism and is recorded, and by " GMA blending ratio (addition the AA blending ratio (quality %) of GMA)={ molar weight (mol) of the molar weight of GMA (mol)/AA } * AA blending ratio (quality %) ", tries to achieve.For example, in synthesis example 4, the AA in base polymer (100 quality %) forms with 46 quality %, and the GMA at the upper addition 2769mmol of the AA of this 46 quality % (3191mmol), is defined as " 40 " by the blending ratio of this GMA (quality %) thus.
[table 1]
Figure BDA00003650366700401
Mark in table 1 is as described below.
BzMI:N-benzyl maleimide
MD: dimethyl-2,2 '-[oxo two (methylene)] two 2-acrylate
AMA: methyl-(α-allyloxy methyl) acrylate
MMA: methyl methacrylate
CHMA: cyclohexyl methacrylate
CHA: cyclohexyl acrylate
T-BMA: Tert-butyl Methacrylate
T-BA: tert-butyl acrylate
HEMA: methacrylic acid-2-hydroxy methacrylate
HEA: 2-Hydroxy ethyl acrylate
MAA: methacrylic acid
AA: acrylic acid
GMA: glycidyl methacrylate
Production example 1
The making of pigment dispersion 1
Using 12.9 parts of propylene glycol methyl ether acetates, as the Disparlon DA-7301 (0.4 part) of spreading agent, as 2.25 parts of C.I. pigment green 36s (Monastral Green6Y-CL, Heubach society manufacture) and 1.5 parts of mixing of C.I. pigment yellow 150 (Yellow Pigment E4GN-GT, Lanxess society manufacture) of colorant, utilize coating rocker to carry out disperseing for 3 hours, thereby obtain pigment dispersion 1.
Embodiment 1
Using resin solution 1 (1.0 parts), resin solution 2 (1.0 parts), as 0.70 part of the dipentaerythritol acrylate of free-radical polymerised compound, 0.35 part of Irgacure 369 (manufacture of Ciba society) as free-radical polymerised Photoepolymerizationinitiater initiater, pigment dispersion 1 (7.88 parts), as 6.57 parts of mixing of propylene glycol methyl ether acetate of solvent, obtain hardening resin composition 1.While carrying out absorbance measurement for this hardening resin composition 1, absorbance is 1.6 * 10 -2.
Embodiment 2～8, comparative example 1～7
Except by mixing shown in table 2 and table 3, obtain respectively similarly to Example 1 hardening resin composition 2～15, measure respectively afterwards absorbance.The results are shown in table 2 and table 3.
[table 2]
[table 3]
Figure BDA00003650366700431
By the results verification of table 2 and table 3 to following content.
Embodiment 1 and comparative example 1,2,5 and 6; Embodiment 2 and comparative example 3 and 4; Embodiment 3,6,7 and 8 and comparative example 7; Embodiment 4 is the examples that obtain respectively solidfied material and carry out absorbance measurement under same condition with comparative example 3 and 4, if but respectively they are compared, to compare with embodiment, the absorbance in comparative example all enlarges markedly, and the transparency of known solidfied material is poor.Herein, when curability, the solvent resistance of hardening resin composition is insufficient, colorant generation stripping and the absorbance of solidfied material can be increased; Thereby from the result of table 2 and table 3, compare with embodiment, curability and the solvent resistance of the hardening resin composition of comparative example are insufficient.In addition, although not shown in table, the developability of the solidfied material obtaining in embodiment, also all excellent with the various physical property such as the adaptation of substrate, thermotolerance.

Claims (6)

1. a hardening resin composition, its hardening resin composition for containing (methyl) acrylic ester polymer, polymerizable compound and Photoepolymerizationinitiater initiater, this hardening resin composition is characterised in that:
This (methyl) acrylic ester polymer has the structural unit of (methyl) acrylic ester monomer of self-contained tertiary carbon;
This hardening resin composition is at least one mode of selecting in the group that free following manner forms: this hardening resin composition further contains the mode of the polymkeric substance with hydroxyl; And this (methyl) acrylic ester polymer further has the mode of hydroxyl.
2. hardening resin composition as claimed in claim 1; it is characterized in that; described (methyl) acrylic ester monomer containing tertiary carbon has the structure that oxygen atom and tertiary carbon atom bonding form, and this oxygen atom is the oxygen atom with (methyl) acryloyl group adjacency.
3. hardening resin composition as claimed in claim 1 or 2, is characterized in that, described (methyl) acrylic ester polymer and/or the polymkeric substance with hydroxyl are for having the polymkeric substance of the two keys of polymerism at side chain.
4. a solidfied material, is characterized in that, this solidfied material is that the hardening resin composition described in claim 1～3 any one is solidify to form.
5. a color filter, is characterized in that, this color filter has solidfied material claimed in claim 4 on substrate.
6. a display device, is characterized in that, this display device right to use requires the color filter described in 5 to form.
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