CN103576457B - Hardening resin composition and application thereof - Google Patents

Hardening resin composition and application thereof Download PDF

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CN103576457B
CN103576457B CN201310348018.6A CN201310348018A CN103576457B CN 103576457 B CN103576457 B CN 103576457B CN 201310348018 A CN201310348018 A CN 201310348018A CN 103576457 B CN103576457 B CN 103576457B
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resin composition
monomer
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CN103576457A (en
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山口稔
前田顺启
田村亮太
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NIPPON CATALYST 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)
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  • Health & Medical Sciences (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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  • Optical Filters (AREA)
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Abstract

The present invention provides a kind of hardening resin composition and application thereof, the hardening resin composition can stablize the various physical property such as adaptation, heat resistance and the transparency of the solvent resistance after playing curability, solidification and substrate (substrate), excellent storage stability is useful in various uses such as colour filters.The solidfied material formed by such hardening resin composition and the colour filter and display device that have used the solidfied material are also provided.Hardening resin composition of the invention is the hardening resin composition containing (methyl) acrylic ester polymer, polymerizable compound and Photoepolymerizationinitiater initiater, wherein, being somebody's turn to do (methyl) acrylic ester polymer is the polymer with the structural unit from (methyl) acrylate monomer containing tertiary carbon；The hardening resin composition further contains the polymer with hydroxyl；And/or (methyl) acrylic ester polymer further has hydroxyl.

Description

Hardening resin composition and application thereof
[technical field]
The present invention relates to hardening resin compositions and application thereof.More particularly it relates to be filled in liquid crystal display Set or solid state image sensor etc. used in colour filter, ink, galley, printed circuit board, semiconductor element, photoresist Useful hardening resin composition in the various uses such as the various optical components such as agent or motor electronics, its solidfied material, Use the colour filter and display device of solidfied material.
[background technique]
Hardening resin composition for that can pass through heat or active energy line curing has studied answers towards for various purposes With, for example, colour filter used in liquid crystal display device or solid state image sensor etc., ink, galley, printed circuit board, The purposes such as the various optical components such as semiconductor element, photoresist or motor electronics are developed each with institute on the way It is required that excellent hardening resin composition.Among these purposes, so-called colour filter be constitute liquid crystal display device or The main component of solid state image sensor etc., usually by substrate, the pixel of at least 3 primary colors (red (R) green (G) indigo plant (B)), with And the resin black bottom (BM) for separating them and protective film furthermore etc. are constituted, the protective film is to pixel and resin black bottom Coating protection is carried out, and is arranged to make these bumps planarizations.
In general, in the case where carrying out the pixel formation of colour filter using hardening resin composition, for each colour Element carries out following processes: (1) in the painting process of substrate entire surface coating hardening resin composition；(2) exposure process, across Photomask carries out pattern exposure on the resist film formed by painting process and exposure portion is solidified, and makes solidified portion insoluble later Change；(3) (baking) treatment process is fired in development, after removing unexposed portion using developer solution, makes to expose by firing (baking) Light portion further solidifies；Using the method that same process is repeated to colors.If in view of in such colour filter Application in purposes etc., then solvent resistance and substrate (substrate) after requiring hardening resin composition that there is curability, solidification The various physical property such as adaptation, heat resistance and the transparency.In addition, in recent years, having carried out optical component, motor electronics etc. Miniaturization slimming save energetic, accompanying this, it is highly desirable used in the components such as colour filter have it is high-grade Performance.
About existing hardening resin composition, as the composition suitable for color filter application, such as disclose following Composition: containing binder resin, (binder resin contains the knot as derived from the monomer with aliphatic polycycle epoxy group Structure unit and the structural unit as derived from unsaturated carboxylic acid system monomer), colorant, photopolymerizable compound, Photoepolymerizationinitiater initiater And the photosensitive composition of solvent (referring to patent document 1)；Containing copolymer, (copolymer contains such as flowering structure Unit: the structural unit of residue made of protecting with carboxyl/phenolic hydroxyl group being thermal decomposited property group has epoxy group/oxa- The structural unit of cyclobutane base and with carboxyl/phenolic hydroxyl group structural unit), radioactivity-sensitive radical polymerization initiator, The photosensitive composition of ethylenically unsaturated compounds and colorant (referring to patent document 2).
[existing technical literature]
[patent document]
Patent document 1: Japanese Unexamined Patent Publication 2007-333847 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2012-22048 bulletin
[summary of the invention]
[problems to be solved by the invention]
As described previously for hardening resin composition, it is desirable that it is with the solvent resistance and base after curability, solidification The various physical property such as adaptation, heat resistance and the transparency of plate (also referred to as substrate).On the other hand, from processing aspect, also It is required that hardening resin composition itself has storage stability (also referred to as storage stability), solidfied material can be played consistently out The transparency, solvent resistance, adaptation, heat resistance etc..Also, in recent years, with the progress of the technologies such as display device, for being made Each component also expects to have higher performance strongly, such as in color filter application, it is desirable that has high transparency after hardening. But in existing resin combination, status is to be unable to fully cope with these an urgent demands.For example, described in the patent document 1,2 Resin combination in, since curability is insufficient, be unable to get the high solidfied material of the transparency；And storage stability does not also fill Point, thus the curability for further increasing resin combination, can stablize play in terms of there are also improvement more than Ground.And also there is room for improvement in terms of the storage stability for improving resin combination.
The present invention is carried out in view of above-mentioned status, and its purpose is to provide a kind of hardening resin compositions, this is solid The property changed resin combination can stablize the solvent resistance after playing curability, solidification, adaptation, heat resistance with substrate (substrate) With the various physical property such as the transparency, excellent storage stability is useful in the various uses such as colour filter.The purpose of the present invention is also It is to provide the solidfied material formed with such hardening resin composition and the colour filter and the display that have used the solidfied material Device.
[means to solve the problem]
The present inventor has carried out various researchs for useful hardening resin composition in the various uses such as colour filter, It is conceived to following the description: that is, if being made containing (methyl) acrylic ester polymer, polymerizable compound and Photoepolymerizationinitiater initiater Resin combination, then can become with curability composition.It has also been found that if making the following sides of the hardening resin composition Case (form), then the excellent storage stability of hardening resin composition, in addition curability and the solvent resistance after solidify leap Property improve, it is available steadily to show high transparency, with adaptation, heat resistance, the high rigidity of substrate (substrate) etc. The solidfied material of various physical property；The scheme is that (methyl) acrylic ester polymer has from (methyl) acrylic acid containing tertiary carbon The structural unit and the hardening resin composition of ester system monomer further contain the scheme of the polymer with hydroxyl；And/or It is somebody's turn to do the scheme that (methyl) acrylic ester polymer further has hydroxyl.Such hardening resin composition is used in colour filter It is particularly useful on the way, wherein being suitable as the resin combination for being used to form colour filter protective film or insulating film etc. 's.Consequently found that the solidfied material formed by such hardening resin composition, colour filter and display device can be coped with sufficiently closely An urgent demand of high performance over year, in optical field, motor electronic field be it is extremely useful, thus expecting can be perfect Ground solves the above subject, so as to complete the present invention.
Herein, (methyl) acrylic ester polymer contained by hardening resin composition of the invention has to come from and contain The structural unit of (methyl) acrylate monomer of tertiary carbon, the structural unit are easy to be thermally decomposed.Specifically, with (methyl) O-C key between the adjacent oxygen atom of acryloyl group and the tertiary carbon atom being adjacent is easy to be cut off, to be decomposed into (first Base) acrylic acid and tertiary carbon atom side generate stable compound.Thus, for example hardening resin composition of the invention is used In the case that the pixel of colour filter is formed, by the heating process (also referred to as ablating work procedure or then bake process) after development, The above-mentioned structural unit from (methyl) acrylate monomer containing tertiary carbon is decomposed, and generates (methyl) acrylic acid and in uncle The stable compound that carbon atom side generates.And think, hardening resin composition can further contain poly- with hydroxyl Close hydroxyl and (methyl) third generated that hydroxyl, and/or (methyl) acrylic ester polymer in object can further have Ester cross-linked structure is generated between olefin(e) acid, due to this reason, the curability of resin combination and solvent resistance after solidification are tremendous Ground is improved.
In addition, above-mentioned (methyl) acrylic ester polymer, the polymer with hydroxyl are preferably as described later in side chain Polymer with polymeric double bond.Curability can be further improved as a result, and there is polymeric double bond with side chain is used only in Polymer the case where compare, the present invention curability of hardening resin composition can be improved and meanwhile also can be improved preservation stablize Property.It is as described above this is because, in the present invention, in (methyl) that thermal decomposition generates between acrylic acid and hydroxyl it can be expected that It, in this case, can also table even if reducing the content of the polymeric double bond in polymer based on the curing reaction of ester cross-linked structure Reveal sufficient curability, can further decrease the polymeric double bond of side chain in preservation react and generate gelation can It can property.
That is, the present invention relates to a kind of hardening resin composition, to contain (methyl) acrylic ester polymer, polymerization Property compound and Photoepolymerizationinitiater initiater hardening resin composition, which is characterized in that: should (first Base) acrylic ester polymer be the polymer with the structural unit from (methyl) acrylate monomer containing tertiary carbon； The hardening resin composition is selected from least one of the group being made of following manner mode, the mode are as follows: the solidification Property resin combination further contains the mode of the polymer with hydroxyl；And (methyl) acrylic ester polymer is somebody's turn to do into one Walk the mode with hydroxyl.
The invention further relates to a kind of solidfied material, being will be made of the solidification of above-mentioned hardening resin composition.
The invention further relates to colour filters, have above-mentioned solidfied material on substrate.
Also, the invention further relates to display devices, are constituted using above-mentioned colour filter.
The present invention described below.It should be noted that by each preferred side of the present invention of 2 kinds or 3 kinds or more of following records The mode that formula is composed is also preferred embodiment of the invention.
It should be added that:
The technical solution of claim 1 include it is following a)~c) three kinds of modes.
A) (methyl) acrylic ester polymer is included at least※1, polymerizable compound, Photoepolymerizationinitiater initiater and have The hardening resin composition of this 4 kinds of ingredients of the polymer of hydroxyl.
※ 1:(methyl) acrylic ester polymer have the structure from (methyl) acrylate monomer containing tertiary carbon Unit, the polymer can also further have hydroxyl.
B) (methyl) acrylic ester polymer is included at least※2, this 3 kinds of polymerizable compound and Photoepolymerizationinitiater initiater The hardening resin composition of ingredient.
※ 2:(methyl) acrylic ester polymer is with from the knot containing tertiary carbon (methyl) acrylate monomer Structure unit and the polymer with hydroxyl.
C) (methyl) acrylic ester polymer is included at least※3, polymerizable compound, Photoepolymerizationinitiater initiater and have The hardening resin composition of this 4 kinds of ingredients of the polymer of hydroxyl.
※ 3:(methyl) acrylic ester polymer is with from the knot containing tertiary carbon (methyl) acrylate monomer Structure unit and the polymer with hydroxyl.
[hardening resin composition]
It is poly- that hardening resin composition of the invention contains (methyl) acrylic ester polymer, polymerizable compound and light Initiator is closed, these contain ingredient can be respectively using one kind or two or more.In addition, can further contain a kind or 2 as needed Kind or more other ingredients.
<(methyl) acrylic ester polymer>
In above-mentioned hardening resin composition, (methyl) acrylic ester polymer has from (methyl) third containing tertiary carbon The structural unit of olefin(e) acid ester system monomer.Structural unit from (methyl) acrylate monomer containing tertiary carbon means the monomer In polymerism carbon-to-carbon double bond (C=C) become the structural unit of singly-bound (C-C), the suitably monomer has oxygen atom and uncle Structure made of carbon atom bonding, and the oxygen atom is the oxygen atom adjacent with (methyl) acryloyl group.That is, above-mentioned containing tertiary carbon Structure made of there is (methyl) acrylate monomer the oxygen atom for being adjacent to (methyl) acryloyl group to be bonded with tertiary carbon atom It is suitable.It should be noted that the carbon original that it is 3 with other carbon atoms of the carbon atom bonding that so-called tertiary carbon atom, which means, Son.
As above-mentioned (methyl) acrylate monomer containing tertiary carbon, suitably there is 1 polymerism carbon-in the molecule The compound of carbon double bond has 1 (methyl) acryloyl group (CH in the molecule2=C (R)-C (=O) -) compound, such as Preferably compound represented by the following general formula (1):
CH2=C(R)-C(=O)-O-A (1)
(R indicates hydrogen atom or methyl.A indicates any monovalent organic radical for being included in the structure that oxygen atom side has tertiary carbon atom Group.).
In above-mentioned general formula (1), organic group represented by A can be with such as-C (R1)(R2)(R3) indicate.Such case Under, R1、R2And R3Identical or different and carbon atom number 1~30 alkyl is that suitably, which can be saturated hydrocarbyl, can also Think unsaturated alkyl.And it is possible to have cyclic structure, substituent group can also be further had.In addition, R1、R2And R3End End position can interconnect to form cyclic structure.
It should be noted that as described later, from O-C key, (the O-C key is between oxygen atom and tertiary carbon atom in the present invention O-C key, which is the oxygen atom adjacent with (methyl) acryloyl group, which is the A for being adjacent to the oxygen atom In tertiary carbon atom) be cut off and the noval chemical compound that generates it is readily volatilized from the aspect of, the carbon of organic group represented by A is former Subnumber is preferably 12 or less.Wherein, organic group represented by A preferably comes from (methyl) tert-butyl acrylate and/or (first Base) t-amyl group.Also, organic group represented by A can have branched structure.
Herein, adjacent with (methyl) acryloyl group about being bonded in above-mentioned (methyl) acrylate monomer containing tertiary carbon The tertiary carbon atom on oxygen atom connect, at least one in carbon atom abutted with the tertiary carbon atom are suitable with bonded hydrogen atoms 's.For example, (methyl) acrylate monomer containing tertiary carbon is compound represented by above-mentioned general formula (1), A is-C (R1) (R2)(R3) represented by group in the case where, R1、R2And R3In at least one have 1 or more hydrogen atom, this is preferred. In such mode, by heating, O-C key (the O-C key is the O-C key between oxygen atom and tertiary carbon atom, the oxygen atom be with The adjacent oxygen atom of (methyl) acryloyl group, which is the tertiary carbon atom for being adjacent to the oxygen atom) it is cut off and generates (methyl) acrylic acid, while double bond (C=C) is formed between the tertiary carbon atom and the carbon atom being adjacent, more steadily give birth to The compound of Cheng Xin.
The noval chemical compound generated as described above is preferably volatile.In this case, the noval chemical compound is from solidfied material It is vaporized, the film thickness of solidfied material (cured film) reduces as a result, while further containing in for example above-mentioned hardening resin composition coloured In the case where material, colorant concentration increases after the heating.Therefore, it can be achieved that further filming, can further seek simultaneously The high shading rate of high color purity and black matrix layer.If considering this aspect, above-mentioned R1、R2And R3It is identical or different and be carbon The saturated hydrocarbyl that atomicity is 1~15 is preferred.Saturated hydrocarbyl, further preferred carbon of the more preferable carbon atom number for 1~10 The saturated hydrocarbyl that saturated hydrocarbyl that atomicity is 1~5, particularly preferred carbon atom number are 1~3.
From developability aspect, preferably above-mentioned (methyl) acrylic ester polymer is to show alkali-soluble polymerization Object, the polymer with acidic group is suitable in the molecule.
As above-mentioned acidic group, it can be cited for example that carboxyl, phenolic hydroxyl group, acid anhydride, phosphate, sulfonic group etc. are sent out with buck The functional group of raw neutralization reaction can only have a kind therein, it is possible to have two or more.Wherein preferred carboxyl, carboxylic acid anhydrides Base, more preferable carboxyl.
It is poly- as this in the case that above-mentioned (methyl) acrylic ester polymer is the polymer in the molecule with acidic group The acid value (AV) for closing object is not particularly limited, for example, 20mgKOH/g or more, less than 300mgKOH/g being suitable.As a result, may be used More sufficient alkali solubility is shown, the more excellent solidfied material of developability can be obtained.Lower limit value as acid value is more preferable For 30mgKOH/g or more, further preferably 40mgKOH/g or more.Furthermore be more preferably 200mgKOH/g or less, further it is excellent It is selected as 150mgKOH/g or less.
The acid value of polymer can for example be found out as described below.
Above-mentioned (methyl) acrylic ester polymer can also be in the molecule with the polymer of hydroxyl.That is, above-mentioned (first Base) acrylic ester polymer can for further with hydroxyl polymer, such mode is also appropriate parties of the invention One of formula.It can further improve the curability of hardening resin composition as a result, can provide transparent further excellent Solidfied material.
Above-mentioned (methyl) acrylic ester polymer for example can be by including (methyl) acrylic ester containing tertiary carbon The monomer component of monomer, which is polymerize, to be obtained.It is preferred that the monomer component further contains the list with acidic group and polymeric double bond Body.In addition, above-mentioned monomer component, which further contains, to be had in the case that above-mentioned (methyl) acrylic ester polymer has hydroxyl Hydroxyl and the monomer of polymeric double bond are to be suitable for.
It should be noted that used each monomer can be respectively using one kind or two or more.
Above-mentioned (methyl) acrylic ester polymer can be as obtained from polymerizeing to such monomer component Polymer (also referred to as base polymer (base polymer)) is also possible to make to have as described below and can be bonded with acidic group Functional group and polymeric double bond compound and the base polymer react obtained from polymer (also referred to as side chain have The polymer or polymer containing pendant double bonds for having polymeric double bond), it is suitable.It is more preferably poly- containing pendant double bonds Object is closed, curability thus can be further improved, the more excellent solidfied material such as the transparency, adaptation can be obtained.It needs to illustrate , it is suitable that the polymeric double bond of side chain, which is free-radical polymerised double bond,.
In above-mentioned monomer component, (methyl) acrylate monomer containing tertiary carbon as discussed previously with respect to above-mentioned monomer at The 100 mass % of total amount divided, the content ratio of the monomer is suitably 5 mass % or more.The present invention can be further shown as a result, Effect, effect of the present invention are generated from the structural unit containing tertiary carbon (methyl) acrylate monomer.The content ratio More preferably 15 mass % or more, particularly preferably 20 mass % or more.Also, the upper limit of above-mentioned content ratio considers other monomers Content ratio take the circumstances into consideration to set, for example, in the case where being used for color filter application, from further increasing pattern properties, aobvious It is suitably 90 mass % or less from the aspect of shadow.More preferably 75 mass % or less, further preferably 60 mass % or less.
As the above-mentioned monomer with acidic group and polymeric double bond, it can be cited for example that: (methyl) acrylic acid, butenoic acid, The unsaturated monocarboxylics class such as cinnamic acid, vinyl benzoic acid；The insatiable hungers such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid With polybasic carboxylic acid class；The mono- 2- of succinic acid (2- acryloxy) hydroxyl ethyl alcohol, the mono- 2- of succinic acid (2- methacryloxy) hydroxyl The unsaturated monocarboxylic class of chain extension occurs between unsaturated groups and carboxyl for ethyl alcohol etc.；The unsaturations such as maleic anhydride, itaconic anhydride Anhydride；The unsaturated compound of the phosphorous acidic groups such as light ester P-1M (manufacture of common prosperity society chemistry)；Etc..Among these, from general Property, it is acquired etc. set out, be suitable for using carboxylic serials monomer (unsaturated monocarboxylic class, unsaturated polybasic carboxylic acid class, unsaturation Anhydride).It is further preferred that from reactivity, alkali solubility etc. consideration, it is preferable to use unsaturated monocarboxylic class, further excellent (methyl) acrylic acid is selected, wherein particularly preferred methacrylic acid.
It should be noted that (methyl) acrylic acid means acrylic acid and/or methacrylic acid.
The content ratio of the above-mentioned monomer with acidic group and polymeric double bond, which takes the circumstances into consideration to be set in, makes (methyl) acrylic ester The acid value of polymer is in above-mentioned preferred scope.For example, the 100 mass % of total amount relative to above-mentioned monomer component, have acidic group and The content ratio of the monomer of polymeric double bond is preferably 5 mass % or more, more preferably 10 mass % or more, further preferably 20 Quality % or more.And preferably 85 mass % or less, more preferably 60 mass % or less, further preferably 50 mass % or less.
In addition, as described above, above-mentioned monomer component includes that have hydroxyl and the monomer of polymeric double bond be also suitable.This The monomer of sample is preferably the monomer that side chain has hydroxyl, also, is suitably with hydroxyl and (first from reactive aspect Base) acryloyl group monomer.It is preferred that it can be cited for example that (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid -2- hydroxyl Propyl ester, (methyl) acrylic acid -3- hydroxy propyl ester, (methyl) acrylic acid -2- hydroxybutyl, (methyl) acrylic acid -3- hydroxybutyl, (methyl) acrylic acid hydroxy alkyl esters such as (methyl) acrylic acid -4- hydroxybutyl, (methyl) acrylic acid -2,3- hydroxy propyl ester.
It should be noted that so-called (methyl) acryloyl group means methylacryloyl and/or acryloyl group.
Above-mentioned monomer component includes in the case where having hydroxyl and the monomer of polymeric double bond, relative to above-mentioned monomer component 100 mass % of total amount, the content ratio of the monomer is for example suitably 1 mass % or more.The content ratio is more preferably 5 mass % It above, is more preferably 10 mass % or more.In addition, if considering (methyl) acrylate monomer containing tertiary carbon, there is acidic group With the content ratio of the monomer of polymeric double bond, then preferably 70 mass % or less, more preferably 50 mass % or less.
(methyl) acrylic ester polymer contained by hardening resin composition of the invention is with from containing uncle The polymer of the structural unit of (methyl) acrylate monomer of carbon, more preferable main chain have ring structure.It, can as ring structure To enumerate imide ring, amylene oxide ring, tetrahydrofuran ring, lactonic ring etc..In order to have these ring structures, above-mentioned monomer component Also contain other copolymerizable monomers (also referred to as other monomers) in addition to above-mentioned monomer.
As above-mentioned other monomers, such as it is preferable to use N substituted maleimide amine system monomer, the dioxanes other than above-mentioned monomer Base -2,2 '-(oxygroup dimethylene) diacrylate system monomer, α-(unsaturated alkoxyalkyl) acrylate monomer are (excellent Select alkyl-(α-allyloxy methyl) acrylate monomer) etc..Above-mentioned monomer component further contains to be selected from and be taken by N as a result, For maleimide amine system monomer, dialkyl group -2,2 '-(oxygroup dimethylene) diacrylate system monomer and α-(unsaturated alcoxyl Base alkyl) mode of at least one of group monomer of acrylate monomer composition is also one of suitable way of the invention. In addition, can be suitably used according to required physical property in (methyl) acrylate monomer and aromatic vinyl base system monomer etc. It is one kind or two or more.
Herein, such as N substituted maleimide amine system monomer and/or dialkyl group -2,2 '-(oxygroup dimethylene) two are being used When acrylate monomer and/or alkyl-(α-allyloxy methyl) acrylate monomer, can obtain heat resistance, hardness, The solidfied material that colorant dispersibility etc. is further enhanced.Especially using dialkyl group -2,2 '-(oxygroup dimethylene) dipropyl When olefin(e) acid ester system's monomer and/or alkyl-(α-allyloxy methyl) acrylate monomer, it can be obtained in terms of heat-resisting coloring More excellent solidfied material.
It should be noted that the content ratio of above-mentioned other monomers is excellent in the 100 mass % of total amount of above-mentioned monomer component It is selected as 60 mass % or less, preferably 50 mass % or less.Especially contain N substituted maleimide amine system monomer, dialkyl group -2, The feelings of 2 '-(oxygroup dimethylene) diacrylate system monomers and/or α-(unsaturated alkoxyalkyl) acrylate monomer Under condition, from heat resistance, hardness, colorant dispersibility, developing powder, transparency etc., content ratio is preferably 2 matter Measure the mass of %~60 %, more preferably 2 mass of mass %~50 %, further preferably 3 mass of mass %~40 %.
As above-mentioned N substituted maleimide amine system monomer, it can be cited for example that N- N-cyclohexylmaleimide, N- phenyl horse Come acid imide, N- methylmaleimido, n-ethylmaleimide, N- isopropylmaleimide, N- tert-butyl Malaysia acyl Imines, N- dodecyl maleimide, N- benzyl maleimide, N- naphthalene maleimide etc., can be used in them It is one kind or two or more.Wherein, from the aspect of the transparency, preferably N-phenylmaleimide, N- benzyl maleimide, Particularly suitable is N- benzyl maleimide.
As above-mentioned N- benzyl maleimide, it can be cited for example that: benzyl maleimide；To methylbenzyl Malaysia acyl Imines, to the alkyl substituted benzyls base maleimide such as butyl benzyl maleimide；To the phenol hydroxyl such as hydroxybenzyl maleimide Base substituted benzyl maleimide；O-chlorobenzyl maleimide, adjacent dichloro benzyl maleimide, to dichloro benzyl Malaysia acyl The halogens substituted benzyl maleimide such as imines；Etc..
As above-mentioned dialkyl group -2,2 '-(oxygroup dimethylene) diacrylate system monomer, it can be cited for example that 2,2 ' - [oxo is bis- (methylene)] double acrylic acid, the double 2- acrylate of dialkyl group -2,2 '-[oxo is bis- (methylene)], dialkyl group -2, At least one in the esteratic sites such as 2 '-[oxo is bis- (methylene)] double 2- acrylate contains tertiary carbon compound etc..These it In, the easiness etc. obtained from the transparency, dispersibility, industry, suitable for [oxo is double using such as dimethyl -2,2 ' - (methylene)] double 2- acrylate etc..
As above-mentioned α-(unsaturated alkoxyalkyl) acrylate monomer, it can be cited for example that α-allyloxy methyl Acrylic acid, α-allyloxy methyl methacrylate, α-allyloxy ethyl methacrylate, α-allyloxy methacrylic acid N-propyl, α-allyloxy isopropyl methacrylate, α-allyloxy n-BMA, α-allyloxy methyl-prop The secondary butyl ester of olefin(e) acid, α-allyloxy Tert-butyl Methacrylate, α-allyloxy n-amylmethacrylate, α-allyloxy first The secondary pentyl ester of base acrylic acid, α-allyloxy t-amyl methacrylate, α-allyloxy methacrylic acid peopentyl ester etc..Wherein fit Preferably alkyl-(α-allyloxy methyl) acrylate monomer.As alkyl-(α-allyloxy methyl) acrylic ester list Body, the easiness etc. obtained from the transparency, dispersibility, industry, is suitable for using such as methyl-(α-allyloxy first Base) acrylate etc..
Above-mentioned α-(unsaturated alkoxyalkyl) acrylate can for example pass through No. 2010/114077 brochure of International Publication No. Manufacturing method disclosed in son is manufactured.
As above-mentioned (methyl) acrylate monomer, for example, if considering the surface hardness etc. of solidfied material, it is preferred to have There is the monomer of alicyclic ring skeleton.Specifically, it can be cited for example that (methyl) cyclohexyl acrylate, (methyl) acrylic acid (cyclohexyl) Methyl esters, (methyl) isobornyl acrylate, (methyl) acrylic acid -1- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid (3,4- epoxy hexamethylene Base) methyl esters, (methyl) acrylic acid dicyclopentenyl ester, dicyclopentenyl oxygroup (methyl) ethyl acrylate, the methacrylic acid tricyclic [last of the ten Heavenly stems Ester, dihydroxymethyl-tristane two (methyl) acrylate, pentacyclopentadecane dimethanol two (methyl) acrylate, hexamethylene Dimethanol two (methyl) acrylate, norcamphane dimethanol two (methyl) acrylate, terpane -1,8- glycol two (methyl) propylene Acid esters, terpane -2,8- glycol two (methyl) acrylate, terpane -3,8- glycol two (methyl) acrylate, bicyclic [2.2.2] - Two (methyl) acrylate of octane -1- methyl -4- isopropyl -5,6- dihydroxymethyl etc..Among these, from versatility, acquired Etc. set out, be suitable for using (methyl) cyclohexyl acrylate, (methyl) acrylic acid (cyclohexyl) methyl esters, (methyl) acrylic acid different Norbornene ester, methacrylic acid tricyclodecyl.In addition, being further adapted for using (methyl) glycidyl acrylate, (methyl) acrylic acid The cycloaliphatic epoxies such as methylglycidyl esters, (methyl) acrylic acid ethyl ethylene oxidic ester.
Above-mentioned (methyl) acrylate monomer can also be enumerated for example: (methyl) methyl acrylate, (methyl) acrylic acid Ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid are secondary Butyl ester, (methyl) acrylic acid n-pentyl ester, the secondary pentyl ester of (methyl) acrylic acid, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid -2- Ethylhexyl, (methyl) isodecyl acrylate, (methyl) tridecyl acrylate, (methyl) acryllic acid monooctyl ester, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) stearyl acrylate, (methyl) benzyl acrylate, (methyl) third Olefin(e) acid phenyl ester, (methyl) acrylic acid -2- methoxy acrylate, (methyl) acrylic acid -2- ethoxy ethyl ester, (methyl) acrylic acid benzene oxygen Base ethyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid N, N- dimethylaminoethyl, Alpha-hydroxy methyl methacrylate Ester, Alpha-hydroxy ethyl methacrylate, Alpha-hydroxy Tert-butyl Methacrylate, Alpha-hydroxy t-amyl methacrylate etc., and 1,4- dioxo spiro [4,5] decane -2- methacrylic acid, (methyl) acryloyl morpholine, tetrahydrofurfuryl acrylate, 4- (methyl) acryloyloxymethyl -2- methyl -2- ethyl -1,3- dioxolanes, 4- (methyl) acryloyloxymethyl -2- first Base -2- isobutyl group -1,3- dioxolanes, 4- (methyl) acryloyloxymethyl -2- methyl -2- cyclohexyl -1,3- dioxolanes, 4- (methyl) acryloyloxymethyl -2,2- dimethyl -1,3- dioxolanes etc..Wherein, from easy acquirement heat resistance, colorant point From the aspect of dissipating property, the balance of solvent redissolution property, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third (methyl) alkyl acrylates such as olefin(e) acid butyl ester, (methyl) benzyl acrylate are to be suitable for.
As above-mentioned aromatic vinyl base system monomer, it can be cited for example that, styrene, vinyltoluene, Alpha-Methyl benzene second Alkene, methoxy styrene etc..Wherein, from the aspect of the heat-resisting coloring of resin, resistance to pyrolytic, styrene and/or second Alkenyl toluene is to be suitable for.
It, can be one kind or two or more in such as following compounds for as above-mentioned other monomers.
(methyl) acrylic amides such as N, N- dimethyl (methyl) acrylamide, N- methylol (methyl) acrylamide；It is poly- Styrene, poly- (methyl) methyl acrylate, polyoxyethylene, polypropylene oxide, polysiloxanes, polycaprolactone, polycaprolactam etc. There is the polymeric monomer class of (methyl) acryloyl group in an end of polymer molecular chain；1,3- butadiene, isoprene, neoprene Diene equiconjugate dienes；The vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate；First Base vinyl ethers, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2- ethylhexyl vinyl ether, n-nonyl second Alkene ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxy-ethylvinyl ether, ethoxy ethyl vinyl ether, first Oxygroup ethoxy ethyl vinyl ether, methoxy poly (ethylene glycol) vinyl ethers, 2- hydroxyethyl vinyl ether, 4- hydroxybutyl second The vinyl ethers such as alkene ether；N-vinyl pyrrolidone, N- caprolactam, N- vinyl imidazole, N- vinyl The N- vinyl compound class such as quinoline, N- vinyl acetamide；(methyl) acrylic acid isocyanates root closes ethyl ester, allyl isocyanic acid The unsaturated isocyanates class such as ester；Etc..
As by the method for above-mentioned polymerizing monomer components, it is usual that bulk polymerization, polymerisation in solution, emulsion polymerization etc. can be used The method used can be suitable for selection according to purpose, purposes.Wherein, for industrially it is advantageous, be also easy to carry out molecular weight etc. The reason of structural adjustment, polymerisation in solution are to be suitable for.Furthermore the mechanism of polymerization that above-mentioned monomer component can be used is based on free radical The polymerization of the mechanism such as polymerization, anionic polymerisation, cationic polymerization, coordination polymerization, the polymerization based on radical polymerization mechanism Method is industrially also advantageous, thus preferably.
As long as polymerization initiation methods in above-mentioned polymerization reaction can be by warm, electromagnetic wave (such as infrared ray, ultraviolet light, X-ray Deng), electron ray isoreactivity energy source to monomer component supply polymerization cause needed for energy, if further sharing polymerization Initiator can then substantially reduce energy required for polymerization causes, and be easy to control reaction, thus be suitable.
In addition, the molecular weight of polymer obtained from polymerizeing to above-mentioned monomer component can be by adjusting polymerization initiator Amount or type, polymerization temperature, the type of chain-transferring agent or amount etc. controlled.
In the case where being polymerize using solution polymerization process to above-mentioned monomer component, as molten used in polymerization Agent, as long as in the polymerization to be not particularly limited as long as inert.For example, can be according to mechanism of polymerization, used monomer Type or the polymerizing conditions such as amount, polymerization temperature, polymerization concentration set as one sees fit, thereafter curable resin combination is being made When object, in the case where using solvent as diluent etc., the solvent containing the solvent is used for the polymerisation in solution of monomer component In, this is efficient and is preferred.
As above-mentioned solvent, such as can suitably enumerate following compounds etc., can be used a kind or 2 kinds in them with On.
The single methanols class such as methanol, ethyl alcohol, isopropanol, n-butanol, sec-butyl alcohol；The glycols such as ethylene glycol, propylene glycol；Tetrahydro furan It mutters, the ring-type ethers such as dioxane；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, two Glycol list ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, 3- methoxybutanol etc. Glycol monoether；Glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl The glycol ethers such as ether, diethylene glycol (DEG) ethyl methyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether；Ethylene glycol monomethyl ether acetate, second two It is alcohol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, two sweet Alcohol monobutyl ether-acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic acid esters, dipropyl Glycol monomethylether acetate, dipropylene glycol monoethyl ether acetic acid esters, dipropylene glycol monobutyl ether acetic acid ester, 3- acetic acid methoxyl group fourth The esters of the glycol monoethers such as ester；Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, third Acetoacetic ester, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, 3- methoxy methyl propionate, 3- methoxypropionate, The alkyl esters such as 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, methyl acetoacetate, ethyl acetoacetate；Acetone, first The ketones such as base ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Benzene,toluene,xylene, ethylbenzene etc. are aromatic hydrocarbon；Hexane, hexamethylene The aliphatic hydrocarbons such as alkane, octane；The amides such as dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone；Etc..
Among these solvents, from the dissolubility of obtained polymer, form film when surface smoothness, to human body and The influence of environment is set out less, in terms of the easiness of industry acquisition, is more suitable for using propylene glycol monomethyl ether, propylene glycol monomethyl ether second Acid esters, diethylene glycol dimethyl ether, diethylene glycol (DEG) ethyl methyl ether, ethyl lactate.
It relative to above-mentioned 100 mass parts of monomer component is suitably 50 mass parts~1000 as the dosage of above-mentioned solvent Mass parts.More preferably 100 mass parts~500 mass parts.
In the case where being polymerize using radical polymerization mechanism to above-mentioned monomer component, it is produced from using based on heat It is industrially advantageous by the polymerization initiator of base, it is preferred.As such polymerization initiator, as long as passing through heat supply amount And generate free radicals and be just not particularly limited, it can be polymerize according to type of polymerization temperature or solvent, the monomer being polymerize etc. Condition carries out being suitable for selection.Alternatively, it is also possible to share the reducing agents such as transition metal salt, amine together with polymerization initiator.
As above-mentioned polymerization initiator, it can be cited for example that cumene hydroperoxide, di-isopropylbenzene hydroperoxide, di-t-butyl Peroxide, lauroyl peroxide, benzoyl peroxide, tert-butylperoxy isopropyl carbonate, peroxidating (2 ethyl hexanoic acid) The tert-butyl ester, azodiisobutyronitrile, 1,1 '-azos bis- (cyclohexane carbonitriles), 2,2 '-azos two (2,4- methyl pentane nitrile), diformazan The peroxidating that base 2,2 '-azo two (2 Methylpropionic acid ester), hydrogen peroxide, persulfate etc. are used usually as polymerization initiator Object, azo-compound etc., they can be used alone or in combination with two or more.
The dosage of above-mentioned polymerization initiator can be according to the type or amount of used monomer, polymerization temperature, polymerization concentration It waits molecular weight of polymerizing conditions, subject polymer etc. to set as one sees fit, is not particularly limited.For example, Weight-average molecular in order to obtain Amount is thousands of~tens of thousands of polymer, relative to above-mentioned 100 mass parts of monomer component, the polymerization initiator be 0.1 mass parts~ 20 mass parts are suitable.More preferably 0.5 mass parts~15 mass parts.
In above-mentioned polymerization, conventionally used chain-transferring agent can also be used as needed.It is preferred that polymerization initiator and chain are turned Agent is moved to share.It should be noted that if using chain-transferring agent in polymerization, then there are the increase that can inhibit molecular weight distribution and gel The tendency of change.
As above-mentioned chain-transferring agent, it can be cited for example that: mercaptan carboxylic acids' class such as thioacetic acid, 3- mercaptopropionic acid；Sulfydryl second Sour methyl esters, 3- mercapto-propionate, 3- mercaptopropionic acid -2- ethylhexyl, 3- mercaptopropionic acid n-octyl, 3- mercaptopropionic acid methoxyl group Butyl ester, 3- mercaptopropionic acid stearyl ester, trimethylolpropane tris (3-thiopropionate), pentaerythrite four (3-thiopropionate), Mercaptan carboxylic acids' esters such as dipentaerythritol six (3-thiopropionate)；Ethanethio, tert-butyl mercaptan, n-dodecyl mercaptan, The alkyl mercaptos alcohols such as 1,2- dimercaptoethane；The sulfydryls alcohols such as 2 mercapto ethanol, 4- sulfydryl-n-butyl alcohol；Benzenethiol, toluene sulphur Alcohol, to aromatic mercaptans classes such as toluenethiol, 2- naphthyl mercaptans；Three [(3- mercaptopropionyl oxygroup)-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) etc. sulfydryls isocyanuric acid esters；2- hydroxyl The disulfides such as base ethyl disulfide, Thiuram disulphide；Benzyl diethyldithiocarbamate etc. Dithiocarbamate；The monomers dimerization species such as α-methylstyrenedimer；Alkyl halides base class such as carbon tetrabromide etc..It Can be used alone, can also share two or more.
It among these, reduces that degree is small etc. to be considered from acquired, anti-crosslinking ability, polymerization speed, uses sulfydryl carboxylic Acids, mercaptan carboxylic acid's esters, alkyl thiol alcohols, sulfydryl alcohols, aromatic mercaptans class, sulfydryl isocyanuric acid esters etc. have mercapto The compound of base is to be suitable for.More preferably alkyl thiol alcohols, mercaptan carboxylic acid's class, mercaptan carboxylic acid's esters, further preferably N-dodecyl mercaptan, mercaptopropionic acid.
The dosage of above-mentioned chain-transferring agent polymerize according to the type or amount of used monomer, polymerization temperature, polymerization concentration etc. Condition, subject polymer molecular weight etc. set as one sees fit, be not particularly limited.For example, weight average molecular weight in order to obtain For thousands of~tens of thousands of polymer, relative to above-mentioned 100 mass parts of monomer component, the dosage of the chain-transferring agent is 0.1 mass parts ~20 mass parts are suitable.More preferably 0.5 mass parts~15 mass %.
About above-mentioned polymerizing condition, as polymerization temperature, according to the type of used monomer or amount, polymerization initiator Type or amount etc. take the circumstances into consideration to set, such as preferably 50 DEG C~150 DEG C, more preferably 70 DEG C~120 DEG C.Also, it can also be same Sample polymerization time is set as one sees fit, such as preferably 1 hour~6 hours, more preferably 2 hours~5 hours.
Above-mentioned (methyl) acrylic ester polymer is to make functional group and polymeric double bond with that can be bonded with acidic group Obtained from compound and base polymer (base polymer is will be obtained from above-mentioned polymerizing monomer components) react In the case where polymer (also referred to as polymer containing pendant double bonds), as double with the functional group and polymerism that can be bonded with acidic group The compound of key can be used one kind or two or more.In such compound, as polymeric double bond, it can be cited for example that (first Base) acryloyl group, vinyl, allyl, methylallyl etc., as the compound, with a kind in these polymeric double bonds Or two or more is to be suitable for.Wherein, from the aspect of reactive, preferred (methyl) acryloyl group.In addition, as can be with acid The functional group of base bonding, it can be cited for example that hydroxyl, epoxy group, oxetanyl, isocyanate group etc.；As the chemical combination Object, with one kind or two or more to be suitable in these functional groups.Wherein, from modification react speed, heat resistance, point From the aspect of dissipating property, preferred epoxy group (including glycidyl).
As the compound with the functional group and polymeric double bond that can be bonded with above-mentioned acidic group, it can be cited for example that (first Base) glycidyl acrylate, (methyl) senecioate-methylglycidyl esters, (methyl) senecioate-ethyl glycidyl Ester, vinylbenzyl glycidyl ether, allyl glycidyl ether, (methyl) acrylic acid (3,4- epoxycyclohexyl) methyl esters, second Alkenyl 7-oxa-bicyclo[4.1.0 etc. can be used one kind or two or more in them.Wherein, it is suitable for using with epoxy group and (methyl) The compound (monomer) of acryloyl group.
As the method for obtaining the above-mentioned polymer containing pendant double bonds, it can be cited for example that following methods: making above-mentioned basis Polymer makes the base polymer with when there is the compound of the functional group and polymeric double bond that can be bonded with acidic group to react Acidic group (preferably carboxyl) amount there is the amount surplus for the compound of functional group and polymeric double bond that can be bonded with acidic group than this Method；Above-mentioned base polymer is set to react with having the compound of the functional group and polymeric double bond that can be bonded with acidic group Afterwards, the method for further making that there is the compound of polyacid anhydride group to be reacted；Etc..
It is above-mentioned make base polymer (polymer preferably with carboxyl as acidic group) with have and can be bonded with acidic group In the process that the compound of functional group and polymeric double bond reacts, in order to ensure good reaction speed and gel is prevented Change, preferably the temperature range at 50 DEG C~160 DEG C carries out the process.The temperature be more preferably 70 DEG C~140 DEG C, further preferably It is 90 DEG C~130 DEG C.In addition, as catalyst, usually used esterification or transesterification can be used to improve reaction speed With basic catalyst, acidic catalyst.Wherein, for side reaction reduce the reason of, it is preferable to use basic catalyst.
As above-mentioned basic catalyst, it can be cited for example that: dimethyl benzyl amine, triethylamine, three n-octylamines, tetramethyl The tertiary amines such as ethylenediamine；Tetramethyl ammonium chloride, 4 bromide, tetrabutylammonium bromide, dodecyl trimethyl ammonium chloride etc. Quaternary ammonium salt；The carbamide compounds such as tetramethylurea；The alkyl guanidines such as tetramethylguanidine；The amidations such as dimethylformamide, dimethyl acetamide Close object；The tertiary phosphines such as triphenylphosphine, tributylphosphine；The quaternary alkylphosphonium salts such as 4-phenyl phosphonium bromide, three phenyl-bromide Phosphonium of benzyl；Etc., it can be with Using one kind or two or more in them.Wherein, consider from reactivity, treatability, halogen-free etc., preferably dimethyl benzyl Amine, triethylamine, tetramethylurea, triphenylphosphine.
It is double with the functional group's (such as epoxy group etc.) and polymerism that can be bonded with acidic group relative to above-mentioned monomer component 100 mass parts of total amount of the compound of key, the dosage of above-mentioned catalyst are preferably 0.01 mass parts~5.0 mass parts.More preferably For 0.1 mass parts~3.0 mass parts.
It is above-mentioned to occur that base polymer instead with the compound with the functional group and polymeric double bond that be bonded with acidic group In the process answered, gelation in order to prevent, preferably addition polymerization inhibitor are simultaneously somebody's turn to do in the presence of the gas containing molecularity oxygen Process.It is blown into anti-as the gas containing molecularity oxygen usually using the air or oxygen after the dilution of the inert gases such as nitrogen It answers in container.
As above-mentioned polymerization inhibitor, conventionally used free radical polymerization monomer polymerization inhibitor can be used, example can be enumerated Such as: quinhydrones, methylnaphthohydroquinone, trimethylhydroquinone, tert-butyl hydroquinone, p-hydroxyanisole, 6- tert-butyl -2,4- dimethlbenzene, 2, 6- DI-tert-butylphenol compounds, 2,6- di-t-butyl -4- metoxyphenol, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol) etc. Phenol system polymerization inhibitor；Organic acid mantoquita, phenthazine etc. can be used one kind or two or more in them.Wherein, from less colored, anti- Ability only polymerizeing etc. consideration, preferably phenol system polymerization inhibitor；For the reason of the accessibility, economy, more preferable 2,2 '-is sub- Methyl bis- (4- methyl-6-tert-butylphenols), p-hydroxyanisole, 6- tert-butyl -2,4- dimethlbenzene, 2,6- di-tert-butyl Phenol.
As the dosage of above-mentioned polymerization inhibitor, from the effect for ensuring adequately to prevent polymerization and curable resin combination is made Curability when object etc. is set out, double with the functional group and polymerism that can be bonded with acidic group relative to above-mentioned monomer component 100 mass parts of total amount of the compound of key, the dosage of the polymerization inhibitor are preferably 0.001 mass parts~1.0 mass parts.More preferably 0.01 mass parts~0.5 mass parts.
As the above-mentioned compound with polyacid anhydride group, it can be cited for example that, succinic anhydride, dodecenyl succinic Acid, pentadecane alkenyl succinic acid, octadecenyl succinic acid, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, six Hydrogenated phthalic anhydride, methyl hexahydro phthalic anhydride, Nadic anhydride, methylendomethylenetetrahydrophthalic Tetrabydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, inclined benzene three Acid anhydrides, pyromellitic acid dianhydride etc. can be used one kind or two or more in them.
It is suitable that the weight average molecular weight of above-mentioned (methyl) acrylic ester polymer, which is 2000~250000,.Due to being in Such range can play be more good developability.The weight average molecular weight is more preferably 3000~100000, is further excellent It is selected as 4000~50000.It should be noted that above-mentioned (methyl) acrylic ester polymer is high molecular weight (for example, 10000 ~50000) in the case where, has the tendency that obtaining the solidfied material of more high rigidity；By controlling as high acid value (preferably 150mgKOH/g or more, 200mgKOH/g or less), there is the tendency for being easy to develop.
The weight average molecular weight of polymer can for example acquire as be described hereinafter.
Above-mentioned (methyl) acrylic ester polymer is that the polymer for having double bond in side chain (polymerize containing pendant double bonds Object) in the case where, double bond equivalent is preferably 200~10000.Due to being in such range, the preservation of polymer can be made to stablize Property is be more good.The double bond equivalent is more preferably 200~5000, further preferably 250~4000, particularly preferably 300~ 4000。
So-called double bond equivalent is consolidating for polymer solution (the also referred to as resin solution) relative to every 1mol polymer double bond The quality of body ingredient.The quality of the solid component of polymer solution described herein is the matter of the constituent of above-mentioned monomer component Total quality of amount and the quality of polymerization inhibitor.Pass through the double bond by the quality of the solid component of polymer solution divided by polymer Amount, can acquire the double bond equivalent.The double bond amount of polymer can by input acidic group with there is the functional group that can be bonded and gather The amount of the compound of conjunction property double bond acquires.
In addition, hardening resin composition of the invention is to have selected from further being contained by the hardening resin composition In the group that further there is the mode of hydroxyl to form for the mode of the polymer of hydroxyl and (methyl) acrylic ester polymer At least one mode.So by having hydroxyl in system, by above-mentioned from (methyl) acrylic ester list containing tertiary carbon The structural unit of body decomposes and generates (methyl) acrylic acid, and ester cross-linked structure is generated between generated (methyl) acrylic acid, Based on the reason, curability is especially high, can obtain the especially excellent solidfied material of the transparency.It should be noted that above-mentioned solid While the property changed resin combination further contains the polymer with hydroxyl, above-mentioned (methyl) acrylic ester polymer can also Further to have hydroxyl.
Further there is the mode of hydroxyl as above-mentioned (methyl) acrylic ester polymer, it may be preferable to Enumerate: base polymer, the base polymer are obtained from polymerizeing monomer component, which contains containing tertiary carbon (methyl) acrylate monomer and monomer with hydroxyl and polymeric double bond, preferably further containing having acidic group With the monomer of polymeric double bond；Polymer containing pendant double bonds, it is to make the base polymer and have that this, which contains pendant double bonds polymer, Obtained from the compound of the functional group and polymeric double bond that can be bonded with acidic group reacts.Wherein preferred the latter contain side chain Double-bond polymerization object.
<polymer with hydroxyl>
Above-mentioned hardening resin composition also further contains other than containing above-mentioned (methyl) acrylic ester polymer In the case where having the polymer with hydroxyl, as the polymer with hydroxyl, do not have as long as there is hydroxyl in the molecule It is particularly limited to.Wherein, it from the aspect of further increasing developability, preferably shows alkali-soluble polymer, is suitably In the molecule with the polymer of acidic group.About acidic group, such as in above-mentioned (methyl) acrylic ester polymer as described above；It closes Above-mentioned suitable model in the acid value of the above-mentioned polymer with hydroxyl, preferably also above-mentioned (methyl) acrylic ester polymer In enclosing.
As the above-mentioned polymer with hydroxyl, preferably it can be cited for example that: base polymer, the base polymer are to make Monomer containing hydroxyl and polymeric double bond, the monomer component preferably further containing the monomer with acidic group and polymeric double bond Obtained from being polymerize；Polymer containing pendant double bonds, this contain pendant double bonds polymer be make the base polymer with have can Obtained from the compound of the functional group and polymeric double bond that are bonded with acidic group reacts.Wherein preferred the latter's is double containing side chain Key polymer.
In this way, above-mentioned (methyl) acrylic ester polymer and/or the polymer with hydroxyl are to have polymerization in side chain Property double bond polymer mode be included in suitable way of the invention in.
In the monomer component that above-mentioned formation has the polymer of hydroxyl, monomer with hydroxyl and polymeric double bond, with And preferred embodiment, concrete example of the monomer with acidic group and polymeric double bond etc. is as described above, each monomer can use a kind respectively Or two or more.
For the content ratio of the above-mentioned monomer with hydroxyl and polymeric double bond, for example, having relative to above-mentioned formation The 100 mass % of total amount of the monomer component of the polymer of hydroxyl, the content ratio are preferably 1 mass % or more.More preferably 5 matter Measure % or more, further preferably 10 mass % or more.And preferably 90 mass % or less, more preferably 50 mass % or less, into One step is preferably 25 mass % or less.
The content ratio of the above-mentioned monomer with acidic group and polymeric double bond is suitable for being set as that acid value is made to be in above-mentioned preferred In the range of, for example, having the 100 mass % of total amount of the monomer component of the polymer of hydroxyl relative to above-mentioned formation, there is acidic group Content ratio with the monomer of polymeric double bond is preferably 5 mass % or more.More preferably 10 mass % or more, it is more preferably 20 mass % or more.And preferably 99 mass % or less, more preferably 85 mass % or less, further preferably 60 mass % with Under, particularly preferably 50 mass % or less.
Formed in the monomer component of the above-mentioned polymer with hydroxyl, in addition to above-mentioned monomer, can also containing it is other can The monomer of copolymerization.As other monomers, the suitable N substituted maleimide amine system monomer using for example in addition to above-mentioned monomer, two Alkyl -2,2 '-(oxygroup dimethylene) diacrylate system monomer, alkyl-(α-allyloxy methyl) acrylate monomer, It is one kind or two or more in (methyl) acrylate monomer, aromatic vinyl base system monomer etc..Their suitable way and tool Body example etc. is as above-mentioned.
It should be noted that in the 100 mass % of total amount of monomer component for forming the above-mentioned polymer with hydroxyl, The content ratio of its monomer is preferably 60 mass % or less, preferably 50 mass % or less.Especially replacing Malaysia acyl containing N In the case where imines system monomer, from heat resistance, hardness, colorant dispersibility, developing powder, transparency etc., contain Ratio is preferably 2 mass of mass %~60 %, more preferably 2 mass of mass %~50 %, further preferably 3 matter of mass %~40 Measure %.
About above-mentioned monomer component polymerization, make with the change of functional group and polymeric double bond that can be bonded with acidic group Close object with above-mentioned monomer component is polymerize obtained from the method that reacts of base polymer it is for example above-mentioned.
In above-mentioned hardening resin composition, (methyl) acrylic ester polymer and the polymer with hydroxyl contain Ratio can depending on the application or the mixing of other ingredients etc. is set as one sees fit, for example, the solid relative to hardening resin composition 100 mass % of ingredient total amount, their total solid component content (without containing the polymer with hydroxyl, are meaned The only solid component content of (methyl) acrylic ester polymer.) it is preferably 5 mass % or more.It and is suitably 80 mass % Below.By being in such range, effect of the invention can be played more significantly.The content be more preferably 7 mass %~ 70 mass %, further preferably 10 mass of mass %~60 %.
It should be noted that so-called " solid component total amount " refers to that form the ingredient of solidfied material (waves when the formation of solidfied material Except solvent of hair etc.) total amount.
Herein, containing above-mentioned (methyl) acrylic ester polymer and there is the case where both polymer of hydroxyl Under, about their mixing ratio, as long as the heat of the structural unit according to (methyl) acrylate monomer of the self-contained tertiary carbon of origin (methyl) acrylic acid for decomposing and generating is easy to happen the mode of ester crosslinking with the hydroxyl in system to set to its mixing ratio It is fixed, it is not particularly limited.For example, their mass ratio ((methyl) acrylic ester polymer/polymerization with hydroxyl Object)=1~99/99~1 be suitable for.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 polymerism list Body, be can by free radical, electromagnetic wave (such as infrared ray, ultraviolet light, X-ray etc.), electron ray isoreactivity energy line photograph Penetrate etc. and low molecular compound polymerize, with polyunsaturated bond (also referred to as polymerism unsaturated group).Example The monofunctional compound with 1 polymerism unsaturated group in the molecule can such as be enumerated and there are 2 or more polymerisms The polyfunctional compound of unsaturated group.
As above-mentioned simple function polymerizable monomer, it can be cited for example that as in above-mentioned (methyl) acrylic ester polymer Monomer component in other monomers for preferably comprising and N substituted maleimide amine or (methyl) third among compound that example goes out Olefin(e) acid esters；(methyl) acrylic amide；Unsaturated monocarboxylic class；Unsaturated polybasic carboxylic acid class；Between unsaturated group and carboxyl The unsaturated monocarboxylic class of chain extension occurs；Unsaturated acids anhydride；Aromatic vinyl base class；Conjugated diene；Vinyl ester；Second Alkenyl ethers；N- vinyl compound class；Unsaturated isocyanate class；Etc..
As above-mentioned multifunctional polymerizable monomer, it can be cited for example that following compounds etc..
Ethylene glycol two (methyl) acrylate, diethylene glycol (deg) two (methyl) acrylate, polyethylene glycol two (methyl) acrylic acid Ester, propylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, hexamethylene Alkane dimethanol two (methyl) acrylate, bisphenol-A epoxy alkane two (methyl) acrylate, Bisphenol F epoxy alkane two (methyl) 2 function such as acrylate (methyl) acrylate compounds；
Trimethylolpropane tris (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, three (first of glycerol Base) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, five (first of dipentaerythritol Base) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tripentaerythritol Eight (methyl) acrylate, ethylene oxide addition trimethylolpropane tris (methyl) acrylate, double three hydroxyls of ethylene oxide addition Methylpropane four (methyl) acrylate, ethylene oxide addition pentaerythrite four (methyl) acrylate, ethylene oxide addition two Pentaerythrite six (methyl) acrylate, propylene oxide addition trimethylolpropane tris (methyl) acrylate, propylene oxide add At double trimethylolpropane four (methyl) acrylate, propylene oxide addition pentaerythrite four (methyl) acrylate, oxidation third Alkene addition dipentaerythritol six (methyl) acrylate, 6-caprolactone addition trimethylolpropane tris (methyl) acrylate, ε- Caprolactone addition double trimethylolpropane four (methyl) acrylate, 6-caprolactone addition pentaerythrite four (methyl) acrylic acid Multifunctional (methyl) acrylates more than 3 functions such as ester, 6-caprolactone addition dipentaerythritol six (methyl) acrylate Close object；
Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl Ether, butanediol divinyl ether, hexylene glycol divinyl ether, bisphenol-A epoxy alkane divinyl ether, Bisphenol F epoxy alkane two Vinyl ethers, trimethylolpropane tris vinyl ethers, double trimethylolpropane tetravinyl ether, glycerol trivinyl ether, season penta Tetrol tetravinyl ether, five vinyl ethers of dipentaerythritol, six vinyl ethers of dipentaerythritol, ethylene oxide addition trihydroxy methyl Propane trivinyl ether, ethylene oxide addition double trimethylolpropane tetravinyl ether, ethylene oxide addition pentaerythrite tetrem The polyfunctional vinyls ethers such as alkene ether, six vinyl ethers of ethylene oxide addition dipentaerythritol；
(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 fourth Ester, (methyl) acrylic acid -4- ethyleneoxy cyclohexyl, (methyl) acrylic acid -5- ethyleneoxy pentyl ester, (methyl) acrylic acid -6- The own ester of ethyleneoxy, (methyl) acrylic acid -4- ethyleneoxy methylcyclohexyl methyl esters, (methyl) acrylic acid are to ethyleneoxy methyl Phenyl methyl esters, (methyl) acrylic acid -2- (vinyloxyethoxy) ethyl ester, (methyl) acrylic acid -2- (vinyloxyethoxy second Oxygroup ethyoxyl) (methyl) esters of acrylic acid containing vinyl ether group such as ethyl ester；
Ethylene glycol diallyl ether, diethylene glycol (DEG) diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl Ether, butanediol diallyl ether, hexylene glycol diallyl ether, bisphenol-A epoxy alkane diallyl ether, Bisphenol F epoxy alkane two Allyl ether, trimethylolpropane tris allyl ether, double trimethylolpropane tetraallyl ether, glycerol triallyl ether, season penta Tetrol tetraallyl ether, five allyl ether of dipentaerythritol, six allyl ether of dipentaerythritol, ethylene oxide addition trihydroxy methyl Propane triallyl ether, ethylene oxide addition double trimethylolpropane tetraallyl ether, ethylene oxide addition pentaerythrite tetraene The multifunctional allyl ether series such as propyl ether, six allyl ether of ethylene oxide addition dipentaerythritol；
(methyl) esters of acrylic acid containing allyl such as (methyl) allyl acrylate；
Three (acryloyl-oxyethyl) isocyanuric acid esters, three (methacryloxyethyl) isocyanuric acid esters, alkylene oxide Hydrocarbon addition three (acryloyl-oxyethyl) isocyanuric acid ester, epoxyalkane addition three (methacryloxyethyl) isocyanuric acid Ester etc. contains the isocyanuric acid esters of multifunctional (methyl) acryloyl group；
Triallyl isocyanurate etc. contains the isocyanuric acid esters of multifunctional allyl；
It is multifunctional different by toluene di-isocyanate(TDI), isophorone diisocyanate, benzene dimethylene diisocyanate etc. (methyl) acrylic acid of the hydroxyls such as cyanate and (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate Polyfunctional carbamate obtained from the reaction of esters (methyl) esters of acrylic acid；
The multifunctional aromatic vinyl base class such as divinylbenzene；Deng.
In above-mentioned polymerizable compound, examined in terms of the curability for further increasing hardening resin composition of the present invention Consider, is suitable for using multifunctional polymerizable compound.In the case where using multifunctional polymerizable compound as polymerizable compound, It is preferably 3 or more, more preferably 4 or more, further preferably 5 or more as its functional number.In addition, from solidification is further suppressed From the aspect of contraction, functional number is preferably 10 or less, more preferably 8 or less.
In addition, the molecular weight as above-mentioned polymerizable compound is not particularly limited, and from processing aspect, for example, it is suitable Preferably 2000 or less.
In the case where using multifunctional polymerizable compound as above-mentioned polymerizable compound, in the polymerizable compound, From reactivity, economy, acquired etc., it is suitable for using multifunctional (methyl) acrylate compounds, multifunctional ammonia Carbamate (methyl) acrylate compounds, isocyanurate compound containing (methyl) acryloyl group etc. have (methyl) The compound of acryloyl group.Thus more preferably multifunctional (methyl) acrylate compounds can make hardening resin composition Photonasty and curability it is more excellent, it is available further with more high rigidity high transparency solidfied material.Further It is preferable to use multifunctional (methyl) acrylate compounds more than 3 functions.
It, can be according to used polymerizable compound or above-mentioned (first as the content ratio of above-mentioned polymerizable compound Base) acrylic ester polymer type and purpose or purposes etc. set as one sees fit, it is more excellent from developability, plate-making property From the aspect of, relative to the 100 mass % of solid component total amount of hardening resin composition, which is preferably 2 matter % or more is measured, and is suitably 80 mass % or less.5 mass % or more, further preferably 8 mass % are more preferably as lower limit value Above, 10 mass % or more are particularly preferably, are more preferably 70 mass % or less, further preferably 50 mass % as upper limit value Below, 30 mass % or less are particularly preferably, are most preferably 20 mass % or less.
<Photoepolymerizationinitiater initiater>
Above-mentioned hardening resin composition further contains Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, preferably certainly By base polymerism Photoepolymerizationinitiater initiater.So-called free-radical polymerised Photoepolymerizationinitiater initiater is to pass through electromagnetic wave or electron ray etc. The irradiation of active energy ray and the substance for generating polymerization initiation radical, can be used one kind or two or more conventionally used object Matter.In addition it is also possible to share one kind or two or more photosensitizer or optical free radical polymerization accelerant etc. as needed.Photosensitizer And/or optical free radical polymerization accelerant can be used together with Photoepolymerizationinitiater initiater, can also not use photosensitizer and/or light certainly By base polymerization accelerant.The application hair can also be given full play of even if inadequacy photosensitizer and/or optical free radical polymerization accelerant Bright effect can further improve sensitivity, curability in the case where sharing.
As above-mentioned Photoepolymerizationinitiater initiater, specifically, it can be cited for example that following compound etc..
2,2- diethoxy acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 1- hydroxycyclohexyl 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-1- (4- methyl mercapto phenyl) -2- morphoinopropyl 1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1,2- The alkyl phenones system chemical combination such as (dimethylamino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] -1- butanone Object；The benzophenone based compounds such as benzophenone, 4,4 '-bis- (dimethylamino) benzophenone, 2- carboxyl benzophenone；Benzoin The benzoins based compound such as methyl ether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether；Thioxanthones, 2- ethyl thioxanthene The thioxanthones system such as ketone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone chemical combination Object；
Bis- (the trichloromethyl)-s- triazines of 2- (4- methoxyphenyl) -4,6-, 2- (4- methoxyl group naphthalene) bis- (trichlorines of -4,6- Methyl)-s- triazine, bis- (the trichloromethyl)-s- triazines of 2- (4- ethoxynaphthyl) -4,6-, 2- (4- ethoxy carbonyl naphthalene) -4, The halomethylations triazine based compounds such as bis- (the trichloromethyl)-s- triazines of 6-；2- trichloromethyl -5- (2 '-benzofuranyl) -1,3, 4- oxadiazoles, 2- trichloromethyl -5- [β-(2 '-benzofuranyl) vinyl] -1,3,4- oxadiazoles, 4- oxadiazoles, 2- trichlorine The halomethylations oxadiazoles based compounds such as methyl -5- furyl -1,3,4- oxadiazoles；2,2 '-bis- (2- chlorphenyls) -4,4 ', 5, 5 '-tetraphenyls -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4 dichloro benzene base) -4,4 ', 5,5 '-tetraphenyls -1,2 '-bisglyoxaline, 2, The bisglyoxalines based compounds such as 2 '-bis- (2,4,6- trichlorophenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines；1,2- octane two Ketone, 1- [4- (thiophenyl) -, 2- (O- benzoyl oximes)], ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- click Azoles -3- base] -, the oximes ester based compound such as 1- (O- acetyl group oxime)；Bis- (η 5-2,4- cyclopentadiene -1- bases)-bis- (2,6- bis- is fluoro- 3- (1H- pyrroles -1- base)-phenyl) the cyclopentadiene titanium sub-group compound such as titanium；P-(dimethylamino)-benzoic acid, to diethylamino benzene The benzoic ethers based compound such as formic acid；Acridines based compound such as 9- phenylacridine etc..
As the photosensitizer or optical free radical polymerization accelerant that can be shared with above-mentioned Photoepolymerizationinitiater initiater, example can be enumerated Such as: xanthene pigment, cumarin pigment, 3- ketone coumarin series compounds, pyrroles's methine pigment pigment based compound；4- diformazan ammonia The dialkyl amidos benzene compounds such as yl benzoic acid ethyl ester, 4- dimethylaminobenzoic acid -2- ethylhexyl；2- sulfydryl benzo thiophene The mercaptan system such as azoles, 2- mercaptobenzoxazole, 2-mercaptobenzimidazole hydrogen donor etc..
The content of above-mentioned Photoepolymerizationinitiater initiater can take the circumstances into consideration to set according to purpose, purposes etc., be not particularly limited；Relative to removing 100 mass parts of solid component total amount of hardening resin composition outside Photoepolymerizationinitiater initiater, the content are suitably 0.1 mass parts More than.The more excellent solidfied material of adaptation can be obtained as a result, stripping can also be more sufficiently suppressed even if after high temperature exposure It falls.In addition, if considering, influence and the balance with economy etc., the content brought by the decomposition product of Photoepolymerizationinitiater initiater are excellent It is selected as 30 below the mass.0.5 mass parts or more are more preferably as lower limit value, are more preferably 1 mass parts or more, special It more than preferably 2 mass parts, is more preferably 25 below the mass, further preferably 20 below the mass as upper limit value.
Above-mentioned photosensitizer and optical free radical polymerization accelerant can not use as described above, in a situation of use where, from admittedly It sets out in terms of the balance of influence and economy brought by the property changed, decomposition product, relative to consolidating for hardening resin composition 100 mass % of body ingredient total amount, the content are preferably 0.001 mass of mass %~20 %.More preferably 0.01~15 mass %, into one Step is preferably 0.05~10 mass %.
<other ingredients>
Solvent-
In addition, above-mentioned hardening resin composition is suitable for containing solvent.Solvent as diluent etc. it is preferable to use.That is, tool It says to body, dissolution is suitably used for following purposes: reducing viscosity, improves treatability；Film is formed by drying； Decentralized medium as colorant；Etc., it is each ingredient contained in dissolvable or dispersion hardening resin composition, low The organic solvent or water of viscosity.
As above-mentioned solvent, usually used solvent can be used, can be suitable for selection according to purpose, purposes, without special It limits, for example, following compounds etc..These solvents can be used alone, and can also share two or more.
The single methanols class such as methanol, ethyl alcohol, isopropanol, n-butanol, sec-butyl alcohol；The glycols such as ethylene glycol, propylene glycol；Tetrahydro furan It mutters, the ring-type ethers such as dioxane；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, two Glycol list ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, 3- methoxybutanol etc. Glycol monoether；Glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl The glycol ethers such as ether, diethylene glycol (DEG) ethyl methyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether；
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether 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, dihydroxypropane single-ether Acetic acid esters, propylene glycol monobutyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, dipropylene glycol monoethyl ether acetic acid esters, a contracting dipropyl The esters of the glycol monoethers such as glycol monobutyl ether acetic acid esters, 3- methoxy butyl acetate；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- methoxypropionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, acetoacetate first The alkyl esters such as ester, ethyl acetoacetate；The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Benzene, toluene, Dimethylbenzene, ethylbenzene etc. are aromatic hydrocarbon；The aliphatic hydrocarbons such as hexane, hexamethylene, octane；Dimethylformamide, dimethylacetamide The amides such as amine, N-Methyl pyrrolidone；Water；Etc..
As the dosage of above-mentioned solvent, it can take the circumstances into consideration to set according to purpose, purposes, be not particularly limited, it is solid in the present invention In the 100 mass % of total amount of the property changed resin combination, preferably make 10 mass of mass %~90 % of its content.More preferably 20 mass % ~80 mass %.
In above-mentioned hardening resin composition, characteristic required by each purposes according to applied by it can also be further Containing one kind or two or more in such as following substances: colorant (also referred to as colorant)；Dispersing agent；Heat-resisting enhancer；Levelling agent； Development promoter；The inorganic particles such as silicon dioxide microparticle；The coupling agents such as silane system, aluminium system, titanium system；Filler, epoxy resin, phenol tree The thermosetting resins such as rouge, polyvinylphenol；The auxiliary curing agents such as multi-functional thiol's compound；Plasticizer；Polymerization inhibitor；Ultraviolet light is inhaled Receive agent；Antioxidant；Matting agent；Defoaming agent；Antistatic agent；Antiseize paste；Surface modifier；Thixotropic agent；Thixotropic agents；Quinone two is folded Nitrogen compound；Polyhydric phenols；Cationically polymerizable compound；Acid agent；Etc..For example, by above-mentioned curable resin In the case that composition is used for color filter application, colorant is preferably comprised.In this way, above-mentioned hardening resin composition further contains The mode of colorant is also one of suitable way of the invention.It is additionally suitably containing selected from by colorant, dispersing agent, heat-resisting raising The mode of at least one of the group that agent, levelling agent, coupling agent and development promoter form.Contain ingredient to these below to say It is bright.
Colorant-
As above-mentioned colorant, such as pigment, dyestuff can be suitably used.They can be used alone, can also be by two or more group It closes and uses.In addition, can be by pigment and dye combinations.For example, in the case where forming red, the blue, green pixel of colour filter, Suitable for using Lan Yuzi, the green method combined with the colorants such as yellow to play required chromatic characteristic.In addition, black being formed In the case where bottom, it is possible to use black material is formed.
In above-mentioned pigment and dyestuff, from the aspect of such as durability, pigment (such as organic pigment or inorganic pigment) It is excellent；In addition, dyestuff is excellent, thus can be according to required from the aspect of the brightness for for example improving panel etc. Characteristic they are suitably selected or are shared.It should be noted that more preferable organic pigment in pigment.
As above-mentioned pigment, it can be cited for example that: azo pigment, phthualocyanine pigment, polycyclic pigment (such as quinacridine Ketone system, perylene system, purple cyclic ketones system, isoindolinone system, isoindoline system, dioxazines system, thioindigo system, anthraquinone system, quinoline Phthalein ketone system, metal complex system, diketopyrrolopyrrolecocrystals system etc.), the organic pigments such as Dye lake system pigment；White constitution Pigment (such as titanium dioxide, zinc oxide, zinc sulphide, clay, talcum, barium sulfate, calcium carbonate etc.), color pigment (such as chrome yellow, Cadmium system, chrome vermilion, NiTi, chromium titanium, yellow iron oxide, iron oxide red, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chromium Green, chromium oxide, pucherite etc.), black pigment (such as carbon black, bone black, graphite, iron oxide black, titanium black etc.), bright materials pigments (example Such as pearl pigment, aluminium pigment, bronze pigments), the inorganic pigments such as fluorescent pigment (such as zinc sulphide, strontium sulfide, strontium aluminate etc.). In addition, the color as workable pigment, can enumerate yellow, red, purple, blue, green, brown, black, white Deng.
Above-mentioned pigment can also carry out rosin processing according to purpose, purposes, surfactant is handled, at resin system dispersing agent The surface treatments such as reason, pigment derivative processing, oxide film thereon processing, silica-coating, wax coating.
Following color separations pass through color index (C.I.；The Society of Dyers and Colourists distribution) it compiles Number the concrete example of above-mentioned pigment is shown, but colorant of the invention is not limited in these.In addition, they can be used alone, It can also be used in combination of two or more.Following " C.I. " means color index, and number means that color index is numbered.
As yellow uitramarine, it can be cited for example that 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, it can be cited for example that 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, it can be cited for example that 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, it can be cited for example that 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, it can be cited for example that 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, it can be cited for example that 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, it can be cited for example that C.I. pigment brown 5,6,23,24,25,32,41,42 etc..
As black pigment, it can be cited for example that nigrosine, carbon black, lampblack, bone black, iron oxide black, titanium are black, C.I. pigment black 1, 6,7,9,10,11,12,13,20,31,32,34 etc..As white pigment, it can be cited for example that 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, such as Japanese Unexamined Patent Publication 2010-9033 bulletin, Japanese Unexamined Patent Publication 2010-211198 can be used Number bulletin, Japanese Unexamined Patent Publication 2009-51896 bulletin, the organic dyestuff recorded in Japanese Unexamined Patent Publication 2008-50599 bulletin.Wherein It is preferred that 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..
The content ratio (i.e. total ratio of pigment and dyestuff) of above-mentioned colorant can take the circumstances into consideration to set according to purpose, purposes, phase For the 100 mass % of solid component total amount of hardening resin composition, the preferred scope of the content ratio of the colorant is 3 mass % ~70 mass %.More preferably 5 mass of mass %~60 %, further preferably 10 mass of mass %~50 %.
Dispersing agent-
Above-mentioned dispersing agent have the position that interacts with colorant and with decentralized medium (such as solvent or binder tree Rouge) interaction position, have the function of making colorant dispersion stability in a dispersion medium, be typically categorized into resin type Dispersing agent (such as macromolecule dispersing agent), surfactant (such as low molecule dispersing agent), pigment derivative.Solidification of the invention Property resin combination be suitable for contain dispersing agent together with colorant.It should be noted that as dispersing agent (i.e. resin type dispersing agent, Surfactant and/or pigment derivative), usually used dispersing agent can be used.In addition, as dispersing agent, it can be independent It is used singly, or in combination of two or more kinds.
As above-mentioned resin type dispersing agent, it can be cited for example that: the multi-carboxylates such as polyurethane, polyacrylate；Insatiable hunger It is poly- with polyamide, polybasic carboxylic acid, polybasic carboxylic acid amine salt, polybasic carboxylic acid ammonium salt, polybasic carboxylic acid alkylamine salt, polysiloxanes, long-chain Amino amides phosphate, the multi-carboxylate containing hydrogen-based；By poly- (rudimentary alkyleneimines) and with the polyester of free carboxy Reaction and the amide formed or its salt；(methyl) acrylic-styrene copolymer, (methyl) acrylic acid-(methyl) acrylic acid Ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, Polyester, modified polyacrylate, ring Oxidative ethane/polypropylene oxide addition product etc..
In addition, the structure as above-mentioned resin type dispersing agent, particularly preferably using Grafting Structure, (such as main chain is to have and color The anchor chain at the position of the interaction of material, grafted chain are the compatibility chain with the interaction with decentralized medium) resin, Or anchor chain and compatibility chain form the resin of block structure.
If enumerating the trade name of above-mentioned resin type dispersing agent, such as following substance can be enumerated.Wherein it is 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 above by EFKA ADDITIVES society)；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 (being manufactured above by Bi Ke chemistry society)；SOLSPERSE3000,5000,9000,12000,13240, 13940,17000,20000,22000,24000,24000GR, 26000,28000 (being manufactured above by Japanese Lu Borun society)； Disperlon7301,325,374,234,1220,2100,2200, KS260, KS273N, 152MS are (above by this chemical conversion of nanmu society Manufacture)；AJISPER PB-711,821,822,880, PN-411, PA-111 are (above by AJINOMOTO FINE TECHNO society Manufacture)；KP series (chemical industry society manufacture)；POLYFLOW series (manufacture of chemistry society, common prosperity society)；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, it can be cited for example that: polyoxyethylene alkyl ether sulfate salt, dodecyl benzene sulfonic acid Sodium, Negel, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, the moon The anionic surfactant such as osmanthus base ammonium sulfate, odium stearate, NaLS；Polyoxyethylene oleyl ether, polyoxy second Alkene lauryl ether, ethylene nonyl phenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate Equal nonionic surface active agent；The cationic surface active agents such as alkyl quaternary ammonium salts or their ethylene oxide adduct；Alkane The amphoteric surfactantes such as alkyl betaines, the alkyl imidazolines such as base dimethylamino acetic acid glycine betaine；Etc..
Above-mentioned pigment derivative is the compound that the structure of functional group has been imported in pigment, as functional group, Ke Yiju Out such as sulfonic group, sulfoamido and its quaternary salt, dialkyl amido, hydroxyl, carboxyl, amide groups, phthalimide-based. As become parent pigmentary structures, it can be cited for example that azo system, anthraquinone system, quinophthalone system, phthalocyanine system, quinacridone, Benzimidazolone system, isoindoline system, dioxazines system, indanthrene system, perylene system, diketopyrrolopyrrolecocrystals system etc..
The content ratio of above-mentioned dispersing agent (i.e. resin type dispersing agent, surfactant and/or pigment derivative) can basis Purpose or purposes take the circumstances into consideration to set, from the balance of dispersion stabilization, durability (heat resistance, light resistance, weatherability etc.) and the transparency Aspect set out, relative to the 100 mass % of solid component total amount of hardening resin composition, which is for example preferably 0.01 mass of mass %~60 %.More preferably 0.1 mass of mass %~50 %, further preferably 0.3 mass of mass %~40 %.
Heat-resisting enhancer-
Above-mentioned heat-resisting enhancer is used to improve heat resistance or intensity.As heat-resisting enhancer, such as N- (alkane Oxygroup methyl) melamine compound, compound with 2 or more epoxy groups or oxetanyl etc. is be suitable for. Especially exhausted with transparent resist, interlayer using above-mentioned hardening resin composition as light spacer resist, protective film In the case where velum resist use, it is preferable to use they.
Levelling agent-
Above-mentioned levelling agent be in order to improve levelability and it is preferable to use.As levelling agent, preferably fluorine system, silicon systems surface is living Property agent.
Coupling agent-
Above-mentioned coupling agent be in order to improve adaptation and it is preferable to use.It, can as coupling agent, preferably silane series coupling agent To enumerate such as epoxy, metha crylic, amino system silane coupling agent.Wherein preferred epoxy silane coupling agent.
Development promoter-
Above-mentioned development promoter be in order to improve developability and it is preferable to use.It is as development promoter, such as following substances Suitable: the monocarboxylic acids class such as (methyl) acrylic acid, acetic acid, propionic acid；Maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid, The polybasic carboxylic acids class such as trimellitic acid；The carboxyanhydrides such as maleic anhydride, succinic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride； Etc..
Manufacturing method as above-mentioned hardening resin composition is not particularly limited, such as can be by using various mixed Conjunction machine or dispersion machine containing ingredient mix above-mentioned dispersion and prepare.Mixing dispersion step is not particularly limited, and utilizes Usual way carries out.It furthermore can also further comprise the other process usually carried out.It should be noted that above-mentioned solid It is suitable for that the decentralized processing process through colorant is manufactured in the case that the property changed resin combination contains colorant.
As the decentralized processing process of above-mentioned colorant, it can be cited for example that following methods: weighing specific quantity respectively first Colorant (preferably organic pigment), dispersing agent and solvent, using paint mixing unit (Paint Conditioner), ball mill, edge runner, The colorant point of liquid is made in colorant micro disperse by the dispersion machines such as ball mill, jet pulverizer, homogenizer, kneader, blender Dispersion liquid (also referred to as millbase).Mixing decentralized processing is carried out preferably by edge runner, kneader, blender etc., is utilized later The Media mills such as the ball mill filled with 0.01mm~1mm mill pearl carry out micro disperse processing.Add in obtained millbase Enter in addition be stirred in advance, contain (methyl) acrylic ester polymer, polymerizable monomer and Photoepolymerizationinitiater initiater, with And the composition (preferably clear liquid) of solvent or levelling agent etc. when necessary, it is mixed, uniform dispersion solution is made, can obtain To hardening resin composition.
In addition, obtained hardening resin composition is filtered processing preferably by filter etc., remove fine Dust.
[solidfied material]
As described above, hardening resin composition of the invention can provide photonasty and curability is especially excellent, developability, The excellent solidfied material of basic performances such as solvent resistance and adaptation, heat resistance and the transparency of substrate (substrate).Such solidification The imaging and surface smoothness of object are also excellent, such as the residue without unexposed portion or dross etc. after development.It is such to incite somebody to action Solidfied material made of above-mentioned hardening resin composition solidification is also one of present invention.
It is suitable that the film thickness (thickness) of above-mentioned solidfied material (cured film), which is 0.1 μm~20 μm,.Can sufficiently cope with as a result, makes Dwarf forms (low back) requirement of component with above-mentioned solidfied material etc., display device etc..More preferably 0.5 μm~10 μm, into one Preferably 0.5 μm~8 μm of step.
Above-mentioned solidfied material for example can the colour filter used in liquid crystal display device, solid state image sensor etc., ink, print The use such as the various optical components such as brush version, printed circuit board, semiconductor element, photoresist or motor electronics are excellent on the way Choosing uses.Wherein it is preferred for colour filter.In this wise using colour filter made of above-mentioned hardening resin composition, i.e. specifically Say that the colour filter on substrate with above-mentioned solidfied material is also one of present invention.Colour filter is illustrated further below.
<colour filter>
Colour filter of the invention is made of the mode on substrate with above-mentioned solidfied material.
In above-mentioned colour filter, it is especially suitable as by the solidfied material that hardening resin composition of the invention is formed for example black Bottom or need to carry out red, green, each pixel shader such as blue, yellow segment (セ グ メ Application ト), but as light spacer, Protective layer, tropism control timber (the hired リ Block of orientation system) etc. are not necessarily required to that the segment of coloring is also suitable.
As substrate used in above-mentioned colour filter, it can be cited for example that: blank glass, green glass sheet, alkalinity enhancing glass The glass substrates such as glass, silicon dioxide coating blueness glass sheet；By the open loop of polyester, polycarbonate, polyolefin, polysulfones, cyclic olefin Sheet material, membrane material or the substrate that the thermoplastic resins such as polymer or its hydride are formed；By epoxy resin, unsaturated polyester resin etc. Sheet material, membrane material or the substrate that thermosetting resin is formed；The metal substrates such as aluminium sheet, copper sheet, nickel plate, stainless steel plate；Ceramic substrate；Tool There is the semiconductor substrate of photo-electric conversion element；Has glass substrate (such as LCD colour filter) of colorant layer etc. by each on surface The component that kind material is constituted；Etc..Wherein, from the aspect of heat resistance, preferably glass substrate, formed by heat-resistant resin Sheet material, membrane material or substrate.In addition, aforesaid substrate is suitably transparent substrate.
In addition, Corona discharge Treatment, ozone treatment can be carried out as needed on above-mentioned substrate, based on silane coupling agent etc. Chemicals processing etc..
<manufacturing method of colour filter>
Above-mentioned colour filter in order to obtain is to be suitable for for example, by using following manufacturing methods, that is, each color pixel is used Method comprising following processes: the process (also referred to as arrangement step) of above-mentioned hardening resin composition is configured on substrate；It is right In the process (also referred to as light irradiation process) of the hardening resin composition irradiation light of configuration on the substrate；Using developer solution into The process (also referred to as developing procedure) of row development treatment；And the process (also referred to as heating process) heated, to each Same method is repeated in color.It should be noted that the formation sequence of each color pixel is not particularly limited.
Arrangement step (preferably painting process)-
Above-mentioned arrangement step carries out being suitable by being coated with.It is combined as above-mentioned curable resin is coated on substrate The method of object, it can be cited for example that rotary coating, slot coated, roller coating cloth, cast coat etc., either method preferably makes With.
In addition, being suitable for that will apply after above-mentioned hardening resin composition is coated on substrate in above-mentioned arrangement step Film is dry.The drying of film can be used such as heating plate, IR baking oven, convection oven and carry out.Drying condition can be according to contained The boiling point of some solvent compositions, the type of cure component, performance of film thickness, drying machine etc. being suitable for selection, usually 50 DEG C~ It is suitable that 10 seconds~300 seconds are carried out at a temperature of 160 DEG C.
Light irradiation process-
In above-mentioned smooth irradiation process, as the light source of used active ray, can be used for example: xenon lamp, halogen lamp, The lamp sources such as tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp； The laser sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser Deng.In addition, the mode as exposure machine, can enumerate proximity mode (プ ロ キ シ ミ テ ィ ー mode), mirror surface projection mode, step Into mode, it is preferable to use proximity mode.
It should be noted that in the irradiation process of active-energy light, it can also be depending on the application across specific mask artwork The irradiation of case progress active-energy light.In this case, exposure portion is cured, and solidified portion is insoluble relative to developer solution Or indissoluble.
Developing procedure-
Above-mentioned developing procedure is unexposed to remove using developer solution progress development treatment after above-mentioned smooth irradiation process Portion, the process for forming pattern.This makes it possible to obtain patterned cured films.Development treatment can be in usually 10 DEG C~50 DEG C of development At a temperature of carried out using the methods of immersion development, spray development, fur brush development, supersonic wave development.
Developer solution used in above-mentioned developing procedure does not have as long as it can dissolve hardening resin composition of the invention It is particularly limited to, usually using organic solvent, aqueous alkali, it is possible to use their mixture.It should be noted that as aobvious In the case that shadow liquid uses aqueous alkali, preferably cleaned after development with water.
The organic solvent suitable as above-mentioned developer solution is it can be cited for example that ether series solvent or alcohol series solvent etc..Specifically Say, it can be cited for example that dialkyl ether, ethylene glycol monoalkyl ether class, glycol dialkyl ether class, diethylene glycol (DEG) dialkyl ether, Triethylene glycol dialkyl ether, alkyl phenyl ethers, aralkyl phenyl ethers, two aromatic series ethers, isopropanol, benzyl alcohol etc..
In above-mentioned aqueous alkali, in addition to alkaline reagent, surfactant can also be contained as needed, organic solvent, delayed Electuary, dyestuff, pigment etc..As organic solvent in this case, can enumerate it is above-mentioned as developer solution be suitable for it is organic molten Agent etc..
As above-mentioned alkaline reagent, it can be cited for example that: sodium metasilicate, potassium silicate, sodium hydroxide, potassium hydroxide, hydroxide The inorganic alkaline agents such as lithium, tertiary sodium phosphate, disodium hydrogen phosphate, sodium carbonate, potassium carbonate, sodium bicarbonate；It is trimethylamine, diethylamine, different The amines such as propylamine, n-butylamine, monoethanolamine, diethanol amine, triethanolamine, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, it Can be used alone, two or more can also be combined.
As above-mentioned surfactant, it can be cited for example that: polyoxyethylene alkyl ether class, polyxyethylated ester class, mountain The nonionic surface active agent such as pears sugar alcohol acid anhydride dialkylaminobenzoic acid esters, single alkyl esters of glycerol class；Alkyl benzene sulfonate, alkylnaphthalene sulphur The anionic surfactant such as Barbiturates, alkylsurfuric acid salt, alkyl sulfonates, sulfosuccinate ester salt class；Alkyl sweet tea Amphoteric surfactantes such as dish bases, amino acids etc., they can be used alone, and can also combine two or more.
Heating process-
Above-mentioned heating process is to solidify exposure portion (solidified portion) further occurrence by firing after above-mentioned developing procedure Process (also referred to as after curing process).It can be cited for example that: using light sources such as high-pressure sodium lamps, with such as 0.5J/cm2~5J/ cm2Light quantity carry out post-exposure process；Such as 60 DEG C~260 DEG C at a temperature of carry out rear heating in 10 seconds~120 minutes Process etc..By carrying out such rear curing process, the hardness of patterned cured film and adaptation can be made more strong.This Outside, using the heating process, the knot of (methyl) acrylic ester polymer contained by above-mentioned hardening resin composition can be made A part (i.e. a part of the part from (methyl) acrylate monomer containing tertiary carbon) of structure unit is decomposed, thus Curability and solvent resistance can be improved.
The cured film obtained by above-mentioned heating process (carries out heat cure to above-mentioned hardening resin composition to obtain Cured film) film thickness be suitably 0.1 μm~20 μm.By using hardening resin composition of the invention, film can be provided The cured film that thickness is sufficiently reduced.The film thickness is more preferably 0.5 μm~10 μm, further preferably 0.5 μm~8 μm.
It should be noted that when setting the film thickness of the film before heating as 100%, the painting that is obtained by above-mentioned heating process The film thickness of film (i.e. cured film) is suitably 90% or less.It more preferably 80% or less, is more preferably 70% or less.
In above-mentioned heating process, heating temperature is suitably 150 DEG C or more.Can making the part as a result, (part is from upper State a part of (methyl) acrylate monomer containing tertiary carbon) more effectively decompose, thus curability can be further realized With the raising of solvent resistance.The heating temperature is more preferably 160 DEG C or more, further preferably 170 DEG C or more, is particularly preferably 180 DEG C or more.And preferably 260 DEG C or less, more preferably 250 DEG C or less.
Heating time in above-mentioned heating process is not particularly limited, such as is suitably 5 minutes~60 minutes.In addition, plus Hot method is also not particularly limited, such as the heating equipments such as heating plate, convection oven, high frequency heating machine can be used to carry out.
[display device]
The invention further relates to display devices, are constituted using above-mentioned colour filter.
It should be noted that having the display device component of the solidfied material formed by above-mentioned hardening resin composition It is also contained in display device in suitable embodiment of the invention.The solidfied material formed by above-mentioned hardening resin composition (cured film) is stablized, the excellent adhesion with substrate etc., and is high rigidity, additionally shows high flatness, has high saturating Cross rate, thus be particularly suitable as transparent component, and as in various display devices protective film or insulating film be also Useful.
It as above-mentioned display device, such as is suitably liquid crystal display device, solid state image sensor, touch-screen type display dress It sets.
It should be noted that in the case that above-mentioned solidfied material (cured film) is used as display device with component, the portion Part can be the membranaceous single-layer or multi-layer component being made of above-mentioned cured film, which can be further group Component made of other layers is closed, and can be the component for containing above-mentioned cured film in composition.
[The effect of invention]
Hardening resin composition of the invention is due to for above-mentioned composition, thus after can stablizing and playing curability, solidification Solvent resistance, filtering with various physical property, excellent storage stabilities such as adaptation, heat resistance and the transparencys of substrate (substrate) The various uses such as color device are useful.Thus, the solidfied material (solidification that there is hardening resin composition in this way to be formed Film) colour filter and display device be highly useful in optical field or motor electronic field.
[specific embodiment]
Embodiment is enumerated below, the present invention is described in more detail, but the present invention is not limited to these embodiments.It needs Bright, as long as not special declaration, " part " means " mass parts ".
In synthesis example below etc., various physical property etc. are measured as follows.
<weight average molecular weight>
Using polystyrene as standard substance, using tetrahydrofuran as eluent, using HLC-8220GPC (manufacture of Tosoh society), Column: TSKgel SuperHZM-M (manufacture of Tosoh society) measures weight average molecular weight by GPC (gel permeation chromatography) method.
<solid component>
It is measured in aluminium cup about 1g polymer solution (also referred to as resin solution or polymer solution), about 3g acetone, which is added, to be made After it is dissolved, spontaneously dry at normal temperature.Thereafter using air drier (Espec society manufactures, trade name: PHH-101), true Under sky after 140 DEG C are 1.5 hours dry, the natural cooling in drier, quality measurement.It is calculated and is polymerize by its Mass lost meter The solid component (quality %) of object solution.
<acid value>
Accurate weighing 3g resin solution, is dissolved in the in the mixed solvent of acetone 90g Yu water 10g, uses the KOH of 0.1 equivalent Aqueous solution is molten using automatic titration device (manufacture of Ping Zhao industry society, trade name: COM-555) measurement polymer as titrating solution The acid value of liquid is found out the acid value (AV) of every 1g solid component by the acid value of solution and the solid component of solution.
<absorbance of hardening resin composition>
Hardening resin composition is spin-coated on the glass substrate of 5cm square, after 3 minutes dry at 80 DEG C, is utilized High-pressure sodium lamp is exposed at 100mJ, and the heat treatment of 30 minutes is carried out at 220 DEG C, and obtaining film thickness is 5 μm thin Film.Thereafter, it is impregnated 2 hours at 25 DEG C in 1-Methyl-2-Pyrrolidone 20g, utilizes spectrophotometer UV3100 (Shimadzu system The manufacture of Zuo Suo society) it measures by the tone of the 1-Methyl-2-Pyrrolidone dissolved out in film, find out the absorbance of 450nm.
Synthesis example 1
The synthesis of resin solution 1 (BzMI-CHMA-t-BMA-MAA copolymer solution)
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol methyl ether acetate 844.57g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, quasi- as dropwise adding tank (A) It is standby that N- benzyl maleimide 50g, cyclohexyl methacrylate 125g, Tert-butyl Methacrylate are stirred in beaker 225g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " of Japanese grease society manufacture) 10g Made of mixed liquor；Prepare to be stirred n-dodecyl mercaptan 21g, propylene glycol methyl ether acetate 84g in dropwise adding tank (B) Made of mixed liquor.It after the temperature of reactive tank reaches 90 DEG C, is kept at this temperature and is added dropwise by dropwise adding tank, carry out 3 Hour polymerization.It after completion of dropwise addition, is kept for 30 minutes at 90 DEG C, is warming up to 115 DEG C later, cure within 90 minutes.
Obtained polymer solution is analyzed, as a result weight average molecular weight is 7800, acid value 129mgKOH/g, sets Rouge solid component is 35.0 mass %.
Synthesis example 2
The synthesis of resin solution 2 (BzMI-CHMA-HEMA-MAA copolymer solution)
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol methyl ether acetate 844.57g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, quasi- as dropwise adding tank (A) It is standby that N- benzyl maleimide 50g, cyclohexyl methacrylate 250g, methacrylic acid -2- hydroxyl are stirred in beaker (Japanese grease society manufactures for ethyl ester 100g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester " PerbutylO ") mixed liquor made of 10g；Prepare to be stirred n-dodecyl mercaptan 21g, propylene glycol in dropwise adding tank (B) Mixed liquor made of methyl ether acetate 84g.After the temperature of reactive tank reaches 90 DEG C, it is kept at this temperature by dropwise adding tank Start to be added dropwise, polymerize within 3 hours.It after completion of dropwise addition, is kept for 30 minutes at 90 DEG C, is warming up to 115 DEG C later, carried out 90 minutes Curing.
Obtained polymer solution is analyzed, as a result weight average molecular weight is 7700, acid value 129mgKOH/g, sets Rouge solid component is 35.0 mass %.
Synthesis example 3
(the copolymer containing pendant double bonds of resin solution 3；BzMI-t-BA-AA//GMA copolymer solution) synthesis
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol monomethyl ether 1006.67g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, as dropwise adding tank (A), preparation is being burnt N- benzyl maleimide 20g, tert-butyl acrylate 250g, acrylic acid 230g and peroxidating (2- ethyl hexyl are stirred in cup Acid) mixed liquor made of the tert-butyl ester " PerbutylO " of manufacture (Japanese grease society) 10g；It is mixed to prepare stirring in dropwise adding tank (B) Close mixed liquor made of n-dodecyl mercaptan 40g, propylene glycol monomethyl ether 160g.After the temperature of reactive tank reaches 90 DEG C, It is kept at this temperature and is added dropwise by dropwise adding tank, polymerize within 3 hours.After completion of dropwise addition, 90 DEG C keep 30 minutes, later 115 DEG C are warming up to, cure within 90 minutes.
Thereafter, the nitrogen for introducing gas into pipe becomes oxygen/nitrogen mixture gas (oxygen/nitrogen=5/95vol%), and addition is used as polymerization inhibitor 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol) (chemistry society, Kawaguchi manufacture, " ANTAGE w-400 ") 1.34g and As the triethylamine 2.68g of catalyst, after being stirred, the glycidyl methacrylate as additive compound is added 393.74g is warming up to 115 DEG C of progress addition reactions, after 8 hours, reaches in the remaining GMA amount based on GC (gas-chromatography) analysis Reaction is terminated when 0.5 mass % or less, the polymer for obtaining Han acidic group copolymer of the side chain with free-radical polymerised double bond is molten Liquid.
Obtained polymer solution is analyzed, as a result weight average molecular weight is 6800, acid value 58mgKOH/g, sets Rouge solid component is 39.0 mass %.
It should be noted that " BzMI-t-BA-AA//GMA copolymer solution ", which is meant that, to be made GMA and uses BzMI, t- Copolymer solution obtained from the base polymer reaction that BA and AA are obtained.
Synthesis example 4
(the copolymer containing pendant double bonds of resin solution 4；BzMI-CHA-HEA-AA//GMA copolymer solution) synthesis
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol monomethyl ether 1006.67g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, as dropwise adding tank (A), preparation is being burnt N- benzyl maleimide 20g, cyclohexyl acrylate 150g, 2-Hydroxy ethyl acrylate 100g, acrylic acid are stirred in cup Mixed liquor made of 230g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " of Japanese grease society manufacture) 10g；? Prepare to be stirred mixed liquor made of n-dodecyl mercaptan 40g, propylene glycol monomethyl ether 160g in dropwise adding tank (B).It is reacting It after the temperature of slot reaches 90 DEG C, is kept at this temperature and is added dropwise by dropwise adding tank, polymerize within 3 hours.After completion of dropwise addition, It is kept for 30 minutes at 90 DEG C, is warming up to 115 DEG C later, cure within 90 minutes.
Thereafter, the nitrogen for introducing gas into pipe is changed to oxygen/nitrogen mixture gas (oxygen/nitrogen=5/95vol%), and addition is as polymerization inhibitor The 2,2 ' of agent-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenol) (chemistry society, Kawaguchi manufacture, " ANTAGE w-400 ") 1.34g, with And the triethylamine 2.68g as catalyst, after being stirred, add the glycidyl methacrylate as additive compound 393.74g is warming up to 115 DEG C of progress addition reactions, after 8 hours, reaches in the remaining GMA amount based on GC (gas-chromatography) analysis Reaction is terminated when 0.5 mass % or less, the polymer for obtaining Han acidic group copolymer of the side chain with free-radical polymerised double bond is molten Liquid.
Obtained polymer solution is analyzed, as a result weight average molecular weight is 6800, acid value 58mgKOH/g, sets Rouge solid component is 39.0 mass %.
It should be noted that " BzMI-CHA-HEA-AA//GMA copolymer solution " be meant that make GMA and using BzMI, Copolymer solution obtained from the base polymer reaction that CHA, HEA and AA are obtained.
Synthesis example 5
The synthesis of resin solution 5 (BzMI-CHMA-t-BMA-HEMA-MAA copolymer solution)
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol methyl ether acetate 844.57g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, quasi- as dropwise adding tank (A) It is standby that N- benzyl maleimide 50g, cyclohexyl methacrylate 125g, Tert-butyl Methacrylate are stirred in beaker 125g, methacrylic acid -2- hydroxy methacrylate 100g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (Japan " PerbutylO " of grease society manufacture) mixed liquor made of 10g；Prepare to be stirred dodecyl sulphur in dropwise adding tank (B) Mixed liquor made of alcohol 21g, propylene glycol methyl ether acetate 84g.After the temperature of reactive tank reaches 90 DEG C, it is maintained at the temperature It is added dropwise, polymerize within 3 hours by dropwise adding tank under degree.After completion of dropwise addition, is kept for 30 minutes at 90 DEG C, be warming up to 115 later DEG C, cure within 90 minutes.
Obtained polymer solution is analyzed, as a result weight average molecular weight is 7700, acid value 133mgKOH/g, sets Rouge solid component is 35.0 mass %.
Synthesis example 6
(the copolymer containing pendant double bonds of resin solution 6；BzMI-t-BA-HEA-AA//GMA copolymer solution) synthesis
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol monomethyl ether 1006.67g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, as dropwise adding tank (A), preparation is being burnt N- benzyl maleimide 20g, tert-butyl acrylate 150g, 2-Hydroxy ethyl acrylate 100g, acrylic acid are stirred in cup Mixed liquor made of 230g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester (" PerbutylO " of Japanese grease society manufacture) 10g；? Prepare to be stirred mixed liquor made of n-dodecyl mercaptan 40g, propylene glycol monomethyl ether 160g in dropwise adding tank (B).It is reacting It after the temperature of slot reaches 90 DEG C, is kept at this temperature and is added dropwise by dropwise adding tank, polymerize within 3 hours.After completion of dropwise addition, It is kept for 30 minutes at 90 DEG C, is warming up to 115 DEG C later, cure within 90 minutes.
Thereafter, the nitrogen for introducing gas into pipe is changed to oxygen/nitrogen mixture gas (oxygen/nitrogen=5/95vol%), and addition is as polymerization inhibitor The 2,2 ' of agent-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenol) (chemistry society, Kawaguchi manufacture, " ANTAGE w-400 ") 1.34g, with And the triethylamine 2.68g as catalyst, after being stirred, add the glycidyl methacrylate as additive compound 393.74g is warming up to 115 DEG C of progress addition reactions, after 8 hours, reaches in the remaining GMA amount based on GC (gas-chromatography) analysis Reaction is terminated when 0.5 mass % or less, the polymer for obtaining Han acidic group copolymer of the side chain with free-radical polymerised double bond is molten Liquid.
Obtained polymer solution is analyzed, as a result weight average molecular weight is 6800, acid value 58mgKOH/g, sets Rouge solid component is 39.0 mass %.
It should be noted that " BzMI-t-BA-HEA-AA//GMA copolymer solution ", which is meant that, to be made GMA and uses Copolymer solution obtained from the base polymer reaction that BzMI, t-BA, HEA and AA are obtained.
Synthesis example 7
The synthesis of resin solution 7 (MMA-MAA copolymer solution)
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol methyl ether acetate 844.57g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, quasi- as dropwise adding tank (A) It is standby that methyl methacrylate 400g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester are stirred in beaker Mixed liquor made of (" the Perbutyl O " of Japanese grease society manufacture) 10g；Prepare to be stirred positive 12 in dropwise adding tank (B) Mixed liquor made of alkyl hydrosulfide 21g, propylene glycol methyl ether acetate 84g.After the temperature of reactive tank reaches 90 DEG C, keep It is added dropwise, polymerize within 3 hours by dropwise adding tank at such a temperature.After completion of dropwise addition, is kept for 30 minutes at 90 DEG C, heated up later To 115 DEG C, cure within 90 minutes.
Obtained polymer solution is analyzed, as a result weight average molecular weight is 7700, acid value 133mgKOH/g, sets Rouge solid component is 35.0 mass %.
Synthesis example 8
The synthesis of resin solution 8 (BzMI-t-BMA-HEMA-MAA copolymer solution)
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol methyl ether acetate 874.57g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, quasi- as dropwise adding tank (A) It is standby that N- benzyl maleimide 50g, Tert-butyl Methacrylate 235g, methacrylic acid -2- hydroxyl are stirred in beaker (Japanese grease society manufactures for ethyl ester 100g, methacrylic acid 115g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester " PerbutylO ") mixed liquor made of 10g；Prepare to be stirred n-dodecyl mercaptan 6g, propylene glycol in dropwise adding tank (B) Mixed liquor made of methyl ether acetate 54g.After the temperature of reactive tank reaches 90 DEG C, it is kept at this temperature by dropwise adding tank Start to be added dropwise, polymerize within 3 hours.It after completion of dropwise addition, is kept for 30 minutes at 90 DEG C, is warming up to 115 DEG C later, carried out 90 minutes Curing.
Obtained polymer solution is analyzed, as a result weight average molecular weight be 15500, acid value 150mgKOH/g, Resin solid content is 35.0 mass %.
Synthesis example 9
The synthesis of resin solution 9 (MD-t-BMA-HEMA-MAA copolymer solution)
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol methyl ether acetate 844.57g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, quasi- as dropwise adding tank (A) It is standby that double 2- acrylate (MD) 50g of dimethyl -2,2 '-[oxo is bis- (methylene)], methacrylic acid are stirred in beaker Tert-butyl ester 250g, methacrylic acid -2- hydroxy methacrylate 100g, methacrylic acid 100g and peroxidating (2 ethyl hexanoic acid) tert-butyl ester Mixed liquor made of (" PerbutylO " of Japanese grease society manufacture) 10g；Prepare to be stirred positive 12 in dropwise adding tank (B) Mixed liquor made of alkyl hydrosulfide 15g, propylene glycol methyl ether acetate 84g.After the temperature of reactive tank reaches 90 DEG C, keep It is added dropwise, polymerize within 3 hours by dropwise adding tank at such a temperature.After completion of dropwise addition, is kept for 30 minutes at 90 DEG C, heated up later To 115 DEG C, cure within 90 minutes.
Obtained polymer solution is analyzed, as a result weight average molecular weight be 12000, acid value 133mgKOH/g, Resin solid content is 35.0 mass %.
Synthesis example 10
The synthesis of resin solution 10 (AMA-t-BMA-HEMA-MAA copolymer solution)
The investment the third two in the reactive tank for having thermometer, blender, gas introduction tube, cooling tube and dropwise adding tank introducing port Alcohol methyl ether acetate 844.57g is heated to 90 DEG C after carrying out nitrogen displacement.On the other hand, quasi- as dropwise adding tank (A) It is standby be stirred in beaker 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 (Japanese grease society " PerbutylO " of manufacture) mixed liquor made of 10g；Prepare in the dropwise adding tank (B) to be stirred n-dodecyl mercaptan 15g, Mixed liquor made of propylene glycol methyl ether acetate 84g.After the temperature of reactive tank reaches 90 DEG C, be kept at this temperature by Dropwise adding tank starts to be added dropwise, and polymerize within 3 hours.It after completion of dropwise addition, is kept for 30 minutes at 90 DEG C, is warming up to 115 DEG C later, carried out It cures within 90 minutes.
Obtained polymer solution is analyzed, as a result weight average molecular weight be 12300, acid value 132mgKOH/g, Resin solid content is 35.2 mass %.
Resin solution 1~10 is shown in detail in table 1.
It should be noted that the combined amount about the monomer for constituting resin in table 1, each monomer of formation base polymer Numerical values be each monomer when their total amount to be set as to 100 mass % mixed proportion (quality %).In addition, in synthesis example 4 In 6, GMA (compound with the functional group and polymeric double bond that can with acidic group be bonded) of the addition on the base polymer Numerical value with acidic group and polymeric double bond monomer (in this case on the carboxylic acid composition for AA) institute's addition GMA ratio The form of example is recorded, and " GMA mixed proportion (addition the AA mixed proportion (quality %) of GMA)={ mole of GMA is passed through (mol)/AA mole (mol) } × AA mixed proportion (quality %) " it acquires.For example, in synthesis example 4, base polymer AA in (100 mass %) is constituted with 46 mass %, the GMA of addition 2769mmol on the AA of 46 mass % (3191mmol), by The mixed proportion (quality %) of the GMA is defined as " 40 " by this.
[table 1]
Mark in table 1 is as described below.
BzMI:N- benzyl maleimide
MD: dimethyl -2,2 '-[oxo is bis- (methylene)] double 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
Make example 1
The production of pigment dispersion 1
By 12.9 parts of propylene glycol methyl ether acetate, as the Disparlon DA-7301 (0.4 part) of dispersing agent, conduct 2.25 parts of the C.I. pigment green 36 (Monastral Green6Y-CL, the manufacture of Heubach society) and C.I. pigment yellow of colorant 150 1.5 parts of (Yellow Pigment E4GN-GT, the manufacture of Lanxess society) mixing, carried out for 3 small time-divisions using coating rocker It dissipates, to obtain pigment dispersion 1.
Embodiment 1
By resin solution 1 (1.0 parts), resin solution 2 (1.0 parts), as two Ji Wusi of free-radical polymerised compound 0.70 part of six acrylate of alcohol, the Irgacure 369 (manufacture of Ciba society) as free-radical polymerised Photoepolymerizationinitiater initiater 0.35 part, pigment dispersion 1 (7.88 parts), 6.57 parts of the propylene glycol methyl ether acetate mixing as solvent, obtain curability Resin combination 1.When carrying out absorbance measurement for the hardening resin composition 1, absorbance is 1.6 × 10-2。
Embodiment 2~8, comparative example 1~7
Other than by being mixed shown in table 2 and table 3, curable resin combination is respectively obtained similarly to Example 1 Object 2~15, measures absorbance respectively later.As a result table 2 and table 3 are shown in.
[table 2]
[table 3]
Following the description is confirmed by the result of table 2 and table 3.
Embodiment 1 and Comparative Examples 1 and 2,5 and 6；Embodiment 2 and comparative example 3 and 4；Embodiment 3,6,7 and 8 and comparative example 7； Embodiment 4 and comparative example 3 and 4 are the examples for obtaining solidfied material under identical condition respectively and carrying out absorbance measurement, if but They are compared respectively, then the absorbance compared to the examples, in comparative example significantly increases, it is known that solidfied material it is transparent Property is poor.Herein, when the curability of hardening resin composition, solvent resistance are insufficient, colorant occurs dissolution and to solidify The absorbance of object will increase；Thus by the result of table 2 and table 3 it is found that the curable resin of comparative example combines compared to the examples, The curability and solvent resistance of object are insufficient.In addition, although being not shown in table, the development of solidfied material obtained in embodiment It is property, also excellent with the various physical property such as the adaptation of substrate, heat resistance.

Claims (6)

1. a kind of hardening resin composition is poly- containing (methyl) acrylic ester polymer, polymerizable compound and light The hardening resin composition of initiator is closed, which is characterized in that:
Being somebody's turn to do (methyl) acrylic ester polymer has the structural unit from (methyl) acrylate monomer containing tertiary carbon, and And also there is ring structure in main chain, the acid value of the polymer is 30~200mgKOH/g,
(methyl) acrylic ester polymer is also included to come from and is selected from by N substituted maleimide amine system monomer, dialkyl group -2, What 2 '-(oxygroup dimethylene) diacrylate system monomers and α-(unsaturated alkoxyalkyl) acrylate monomer formed The structural unit of at least one of group monomer；
The hardening resin composition is selected from least one of the group being made of following manner mode: the curable resin group Close the mode that object further contains the polymer with hydroxyl；And (methyl) acrylic ester polymer further has hydroxyl The mode of base.
2. hardening resin composition as described in claim 1, which is characterized in that described (methyl) acrylate containing tertiary carbon It is structure made of there is monomer oxygen atom to be bonded with tertiary carbon atom, which is former with the adjacent oxygen of (methyl) acryloyl group Son.
3. hardening resin composition as claimed in claim 1 or 2, which is characterized in that (methyl) acrylic ester is poly- Closing object and/or the polymer with hydroxyl is the polymer for having polymeric double bond in side chain.
4. a kind of solidfied material, which is characterized in that the solidfied material is by the described in any item curable resin groups of claims 1 to 3 Close what object was formed by curing.
5. a kind of colour filter, which is characterized in that the colour filter has solidfied material as claimed in claim 4 on substrate.
6. a kind of display device, which is characterized in that the display device is constituted using the colour filter described in claim 5.
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