CN103224609A - Reactive carboxylate compound, active-energy-ray-curable resin composition utilizing the same, and use of the same - Google Patents

Reactive carboxylate compound, active-energy-ray-curable resin composition utilizing the same, and use of the same Download PDF

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CN103224609A
CN103224609A CN201310088076XA CN201310088076A CN103224609A CN 103224609 A CN103224609 A CN 103224609A CN 201310088076X A CN201310088076X A CN 201310088076XA CN 201310088076 A CN201310088076 A CN 201310088076A CN 103224609 A CN103224609 A CN 103224609A
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epoxy
curable resin
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active energy
resin composition
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CN103224609B (en
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山本和义
栗桥透
堀口尚文
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority claimed from JP2007274912A external-priority patent/JP5473208B2/en
Priority claimed from JP2008129547A external-priority patent/JP2009275167A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/186—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

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  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
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  • Materials For Photolithography (AREA)

Abstract

To provide a resin composition which can be cured with an active energy ray such as ultraviolet ray or the like and enables to produce a rigid film or a molding material. Disclosed is a reactive compound derived from a phenolic epoxy resin containing a specific structure in the molecule, a compound having both of at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in the molecule, and a compound having both of at least one hydroxyl group and at least one carboxyl group in the molecule. Also disclosed is a curable resin composition utilizing the reactive compound. A rigid cured article can be produced from the curable resin composition. The reactive compound has a good pigment-dispersing property.

Description

Reactive epoxy carbonate, reactive polycarboxylic acid compound, active energy ray-curable resin composition and article
The application divides an application, the China national application number of its original application is 200880103586.7, the applying date is on August 8th, 2008, and denomination of invention is " reactive carbonate, use active energy ray-curable resin composition of this reactivity carbonate and uses thereof ".
Technical field
The present invention relates to reactive epoxy carbonate (A) and as the reactive polycarboxylic acid compound (B) of its sour modifier, this reactivity epoxy carbonate (A) make in molecule, having concurrently more than of representative such as vinylformic acid can polymeric ethylenic unsaturated group and the compound (b) of an above carboxyl and molecule in have an above hydroxyl and an above carboxyl concurrently compound (c) and molecule in comprise ad hoc structure phenol-type epoxy resin (a) reaction obtain.These reactive epoxy carbonates (A) and reactive polycarboxylic acid compound (B) have good affinity with pigment, and can access tough cured article by the resin combination that comprises these compounds.
Background technology
With the purpose that rises to of the miniaturization and of portable machine and communication speed, printed circuit board (PCB) just is being required high precision, densification.Accompany therewith, the requirement of the solder resist of this circuit that is covered itself is also improved day by day, compare, also require it when keeping thermotolerance, thermostability, have substrate adaptation, high-insulativity, can tolerate the performance of electroless plating gold with existing the requirement.People's demand has the tunicle formation material of more tough curing rerum natura.
In order to adapt to high performance requirement to solder resist, developed the Resins, epoxy that in molecule, comprises ad hoc structure, it is well-known comprising the resin of these Resins, epoxy or the cured article of its sour modified epoxy carboxylicesters resin.
With phenol aralkyl-type epoxy resin for example (for example, the NC-3000 series that Japan's chemical drug is made, NC-2000 series etc.) for the sour modified epoxy acrylic ester of basic framework is recorded in patent documentation 1 or patent documentation 2, and it is a common general knowledge as the material that demonstrates high-strong toughness after solidifying.And, also to studying as the purposes of the solder resist that uses this material.
It is the sour modified epoxy acrylic ester compound and the cured article thereof of basic framework that patent documentation 3 has been put down in writing with the Resins, epoxy with multi-ring alkyl, and has recorded and narrated it have the higher strength and toughness of ratio after curing.And, also put down in writing the solder resist that uses this material.But, though this solder resist have than higher reliability, insufficient have can satisfy the more performance of high reliability, more high reliability is follow in recent years conveying machine etc. electronic desired.
In addition, as the purposes of the sour modified epoxy acrylic ester that generates by these Resins, epoxy, also attempt being applied to the black matrix layer resist (Block ラ ッ Network マ ト リ Network ス レ ジ ス ト) that display panels etc. uses by painted pigment such as disperse black carbons.
Above-mentioned be that painted pigment such as disperse black carbon obtains the black matrix layer resist in the sour modified epoxy acrylic ester of basic framework with the phenol aralkyl-type epoxy resin, be recorded in patent documentation 4, patent documentation 5 towards the application examples of described black matrix layer resist.
In addition, painted pigment such as disperse black carbon is applied to the black matrix layer resist in the sour modified epoxy acrylic ester compound that with the Resins, epoxy with multi-ring alkyl is basic framework, and this trial also is well-known.(patent documentation 6)
But, in employed black matrix layer resist purposes such as display panels, when painted pigment compoundings such as carbon black are become high density, disperse well because pigment and resin are affine, even thereby pigment exists with high density, also demonstrate good development, the development of no pigment residue becomes possibility.In this case, the more development under the high pigment levels, that is, and higher pigment-dispersing.Though existing sour modified epoxy acrylic ester class demonstrates better pigment-dispersing, has the dispersible pigment dispersion pseudo agglutination, the bad such difficult problem of stability.
On the other hand, make vinylformic acid and have a carbonate that the carboxylic acid cpd of hydroxyl obtains with general Resins, epoxy reaction simultaneously low as acid number but material that have an excellent development is known, patent documentation 7 has also been put down in writing this compound and has been had the suitable property of oil resistant China ink.
Patent documentation 1: Japanese kokai publication hei 11-140144 communique
Patent documentation 2: Japanese kokai publication hei 5-194708 communique
Patent documentation 3: Japanese kokai publication hei 5-214048 communique
Patent documentation 4: TOHKEMY 2005-55814 communique
Patent documentation 5: TOHKEMY 2003-183354 communique
Patent documentation 6: TOHKEMY 2004-295084 communique
Patent documentation 7: Japanese kokai publication hei 6-324490 communique
Summary of the invention
Though use the above-mentioned curable resin composition that in molecule, comprises the Resins, epoxy of ad hoc structure can access more intense tough cured article, but as material towards the such purposes that requires high reliability of conveying machine, need more tough curing rerum natura, for example, need to tolerate the bending of substrate, or the like.
In addition, in the purposes of anticorrosive additive material as colour system, making under the situation of its composition, need a kind of sour modified epoxy acrylic ester, this acid modified epoxy acrylic ester is better to the dispersion of tinting pigment (particularly carbon black etc.), thereby also has a good developing property even pigment concentration is higher.For this situation, need have higher molecular weight and have the material of right development.And need in dispersible pigment dispersion, not observe cohesion and demonstrate the resin combination that is dispersed with tinting pigment of prolonged preservation stability.
In order to solve above-mentioned problem, the inventor finds, following reactive epoxy carbonate that obtains and reactive polycarboxylic acid compound have especially excellent resin rerum natura and as the resin rerum natura of its cured article, this reactivity epoxy carbonate is to make that have concurrently in the molecule more than one can polymeric ethylenic unsaturated group and the compound (b) of an above carboxyl, the compound (c) that has an above hydroxyl and an above carboxyl in a part concurrently obtains with the Resins, epoxy reaction that comprises ad hoc structure in molecule, and this reactivity polycarboxylic acid compound makes multi-anhydride (d) obtain with this reactivity epoxy carbonate reaction again.
Find that in addition this resin combination particularly has good affinity with tinting pigment, and find, even it can become the anticorrosive additive material that the pigment concentration height also has good development.
Promptly, the present invention relates to a kind of reactive epoxy carbonate (A), its make have concurrently in the Resins, epoxy (a) shown in the following general formula (1), a part more than one can polymeric ethylenic unsaturated group and the compound (b) of an above carboxyl and a part in have an above hydroxyl and an above carboxyl concurrently compound (c) reaction obtain.
[changing 1]
Figure BDA00002935838600031
(in the formula (1), R 1Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually; R 2The expression carbonatoms is that 7～16 divalent multi-ring alkyl or carbonatoms are 7～18 inferior aralkyl; M represents 1～4 integer; And n is in the positive number of mean value expression 1～10.)
The invention still further relates to a kind of reactive epoxy carbonate (A), wherein, Resins, epoxy (a) is shown in general formula (2).
[changing 2]
(in the formula (2), R 3Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually; O represents 1～4 integer; And p is in the positive number of mean value expression 1～10.)
The invention still further relates to a kind of reactive epoxy carbonate (A), wherein, Resins, epoxy (a) is shown in general formula (3).
[changing 3]
Figure BDA00002935838600042
(in the formula (3), R 4Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually; Q represents 1～4 integer; And r is in the positive number of mean value expression 1～10.)
The invention still further relates to a kind of reactive epoxy carbonate (A), wherein, Resins, epoxy (a) is shown in general formula (4).
[changing 4]
Figure BDA00002935838600043
(in the formula (4), R 5Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually; S represents 1～4 integer; And t is in the positive number of mean value expression 1～10.)
The invention still further relates to a kind of reactive polycarboxylic acid compound (B), it obtains multi-anhydride (d) and above-mentioned reactive carbonate (A) reaction that obtains.
The invention still further relates to a kind of active energy ray-curable resin composition, it is characterized in that, described composition comprises above-mentioned reactive carbonate (A) and/or reactive polycarboxylic acid compound (B).
The present invention relates to a kind of active energy ray-curable resin composition, it is characterized in that, described composition also comprises the reactive compounds (C) except that (A), (B).
The present invention relates to a kind of active energy ray-curable resin composition, it is characterized in that, described composition also contains tinting pigment.
The present invention relates to a kind of active energy ray-curable resin composition, it is characterized in that, described composition also comprises Photoepolymerizationinitiater initiater.
The invention still further relates to above-mentioned active energy ray-curable resin composition, wherein, described composition is a molding material.
The invention still further relates to above-mentioned active energy ray-curable resin composition, wherein, described composition is a tunicle formation material.
The invention still further relates to above-mentioned active energy ray-curable resin composition, wherein, described composition is the anticorrosive additive material composition.
The invention still further relates to a kind of cured article, it is the cured article of above-mentioned active energy ray-curable resin composition.
The invention still further relates to a kind of article, it has covered surperficial article for using above-mentioned active energy ray-curable resin composition.
The active energy ray-curable resin composition that is included in the Resins, epoxy that has ad hoc structure in the molecule of the present invention not only provides tough cured article, even and be in and also have excellent resin rerum natura under the state that only makes solvent seasoning.The tunicle that the cured article that is obtained by active energy ray-curable resin composition of the present invention can compatibly be used for requirement thermotolerance and mechanical obdurability forms uses material.As particularly preferred purposes, can enumerate use in printed circuit board solder resist, multilayer printed circuit board with interlayer dielectic, flexible printed circuit board solder resist, resist plating, photosensitivity optical waveguides etc., can be used in the purposes that requires extra high characteristic.
Therefore in addition, painted pigment such as resulting active energy ray-curable resin composition and carbon black have high-affinity, even under the pigment concentration condition with higher, also demonstrate good pigment-dispersing, thereby can bring into play high development.And colo(u)rant dispersion state that can its tinting pigment dispersion liquid of long term maintenance can provide the resin combination of the storage stability that can guarantee high dispersion state.Thereby, as particularly preferred purposes, can compatibly be used for anticorrosive additive material, particularly black matrix layer material etc. that chromatic photoresist, colour filter are used.
Embodiment
Reactive epoxy carbonate of the present invention (A) is to use in giving reactive compound (b) and compound (c) and obtains with phenol-type epoxy resin (a) reaction, wherein, described phenol-type epoxy resin (a) is the phenol-type epoxy resin as shown in the formula the feature skeleton shown in (1) that is connected with phenol type epoxy group(ing) with the alkyl of ad hoc structure, described compound (b) is that have concurrently in the molecule more than one can polymeric ethylenic unsaturated group and the compound of an above carboxyl, and described compound (c) is the compound that has an above hydroxyl and an above carboxyl in a part concurrently.That is, in molecular chain, import ethylenic unsaturated group and hydroxyl simultaneously, make feature of the present invention obtain performance thus by the epoxy carboxylic esterification.
[changing 5]
Figure BDA00002935838600061
Employed Resins, epoxy (a) with general formula (1) expression is characterised in that among the present invention, and it is the phenol-type epoxy resin that is made of the repetition skeleton, and this repetition skeleton is phenol type epoxy group(ing) and R 2Expression, carbonatoms is that 7～16 divalent multi-ring alkyl or carbonatoms are the repetition skeleton of the alkyl of 7～18 the inferior aralkyl of conduct.
In the above-mentioned formula, R 1Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually.Represent fluorine atom, chlorine atom, bromine atoms, iodine atom at this halogen atom.And carbonatoms is that 1～4 alkyl is represented saturated hydrocarbyl and unsaturated alkyls such as methyl, ethyl, vinyl, n-propyl, sec.-propyl, propenyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, butenyl.
R 2The expression carbonatoms is that 7～16 divalent multi-ring alkyl or carbonatoms are 7～18 inferior aralkyl.As carbonatoms is 7～16 divalent multi-ring alkyl, can enumerate dicyclo [2,2,1] heptane two bases, dicyclo [2,2,2] octane two bases, octahydro pentalene two bases, naphthane two bases, tetrahydro-dicyclopentadiene two bases, tetrahydrochysene dicyclo hexadiene two bases.Among these, preferably use tetrahydro-dicyclopentadiene two bases.
And, as carbonatoms is 7～18 inferior aralkyl, can enumerate phenylene dimethylene, phenylene acetylene, biphenylene dimethylene, biphenylene acetylene, naphthylidene dimethylene, anthracene dimethylene, luxuriant and rich with fragrance dimethylene, pyrene dimethylene etc.Among these, preferably use phenylene dimethylene, biphenylene dimethylene.
In addition, in the general formula (1), m represents 1～4 integer, functional group's number that expression is imported.N does not represent 1～10 positive number with the mean value score, is preferably 1～6.When the value of n less than 10, preferably less than 6 the time, Resins, epoxy (a) is in suitable range of viscosities.Need to prove that the mean value of n is meant average repeat number, can calculate by the measured value of utilizing gel permeation chromatography (GPC) to obtain.
As employed Resins, epoxy (a) among the present invention, can preferably use the Resins, epoxy shown in the following general formula (2) with feature biphenyl backbone.
[changing 6]
Figure BDA00002935838600071
In the above-mentioned formula, R 3Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually.Halogen atom is represented fluorine atom, chlorine atom, bromine atoms, iodine atom.In addition, o represents 1～4 integer, and p does not represent 1～10 positive number with the mean value score, is preferably 1～6.When the value of p less than 10, preferably less than 6 the time, Resins, epoxy (a) is in suitable range of viscosities.
Among the Resins, epoxy (a) shown in the general formula (2), R 3The Resins, epoxy (a) that all is hydrogen atom can obtain at low cost, thereby preferred.Generally can obtain NC-3000 series commercially available product by Japanese chemical drug.About NC-3000 series, in the above-mentioned formula, R 3All be hydrogen atom, and p does not represent 1～10 positive number with the mean value score.Among the present invention, can in series, select the product of suitable grade aptly.
And,, can preferably use the phenol aralkyl-type epoxy resin shown in the general formula (3) as employed Resins, epoxy (a) among the present invention.
[changing 7]
Figure BDA00002935838600072
In the above-mentioned formula, R 4Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually.In addition, q is for replacing number, the integer of expression 1～4; And r is in the positive number of mean value expression 1～10.
Among the Resins, epoxy shown in the general formula (3), preferred R 4All be the Resins, epoxy of hydrogen atom or methyl.Resins, epoxy shown in the general formula (3) generally can be obtained as NC-2000 series by Japanese chemical drug.About NC-2000 series, in the above-mentioned formula, R 4All be hydrogen atom, and r count 1～10 positive number with mean value.Among the present invention, can in series, select the product of suitable grade aptly.
And,, can preferably use the Resins, epoxy shown in the general formula (4) with multi-ring alkyl as employed Resins, epoxy (a) among the present invention.
[changing 8]
In the above-mentioned formula, R 5Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually; S is for replacing number, the integer of expression 1～4; And t is in the positive number of mean value expression 1～10.
Wherein, R 5All be the compound or the R of hydrogen atom 5For the compound of methyl can obtain at low cost, thus preferred.R 5All be that hydrogen atom and t can be from Japanese chemical drug (strain) as the acquisitions of XD-1000 series in the compound of the positive number of mean value expression 1～10.In the present invention, can in series, select the compound of suitable grade aptly.
Have concurrently in employed a part among the present invention more than one can polymeric ethylenic unsaturated group and the compound (b) of an above carboxyl be in order to give and make its reaction to the reactivity of active energy beam.Can enumerate monocarboxylic acid compound, polycarboxylic acid compound in these compounds.
As the monocarboxylic acid compound that comprises a carboxyl in a part, can enumerate, for example (methyl) acrylic acid or the like, butenoic acid, alpha-cyano styracin, styracin or saturated or unsaturated dibasic acid and contain the reaction product of single glycidyl compound of unsaturated group.In above-claimed cpd, as acrylic acid or the like, for example can enumerate (methyl) vinylformic acid, β-styrene acrylic, β-furfuryl group vinylformic acid, (methyl) acrylic acid dimer, as the half ester class of the reaction with same mole product of (methyl) acrylate derivative that has 1 hydroxyl in saturated or unsaturated dicarboxylic acid anhydride and 1 molecule, as half ester class of the reaction with same mole product of saturated or unsaturated dibasic acid and (methyl) vinylformic acid list glycidyl ester derivatives class etc.
In addition, for the polycarboxylic acid compound that has 2 above carboxyls in a part, can enumerate, as the half ester class of the reaction with same mole product of (methyl) acrylate derivative that has 2 above hydroxyls in a part and dibasic acid anhydride, as saturated or unsaturated dibasic acid and have the half ester class etc. of reaction with same mole product of (methyl) glycidyl acrylate derivatives class of 2 above epoxy group(ing).
Among these, most preferably, consider from the aspect of making the sensitivity behind the active energy ray-curable resin composition, can enumerate the resultant of reaction or the styracin of (methyl) vinylformic acid, (methyl) vinylformic acid and 6-caprolactone.
Can polymeric ethylenic unsaturated group and the compound (b) of an above carboxyl as having concurrently in a part more than one, do not have the compound of hydroxyl in the preferred compound.
The compound (c) that has an above hydroxyl and an above carboxyl among the present invention in employed a part concurrently makes its reaction in order to import hydroxyl in carbonate.Comprise the compound that has an above hydroxyl and two above carboxyls in the compound that has two above hydroxyls and a carboxyl in the compound that has a hydroxyl and a carboxyl in a part concurrently, a part concurrently, a part concurrently in these compounds.
As the compound that has a hydroxyl and a carboxyl in a part concurrently, can enumerate for example hydroxy-propionic acid, hydroxybutyric acid, oxystearic acid etc.
And,, can enumerate dihydroxymethyl acetate, dimethylol propionic acid, dimethylolpropionic acid etc. as the compound that has two above hydroxyls and a carboxyl in a part concurrently.
As the compound that has an above hydroxyl and two above carboxyls in a part concurrently, can enumerate hydroxyl phthalic etc.
Among these, consider effect of the present invention, comprise the compound of two above hydroxyls in preferred a part.In addition, consider the stability of carboxylic esterification reaction, the carboxyl in preferred a part is one a compound.The compound that most preferably has two hydroxyls and a carboxyl in a part.Consider raw-material acquisition, dimethylol propionic acid and dimethylolpropionic acid are specially suitable.
As the compound (c) that has an above hydroxyl and an above carboxyl in a part concurrently, preferably in compound, do not have can polymeric ethylenic unsaturated group compound (c).
Among these, if consider the stability of above-mentioned Resins, epoxy (a) and two kinds of carboxylic acid cpds (b) and reaction (c), then preferred (b) and (c) be monocarboxylic acid, even when share monocarboxylic acid and polycarboxylic acid, also the value of preferably representing with the total molar weight of the total molar weight/polycarboxylic acid of monocarboxylic acid is more than 15.
Resins, epoxy (a) in this reaction should change according to purposes is suitable with the ingredient proportion of the total of carboxylic acid cpd (b) and carboxylic acid (c).That is, with whole epoxy group(ing) carboxylic esterifications situation under because that unreacted epoxy groups does not have is remaining, thereby higher as the storage stability of reactive carbonate.In this case, the reactivity of only utilizing the two keys imported to provide.
On the other hand, deliberately make unreacted remaining epoxy group(ing) remaining by reducing carboxylic acid cpd (b) and charging capacity (c), can compoundly utilize also that the unsaturated link(age) that imported provides reactive and the reaction that remaining epoxy group(ing) causes, for example, by catalytic polyreaction of light cationic catalyst or heat polymerization.But, in this case, should be noted that the preservation of reactive carbonate and the research of creating conditions.
When making the reactive epoxy carbonate (A) of remaining reactive epoxy group(ing) not, preferably with respect to 1 equivalent epoxy group(ing) of above-mentioned Resins, epoxy (a), carboxylic acid cpd (b) and (c) add up to 90～120 equivalent %.As long as in this scope, just can under more stable condition, make.The charging capacity of carboxylic acid cpd is during more than above-mentioned scope, and carboxylic acid cpd (b) that can remaining surplus is therefore not preferred.
And, deliberately make under the residual situation of epoxy group(ing), preferably with respect to the above-mentioned Resins, epoxy of 1 equivalent (a), carboxylic acid cpd (b) and (c) add up to 20～90 equivalent %.When outside this scope, the effect of composite curing weakens.Certainly, in this case, need give one's full attention to the gelation in the reaction, the ageing stability of carbonate (A).
Can polymeric ethylenic unsaturated group and the compound (b) and the usage ratio that has the compound (c) of an above hydroxyl and an above carboxyl concurrently of an above carboxyl about having concurrently more than one, molar ratio computing with carboxyl, (b): (c) be preferably 9:1～1:9, more preferably the scope of 4:6～8:2.As long as in this scope, just can prevent that the sensitivity when (b) is very few from reducing, and the effect reduction of (c) can prevent that (c) is very few the time.
The reaction of this carboxylic esterification also can be reacted in solvent-free mode, perhaps also can react behind enough solvent cuts.As solvent as used herein,, just be not particularly limited so long as reaction is the inert solvent to carboxylic esterification.
Preferred solvent load should suit to adjust according to the viscosity and the purposes of resulting resin, but the use solvent, makes solids component preferably reach 90～30 quality %, more preferably reach 80～50 quality %.
If example illustrates the concrete example that can be used as above-mentioned solvent, then can enumerate, for example fragrant family hydrocarbon solvents such as toluene, dimethylbenzene, ethylbenzene, tetramethyl-benzene; Fatty family hydrocarbon solvent such as hexane, octane, decane and as their sherwood oil, white gasoline, solvent naphtha etc. of mixture.
And,, can enumerate alkyl acetate classes such as ethyl acetate, propyl acetate, butylacetate as the ester series solvent; Cyclic ester classes such as gamma-butyrolactone; Single alkylene glycol monoalky lether monoacetate class or many alkylene glycols monoalky lether monoacetate classes such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Triethylene glycol ethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol methyl ether acetate, butyleneglycol methyl ether acetate; Polycarboxylic acid alkyl esters such as pentanedioic acid dialkyl, dialkyl succinate, hexanodioic acid dialkyl etc.
And,, can enumerate alkyl ethers such as diethyl ether, ethyl-butyl ether as the ether series solvent; Glycol ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dme, dipropylene glycol diethyl ether, triethylene glycol dme, triethylene glycol diethyl ether; Ring-type ethers such as tetrahydrofuran (THF) etc.
And,, can enumerate acetone, methyl ethyl ketone, pimelinketone, isophorone etc. as the ketone series solvent.
In addition, reaction can also be carried out separately or in the mixed organic solvents at the reactive compounds (C) except that (A) described later, (B) etc.In this case, when using with the form of curing composition, owing to can be directly be used with the form of composition, so be preferred.
Preferably use catalyzer in order to promote reaction during reaction, with respect to reactant, that is, with respect to the total amount of the reactant that comprises solvent of using under above-mentioned epoxy compounds (a), compound (b), compound (c) and some situation etc., this catalyst consumption is 0.1～10 quality %.The temperature of reaction of this moment is 60～150 ℃, and the reaction times is preferably 5～60 hours.Concrete example as spendable catalyzer, can enumerate, for example known general basic catalysts such as triethylamine, benzyldimethylamine, triethylamine hydrochloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, sad chromium, zirconium caprylate etc.
And,, preferably use hydroquinone monomethyl ether, 2-toluhydroquinone, quinhydrones, phenylbenzene bitter taste hydrazides, diphenylamine, 3,5-di-t-butyl-4-hydroxytoluene etc. as hot stopper.
This reaction is suitably sampled, reach below the 5mgKOH/g with the sample acid number simultaneously, preferably reach the terminal point of the following moment of 2mgKOH/g for this reaction.
As the preferred molecular weight range of the reactive carbonate (A) that obtains like this, the scope of the polystyrene conversion weight-average molecular weight that is obtained by GPC is 1,000～30,000, more preferably 1,500～20,000.
When less than this molecular weight, can't give full play to the obdurability of cured article; And when greater than this molecular weight, viscosity raises, and is difficult to coating etc.
Next, the of the present invention reactive polycarboxylic acid compound (B) that obtains by sour addition operation is described.The purpose of carrying out sour addition operation is as required carboxyl to be imported in the reactive carbonate (A) that obtains in preceding operation, to obtain reactive polycarboxylic acid compound (B).The importing of carboxyl is for following purpose: for example needing to form in the purposes of resist pattern etc., giving solubility, and giving and the adaptation of metal, inorganics etc. buck to the non-irradiation of active energy beam portion, or the like.
Specifically, make multi-anhydride (d) and the hydroxyl generation addition reaction that generates by the reaction of epoxy carboxylic esterification, by ester bond carboxyl is imported thus.
Concrete example as multi-anhydride (d), for example, can use all multi-anhydrides, as long as it is the compound that has acid anhydride structure in a part, however excellent succinyl oxide, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic acid 1,2-anhydride or maleic anhydrides such as special preferred bases aqueous solution development, thermotolerance, hydrolytic resistance.
The reaction of addition multi-anhydride (d) can be undertaken by add multi-anhydride (d) in above-mentioned carboxylic esterification reaction solution.Addition should change according to purposes is suitable.
But, in the time will using polycarboxylic acid compound of the present invention (B) as the resist of alkali-developable, the charging capacity of preferred multi-anhydride (d) is to make the solids component acid number (based on JIS K5601-2-1:1999) of the reactive polycarboxylic acid compound (B) that finally obtains reach 30～120mgKOH/g, more preferably reach the value that 40～105mgKOH/g calculates.When the solids component acid number of this moment was this scope, the alkali aqueous solution development of active energy ray-curable resin composition of the present invention demonstrated good development.That is, it is good and to crossing also broad of the span of control of developing that pattern forms property, and acid anhydrides that also can residual surplus.
Preferably use catalyzer in order to promote reaction during reaction, with respect to reactant, promptly, with respect to the total amount that comprises by the reactant of solvent that uses under above-mentioned epoxy compounds (a), carboxylic acid cpd (b) and the carbonate (A) that (c) obtains and multi-anhydride (d), some situation etc., this catalyst consumption is 0.1～10 quality %.The temperature of reaction of this moment is 60～150 ℃, and the reaction times is preferably 5～60 hours.As the concrete example of spendable catalyzer, can enumerate for example triethylamine, benzyldimethylamine, triethylamine hydrochloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, sad chromium, zirconium caprylate etc.
This sour addition reaction also can be reacted in solvent-free mode, perhaps also can react behind enough solvent cuts.As solvent as used herein,, just be not particularly limited so long as sour addition reaction is the inert solvent.Specifically, can use and illustrative solvent phase solvent together in the carboxylic esterification reaction of preceding operation.Under the situation that the use solvent is made in the carboxylic esterification reaction of preceding operation, with solvent described two reactions being inertia is condition, also can not remove and desolvate and direct the confession in the sour addition reaction as subsequent processing.
Preferred solvent load should suit to adjust according to the viscosity and the purposes of resulting resin, but the use solvent, makes solids component preferably reach 90～30 quality %, more preferably reach 80～50 quality %.
In addition, this sour addition reaction can also be carried out separately or in the mixed organic solvents at reactive compounds described later (C) etc.In this case, when using with the form of curing composition, owing to can be directly be used with the form of composition, therefore preferably.
And, the same hot stopper of illustration during preferred use such as hot stopper is reacted with above-mentioned carboxylic esterification.
This reaction is sampled aptly, and simultaneously the point that reaches positive and negative 10% the scope of setting acid number with the acid number of reaction product is the terminal point of this reaction.
Active energy ray-curable resin composition of the present invention comprises epoxy carbonate (A) and/or polycarboxylic acid compound (B).Epoxy carbonate (A) and/or polycarboxylic acid compound (B) can use flexibly according to its purposes is suitable.For example, in the purposes of solder resist and so on, do not develop and when utilizing print process to form pattern or utilize solvent etc. to make under the situation of unreacted position diffluence (so-called solvent develop type), use epoxy carbonate (A) to get final product; Utilize buck to make under the situation of its development, use polycarboxylic acid compound (B) to get final product.Generally under the situation of liquid alkali developing type, easily produce the such aspect consideration of fine pattern, the polycarboxylic acid compounds (B) that use in this purposes more.Certainly, share epoxy carbonate (A) and polycarboxylic acid compound (B) also without any problem.
Active energy ray-curable resin composition of the present invention also can further comprise division ring oxycarboxylic acid ester cpds (A) and polycarboxylic acid compound (B) reactive compounds (C) in addition.
As the concrete example of spendable reactive compounds (C) among the present invention, can enumerate the epoxy compounds class of esters of acrylic acid, cationoid reaction type and the alloytype thereof of free radical reaction type, not only be fit to free radical reaction type but also be fit to the vinyl compound class etc. of cationoid reaction type, so-called reactive oligomers class.
As spendable esters of acrylic acid, can enumerate simple function (methyl) esters of acrylic acid, multifunctional (methyl) acrylate, also have epoxy acrylate, polyester acrylate, urethane acrylate etc.
As simple function (methyl) esters of acrylic acid, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid Lauryl Ester, polyoxyethylene glycol (methyl) acrylate, polyoxyethylene glycol (methyl) acrylate monomethyl ether, (methyl) vinylformic acid phenylethylester, (methyl) isobornyl acrylate, (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid tetrahydro furfuryl ester etc.
As multifunctional (methyl) esters of acrylic acid, can enumerate butyleneglycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, nonanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, three (methyl) acryloxy ethyl isocyanuric acid ester, polypropylene glycol two (methyl) acrylate, hexanodioic acid epoxy two (methyl) acrylate, ethoxylation bis-phenol two (methyl) acrylate, ethoxylation A Hydrogenated Bisphenol A (methyl) acrylate, bis-phenol two (methyl) acrylate, two (methyl) acrylate of the 6-caprolactone affixture of hydroxypivalic acid neopentyl glycol, poly-(methyl) acrylate of the reaction product of Dipentaerythritol and 6-caprolactone, Dipentaerythritol gathers (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, triethylol propane three (methyl) acrylate and ethylene oxide adduct thereof, tetramethylolmethane three (methyl) acrylate and ethylene oxide adduct thereof, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate and ethylene oxide adduct thereof etc.
As spendable vinyl compound class, can enumerate vinyl ethers, styrenic, other vinyl compounds.As vinyl ethers, can enumerate ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol bisthioglycolate vinyl ether etc.As styrenic, can enumerate vinylbenzene, vinyl toluene, ethyl styrene etc.As other vinyl compounds, can enumerate triallyl isocyanurate, front three for allyl group isocyanuric acid ester etc.
In addition, as so-called reactive oligomers class, can enumerate same intramolecularly have concurrently can the urethane acrylate of functional group of reacting under the active energy beam effect and amino-formate bond, same intramolecularly have concurrently equally can the polyester acrylate of functional group of reacting under the active energy beam effect and ester bond, derived from other Resins, epoxy and the combination of epoxy acrylate, these acrylate that has the functional group that can under the active energy beam effect, react at same intramolecularly concurrently by reactive oligomers of compound use etc.
In addition, general so long as have the compound of epoxy group(ing) as cationoid reaction type monomer, just be not particularly limited.For example can enumerate, (methyl) glycidyl acrylate, the methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl base ether, the dihydroxyphenyl propane diglycidyl ether, 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate (" the サ イ ラ キ ュ ア UVR-6110 " that ユ ニ オ ン カ ー バ イ De society makes etc.), 3,4-epoxycyclohexyl ethyl-3, the 4-epoxycyclohexane carboxylate, vinyl cyclohexene diepoxide (" ELR-4206 " that ユ ニ オ ン カ ー バ イ De society makes etc.) limonene dioxide (" the セ ロ キ サ イ De 3000 " that Daicel chemical industry society makes etc.), allyl group tetrahydrobenzene diepoxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-volution-3, the 4-epoxy) hexanaphthene-1, the 3-dioxane, two (3, the 4-epoxycyclohexyl) adipic acid ester (" the サ イ ラ キ ュ ア UVR-6128 " that ユ ニ オ ン カ ー バ イ De society makes etc.), two (3,4-epoxycyclohexyl methyl) adipic acid ester, two (3, the 4-epoxycyclohexyl) ether, two (3,4-epoxycyclohexyl methyl) ether, two (3, the 4-epoxycyclohexyl) di-ethyl siloxane etc.
Among these, as reactive compounds (C), the most preferably esters of acrylic acid of radical-curable.Under the cationic situation,, thereby need make two liquid mixed types because carboxylic acid and epoxy group(ing) can react.
The reactive compounds (C) except that (A), (B) of carbonate of the present invention (A) and/or reactive polycarboxylic acid compound (B) and interpolation is in case of necessity mixed, can access active energy ray-curable resin composition of the present invention.At this moment, can also add other compositions aptly according to purposes.
For active energy ray-curable resin composition of the present invention, in composition, contain 97～5 quality %, be preferably carbonate (A) and/or the reactive polycarboxylic acid compound (B) of 87～10 quality %, contain 3～95 quality %, the reactive compounds (C) except that (A), (B) of 3～90 quality % more preferably.As required, can also contain other compositions that are limited to about 70 quality %.
Spendable tinting pigment is in order to be that coloured material uses with active energy ray-curable resin composition of the present invention among the present invention.The balance of the hydroxyl of the carbonate that uses among the present invention (A), reactive polycarboxylic acid compound (B) is in specified range, therefore can know by inference, can bring into play the excellent especially affinity to pigment, that is, and and dispersiveness.This mechanism is still indeterminate, yet because good dispersion ground carries out, so its result can improve pigment concentration; And, therefore can bring into play good pattern and form characteristic owing in the composition that needs develop, disperse to be in more suitably state; And because the development residue in the development dissolving portion is also less, therefore active energy ray-curable resin composition of the present invention is suitable.
As tinting pigment, can enumerate pigment dyestuffs such as phthalocyanine system, azo system, quinacridone; Mineral dye such as carbon black etc., titanium dioxide.Among these, the high and carbon black most preferably of carbon black dispersion.
In active energy ray-curable resin composition of the present invention,, can add Photoepolymerizationinitiater initiater in order to carry out effectively and fully solidifying.As Photoepolymerizationinitiater initiater, can enumerate the free radical type Photoepolymerizationinitiater initiater, positively charged ion is Photoepolymerizationinitiater initiater, other polymerization starters.
As the free radical type Photoepolymerizationinitiater initiater, can enumerate for example bitter almond oil camphor classes such as bitter almond oil camphor, bitter almond oil camphor methyl ether, bitter almond oil camphor ether, bitter almond oil camphor propyl ether, bitter almond oil camphor ethyl isobutyl ether; Methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-acetophenones such as 1-ketone; Anthraquinone classes such as 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; 2, thioxanthene ketones such as 4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2-clopenthixal ketone; Ketal classes such as methyl phenyl ketone dimethyl ketal, benzyl dimethyl ketal; Benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4,4 '-benzophenones such as two methylamino benzophenone; 2,4, known general free radical type photoreaction initiator such as phosphine oxide class such as 6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl) phenylphosphine oxide.
And, as positively charged ion is Photoepolymerizationinitiater initiater, can enumerate lewis acidic diazonium salt, lewis acidic salt compounded of iodine, lewis acidic sulfonium salt, Lewis acid De phosphonium salt, other halogenide, triazine series initiators, borate-based initiator and other Photoacid generator etc.
As lewis acidic diazonium salt, can enumerate p-methoxyphenyl diazonium fluoride phosphoric acid salt, N, N-diethylamino phenyl diazonium hexafluorophosphate (the サ Application エ イ De SI-60L/SI-80L/SI-100L that three new chemical industry societies make etc.) etc.; As lewis acidic salt compounded of iodine, can enumerate diphenyl iodine hexafluorophosphate, phenylbenzene iodine hexafluoro antimonate etc.; As lewis acidic sulfonium salt, can enumerate triphenylsulfonium hexafluorophosphate (the Cyracure UVI-6990 that Union Carbide society makes etc.), triphenylsulfonium hexafluoro antimonate (the Cyracure UVI-6974 that Union Carbide society makes etc.) etc.; As Lewis acid De phosphonium salt, can enumerate triphenyl phosphorus hexafluoro antimonate etc.
As other halogenide, can enumerate 2,2,2-three chloro-[1-4 '-(dimethyl ethyl) phenyl] ethyl ketone (the Trigonal PI that AKZO society makes etc.), 2,2-two chloro-1-4-(Phenoxyphenyl) ethyl ketones (Sandray1000 that Sandoz society makes etc.), α, α, α-trisbromomethyl phenyl sulfone (BMPS that system iron chemistry society makes etc.) etc.As the triazine series initiators, can enumerate 2,4,6-three (trichloromethyl)-s-triazine, 2,4-trichloromethyl-(4 '-p-methoxy-phenyl)-6-triazine (the Triazine A that Panchim society makes etc.), 2,4-trichloromethyl-(4 '-methoxyl-styrene)-6-triazine (the Triazine PMS that Panchim society makes etc.), 2,4-trichloromethyl-(piperonyl)-6-triazine (the Triazine PP that Panchim society makes etc.), 2,4-trichloromethyl-(4 '-methoxyl group naphthyl)-6-triazine (the Triazine B that Panchim society makes etc.), 2-[2 '-(5 ' '-the methyl furan base) ethylidene]-4, two (the trichloromethyl)-s-triazines of 6-(three and ケ ミ カ Le society make etc.), 2-(2 '-furyl ethylidene)-4, two (the trichloromethyl)-s-triazines of 6-(three and ケ ミ カ Le society make) etc.
As borate-based initiator, can enumerate NK-3876 that Japanese photopigment makes and NK-3881 etc.; As other photic acid producing agent etc., can enumerate the 9-phenylacridine, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2-bisglyoxaline (dark fund changes into the bisglyoxaline of society's manufacturing etc.), 2, two (2-aminopropane) dihydrochlorides of 2-azo (V50 that makes with the pure medicine of light society etc.), 2, two [2-(tetrahydroglyoxaline-2-yl) propane] dihydrochlorides of 2-azo (VA044 that makes with the pure medicine of light society etc.), [η-5-2-4-(cyclopentadecane base) (1,2,3,4,5,6-η)-(methylethyl) benzene] iron (II) hexafluorophosphate (Irgacure261 that Ciba Geigy society makes etc.), two (η 5-cyclopentadienyls) two [2,6-two fluoro-3-(1H-pyrroles-1-yl) phenyl] titanium (CGI-784 that Ciba Geigy society makes etc.) etc.
In addition, can also share azo series initiators, benzoyl peroxides etc. such as Diisopropyl azodicarboxylate to heat sensitive peroxidation system free radical type initiator etc.And also can share free base system and positively charged ion is these two kinds of initiators.Initiator can also be used alone, and can also share two or more.
In addition, be fit for various uses, be limited to other compositions of 70 quality % on also can in resin combination, adding in order to make active energy ray-curable resin composition of the present invention.As other compositions, can enumerate other additives, paint material, coloured material and volatile solvent etc., volatile solvent adds to give the suitable property of coating etc. in order to adjust viscosity.Spendable other composition illustrations are as follows.
As other additives, can use for example thermal curing catalyst such as trimeric cyanamide; Thixotropy imparting agents such as fumed silica; Silicone-based, fluorine are flow agent or defoamer; Stopper such as quinhydrones, hydroquinone monomethyl ether; Stablizer; Antioxidant etc.
And, as other paint materials, for example can also use, not to be colored as the so-called pigment extender of purpose.For example can enumerate talcum, barium sulfate, lime carbonate, magnesiumcarbonate, barium titanate, aluminium hydroxide, silicon-dioxide, clay etc.
In addition, active energy beam is not shown that reactive resene (so-called inert polymer) for example can use other Resins, epoxy, resol, carbamate resins, vibrin, ketone resin, cresol resin, xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin and their modifier.Use in the preferred scope of these resins below 40 quality %.
Particularly, in the time will in the solder resist purposes, using reactive polycarboxylic acid compound (B),, preferably use known general Resins, epoxy as active energy beam is not shown reactive resene.This is because after active energy beam effect reaction down, the curing, the carboxyl from (B) also can residually be arranged, as a result the water tolerance of its cured article or water-disintegrable deterioration.Therefore,, make the further carboxylic esterification of residual carboxyl, form more strong crosslinking structure by using Resins, epoxy.
And,, can also in resin combination below 50 quality %, further add volatile solvent in the scope below the preferred 35 quality % in order to adjust viscosity according to application target.
The present invention relates to form active energy ray-curable resin composition with material or anticorrosive additive material composition as molding material, tunicle.
Molding material among the present invention is meant the material that is used for following purposes: uncured composition is put into mold, perhaps press mold and after molding object, utilize active energy beam to make it curing reaction take place and the purposes of moulding; Perhaps to uncured focused lights such as composition irradiating laser etc., make it curing reaction take place and the purposes of moulding.
As concrete purposes, can enumerate and be shaped to plane sheet material; The sealing material that is used for protecting component; To be impressed into through " mold " of microfabrication and carry out fine moulding, so-called nano impression material on the uncured composition; And particularly heat management requires the peripheral sealing material etc. of harsh photodiode, photo-electric conversion element etc., and these are suitable purposes.
Tunicle among the present invention forms and is utilized in order to be covered substrate surface with material.As concrete purposes, ink materials such as photogravure ink, flexo printing ink, silk-screen ink, flexographic ink; Coating materials such as dura mater, finish paint, overprint varnish zhe, Clear coating; Lamination various joint compounds such as uses with, CD; Adhesivess such as (pressure-sensitive) tackiness agent; Solder resist, anticorrosion layer, micromotor are equivalent to tunicle with anticorrosive additive materials such as resist etc. and form and use material.In addition, so-called dry film also is equivalent to tunicle and forms that use material, so-called dry film be to form like this: tunicle is formed with material temporarily coat on the separability base material and after carrying out film forming, fit on the target substrate formation tunicle originally.
Among these purposes, by importing the carboxyl of reactive polycarboxylic acid compound (B), be improved, so the tunicle among the present invention forms with material and preferably uses in the purposes of be used for being covered plastic basis material or metal base with the adaptation of base material.
In addition, unreacted reactive polycarboxylic acid compound (B) is given full play to and be the feature of solubility in alkali aqueous solution, thereby the active energy ray-curable resin composition among also preferred the present invention is as liquid alkali developing type anticorrosive additive material composition.
Anticorrosive additive material composition among the present invention is meant following composition: on base material, form said composition by rete, thereafter, irradiation ultraviolet radiation isoreactivity energy-ray partly is to utilize irradiation portion, the composition of the active energy beam responsive type drawn of the physical difference of irradiation portion not.Specifically, be the composition that uses with following purpose: utilize some method (for example utilize solvent etc. or basic solution etc. to make its dissolving, or the like) to remove irradiation portion or irradiation portion not, to draw.
Active energy ray-curable resin composition of the present invention utilizes active energy beam to solidify easily.At this,, can enumerate hertzian wave such as ultraviolet ray, visible rays, infrared rays, X ray, gamma-rays, laser rays as the concrete example of active energy beam; Beta lines such as alpha-ray, β ray, electron rays etc.Consider the purposes that the present invention is fit to, among these, preferred ultraviolet ray, laser rays, visible rays or electron rays.
Active energy ray-curable resin composition of the present invention can be suitable for the various materials of patternable, for example particularly, layer insulation material for solder resist material, lamination method (PVC Le De ア ッ プ worker method) usefulness is useful, in addition, as optical waveguides, can also be used in the such electric base material of printed circuit board (PCB), optoelectronic substrate or photopolymer substrate, electronic substrate and light base material etc.
As specially suitable purposes, give full play to the characteristic that can access tough cured article, permanent resist purposes such as preferred solder resist; Give full play to the good such characteristic of pigment-dispersing, chromatic photoresist, particularly black matrix layer such as preferred printing-ink, the colour filter purposes of resist.
In addition, be particularly suitable for the dry film purposes, have physical strength before the curing reaction of dry film purposes requirement under the active energy beam effect.That is, the hydroxyl of the above-mentioned Resins, epoxy (a) that uses among the present invention, the balance of epoxy group(ing) are in specified range, although therefore reactive carbonate of the present invention has higher molecular weight, can give play to good development also.
As the method that forms tunicle, be not particularly limited, however can at random adopt planography ways such as porous printing mode, offset printing such as letterpress mode, silk screen printing such as intaglio printing mode, flexographic printing such as photogravure, various coating method (such as roller coating machine, cutter be coated with machine, mould is coated with machine, curtain coater, spin coater etc.).
The cured article of active energy ray-curable resin composition of the present invention is meant, in order to be used for such use, to active energy ray-curable resin composition irradiation active energy beam of the present invention, makes the cured article that obtains after its curing.
Having covered surperficial article with active energy ray-curable resin composition of the present invention is meant, on suitable base material, form active energy ray-curable resin composition of the present invention by rete, irradiation ultraviolet radiation isoreactivity energy-ray partly, the article that the tunicle cured layer on the base material is formed.At this moment, can be the article that on base material, the cured article of this resin combination formed entirely the tunicle cured layer, also can be to have formed through the resist pattern article of drawing the tunicle cured layer that forms, be not particularly limited.
Embodiment
Below, the present invention will be described in more detail by embodiment, however the present invention is not limited to these embodiment.And, among the embodiment only otherwise special declaration, " part " expression " mass parts ".
Softening temperature, epoxy equivalent (weight) etc. utilize following condition to measure.
1) epoxy equivalent (weight): utilize and measure based on the method for JIS K7236:2001.
2) softening temperature: utilize and measure based on the method for JIS K7234:1986.
3) acid number: utilize and measure based on the method for JIS K0070:1992.
4) condition determination of GPC is as follows.
Type: TOSOH HLC-8220GPC
Post: TSKGEL Super HZM-N
Elutriant: THF (tetrahydrofuran (THF)); Per minute 0.35ml, 40 ℃
Detector: differential refractometer
Molecular weight standard: polystyrene
Reference example 1: utilize the Resins, epoxy shown in the general formula (2) to prepare carbonate (A)
Add the 288g NC-3000H (R that provides in Japanese chemical drug manufacturing, 70 ℃ of softening temperatures, epoxy equivalent (weight) 288g/eq, the general formula (2) 3All be that hydrogen atom, p count 3 with mean value) as the vinylformic acid of the record amount in Resins, epoxy (a), the table 1 (being called for short AA, Mw=72) as have concurrently in the molecule more than one can polymeric ethylenic unsaturated group and the compound (b) of an above carboxyl, the dimethylol propionic acid (being called for short DMPA, Mw=134) of record amount in the table 1 as the compound (c) that has an above hydroxyl and an above carboxyl in the molecule concurrently.Put down in writing each AA, DMPA with respect to the epoxy group(ing) equivalence ratio that feeds intake with mol ratio.
Add the 3g triphenylphosphine as catalyzer, make propylene glycol monomethyl ether monoacetate that solids component reaches 80 quality % as solvent, in 100 ℃ of reactions 24 hours, obtain carbonate of the present invention (A) solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine that measured value is recorded in the table 1.For determination of acid value, utilize reaction soln to measure and be converted into acid number with solid component meter.
Reference example 2: utilize the Resins, epoxy shown in the general formula (3) to prepare carbonate (A)
Add 230g NC-2000 (Japanese chemical drug manufacturing, the R that provides in 60 ℃ of softening temperatures, epoxy equivalent (weight) 230g/eq, the general formula (3) 4All be that hydrogen atom, r count 5 with mean value) as the vinylformic acid of the record amount in Resins, epoxy (a), the table 1 as the dimethylol propionic acid of the record amount in compound (b) and the table 1 as compound (c).Put down in writing each AA, DMPA with respect to the epoxy group(ing) equivalence ratio that feeds intake with mol ratio.
Add the 3g triphenylphosphine as catalyzer, make the propylene glycol monomethyl ether monoacetate of 80 quality % that solids component reaches reaction solution as solvent, in 100 ℃ of reactions 24 hours, obtain carbonate (A) solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine that measured value is recorded in table 1.For determination of acid value, utilize reaction soln to measure and be converted into acid number with solid component meter.
Reference example 3: utilize the Resins, epoxy shown in the general formula (4) to make epoxy carbonate (A)
Add 250g XD-1000 (Japanese chemical drug manufacturing, the R that provides in 70 ℃ of softening temperatures, epoxy equivalent (weight) 250g/eq, the general formula (4) 5All be that hydrogen atom, t count 3 with mean value) as the vinylformic acid of the record amount in Resins, epoxy (a), the table 1 as the dimethylol propionic acid of the record amount in compound (b) and the table 1 as compound (c).Put down in writing each AA, DMPA with respect to the epoxy group(ing) equivalence ratio that feeds intake with mol ratio.
Use the 3g triphenylphosphine as catalyzer, add and make propylene glycol monomethyl ether monoacetate that solids component reaches 80 quality %,, obtain epoxy carbonate (A) solution in 100 ℃ of reactions 24 hours as solvent.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine that measured value is recorded in the table 1.For determination of acid value, utilize reaction soln to measure and be converted into acid number with solid component meter.
Embodiment 1: relatively use the preparation of carbonate
Add 288g NC-3000H, 72g (mol ratio: 1.0) vinylformic acid as compound (b), 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % as solvent, in 100 ℃ of reactions 24 hours, obtain carbonate solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine that measured value is recorded in the table 1.For determination of acid value, utilize reaction soln to measure and be converted into acid number with solid component meter.
Embodiment 2: relatively use the preparation of carbonate
Add 230g NC-2000,72g (mol ratio: 1.0) vinylformic acid as compound (b), 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % of reaction solution as solvent, in 100 ℃ of reactions 24 hours, obtain carbonate solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine that measured value is recorded in table 1.For determination of acid value, utilize reaction soln to measure and be converted into acid number with solid component meter.
Embodiment 3: relatively use the preparation of epoxy carbonate
Add 250g XD-1000,72g (mol ratio: 1.0) vinylformic acid as compound (b), 3g triphenylphosphine as catalyzer, make solids component reach the propylene glycol monomethyl ether monoacetate of 80 quality % as solvent, in 100 ℃ of reactions 24 hours, obtain epoxy carbonate solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine that measured value is recorded in the table 1.For determination of acid value, utilize reaction soln to measure and be converted into acid number with solid component meter.
Comparative example 4-1: relatively use the preparation of carbonate
(mol ratio: 0.5) vinylformic acid can polymeric ethylenic unsaturated group and compound (b), the 67g (mol ratio of an above carboxyl as having concurrently in the molecule more than one to add 200g cresols line style phenol aldehyde type epoxy resin EOCN-103S (Japanese chemical drug manufacturing, 80 ℃ of softening temperatures, epoxy equivalent (weight) 200g/eq), 36g; 0.5) dimethylol propionic acid is as the compound (c) that has an above hydroxyl and an above carboxyl in the molecule concurrently.
Add the 3g triphenylphosphine as catalyzer, make propylene glycol monomethyl ether monoacetate that solids component reaches 80 quality % as solvent, in 100 ℃ of reactions 24 hours, relatively used carbonate solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine that measured value is recorded in the table 1.For determination of acid value, utilize reaction soln to measure and be converted into acid number with solid component meter.
Comparative example 4-2: relatively use the preparation of carbonate
Add 200g cresols line style phenol aldehyde type epoxy resin jER-1002 (ジ ャ パ Application エ Port キ シ レ ジ Application society makes, epoxy equivalent (weight) 400g/eq), (mol ratio: 0.5) (mol ratio: 0.5) dimethylol propionic acid is as compound (c) as compound (b), 34g for vinylformic acid for 18g.
Add the 3g triphenylphosphine as catalyzer, make the propylene glycol monomethyl ether monoacetate of 80 quality % that solids component reaches reaction solution as solvent, in 100 ℃ of reactions 24 hours, relatively used carbonate solution.
Reaction end utilizes solids component acid number (AV; MgKOH/g) determine that measured value is recorded in table 1.For determination of acid value, utilize reaction soln to measure and be converted into acid number with solid component meter.
Table 1
Table 1 reference example 1,2,3 and embodiment 1,2,3, comparative example 4: the preparation of epoxy carbonate (A)
Test example 1: the storage stability of epoxy carbonate (A)
The epoxy carbonate solution that obtains among reference example 1 and the embodiment 1 is stored in refrigeration chamber than low 5 ℃ of freezing point, relatively, lists in table 2 up to producing the crystalline time.
Table 2
Table 2 test example 1: the storage stability of epoxy carbonate
Figure BDA00002935838600222
By above result as can be known, along with the importing of the compound (c) that has an above hydroxyl and an above carboxyl in the molecule concurrently, the storage stability of resin solution has improved.
Reference example 4: utilize the Resins, epoxy preparation feedback polycarboxylic acid compound (B) shown in the general formula (2)
The Tetra Hydro Phthalic Anhydride of the record amount among the carbonate that obtains separately in reference example 1-1,1-2,1-3 (A) the solution 299g in the interpolation table 3 (being called for short THPA) is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 ℃, carry out sour addition reaction, obtain reactive polycarboxylic acid compound of the present invention (B) solution (reference example 4-1,4-2,4-3,4-4).Solids component acid number (mgKOH/g) is listed in table 3.
Reference example 5: utilize the Resins, epoxy preparation feedback polycarboxylic acid compound (B) shown in the general formula (3)
The Tetra Hydro Phthalic Anhydride of amount that adds table 3 record in reference example 2-1,2-2,2-3,2-4 among the carbonate that obtains separately (A) the solution 299g is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % of reaction solution as solvent, be heated to 100 ℃, carry out sour addition reaction in 3 hours, obtain reactive polycarboxylic acid compound of the present invention (B) solution (reference example 5-1,5-2,5-3,5-4,5-5).Solids component acid number (mgKOH/g) is listed in table 3.
Reference example 6: utilize the Resins, epoxy shown in the general formula (4) to make polycarboxylic acid compound (B)
The Tetra Hydro Phthalic Anhydride of the record amount among epoxy carbonate (A) the solution 299g that obtains separately in reference example 3-1,3-2,3-3 in the interpolation table 3 is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 ℃, carry out sour addition reaction, obtain polycarboxylic acid compound (B) solution (reference example 6-1,6-2,6-3,6-4).Solids component acid number (mgKOH/g) is listed in table 3.
Embodiment 5: relatively use the preparation of reactive polycarboxylic acid compound
The Tetra Hydro Phthalic Anhydride of the record amount among the carbonate solution 299g that obtains in embodiment 1 in the interpolation table 3 is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 ℃, carry out sour addition reaction, obtain reactive polycarboxylic acid compound solution (embodiment 5-1,5-2).Solids component acid number (mgKOH/g) is listed in table 3.
Embodiment 6: relatively use the preparation of reactive polycarboxylic acid compound
The Tetra Hydro Phthalic Anhydride of the amount of interpolation table 3 record is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % of reaction solution as solvent among the carbonate solution 299g that obtains in embodiment 2, be heated to 100 ℃, carry out sour addition reaction in 3 hours, obtain reactive polycarboxylic acid compound solution (embodiment 6-1,6-2).Solids component acid number (mgKOH/g) is listed in table 3.
Embodiment 7: relatively use the preparation of reactive polycarboxylic acid compound
The Tetra Hydro Phthalic Anhydride of the record amount among the epoxy carbonate solution 299g that obtains in embodiment 3 in the interpolation table 3 is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 ℃, carry out sour addition reaction, obtain polycarboxylic acid compound solution (embodiment 7-1,7-2).Solids component acid number (mgKOH/g) is listed in table 3.
Comparative example 8: relatively use the preparation of reactive polycarboxylic acid compound
The Tetra Hydro Phthalic Anhydride of the record amount among the epoxy carbonate solution 299g that obtains in comparative example 4-1,4-2 in the interpolation table 3 is as multi-anhydride (d) and make solids component reach the propylene glycol monomethyl ether monoacetate of 65 quality % as solvent, be heated to 100 ℃, carry out sour addition reaction, obtain polycarboxylic acid compound solution (comparative example 8-1,8-2,8-3).Solids component acid number (mgKOH/g) is listed in table 3.
Table 3
Table 3 reference example 4,5,6 and embodiment 5,6,7, comparative example 8: the preparation of reactive polycarboxylic acid compound (B)
Figure BDA00002935838600241
Reference example 7,8,9 and embodiment 9,10,11, comparative example 12: the preparation of dura mater usefulness composition and cured article thereof and their hardness evaluation test, impact evaluation test
With the reactive carbonate (A) of preparation in 20g reference example 1,2,3 and embodiment 1,2,3, the comparative example 4,4g as the dipentaerythritol acrylate of the monomer (C) of radical-curable, 1.5g Irgacure184 heating for dissolving as ultraviolet response type initiator.(among reference example 7-4,8-4, the 9-4, add the UVI-6990 of 1.0g again as the positively charged ion series initiators.)
Utilize manual applicator (Ha Application De ア プ リ ケ ー タ) that they are coated on the polycarbonate plate again, the thickness when being applied to drying reaches 20 microns, implements solvent seasoning at 80 ℃, 30 minutes in the electric oven.After the drying, utilize the ultraviolet vertical exposure device (オ ー Network possess high pressure mercury vapour lamp to make manufacturing) ultraviolet ray of exposure radiation dose 1000mJ, make its curing, obtain multilayer material.
According to JIS K5600-5-4:1999, measure the hardness of filming (test example 2) of this multilayer material, also implement the test (test example 3) of impact, implement the test (test example 4) of thermal shock again according to JIS K5600-7-4:1999 according to ISO6272-1:2002.Respectively test analyte (reference example 7～9, embodiment 9～11, comparative example 12) and each evaluation test result (test example 2～4) of preparing list in table 4.
Table 4
Table 4 reference example 7,8,9 and embodiment 9,10,11, comparative example 12: the dura mater preparation and the evaluation of material
Shock-resistance, cold-resistant thermal shocking metewand:
Zero: not damaged, do not have peel off, △: have slightly damage, *: peel off
By above result as can be known, and do not use the compound (c) that has hydroxyl and carboxyl in a part concurrently and the embodiment 9,10,11 of epoxy group(ing) all acrylateization is compared, the dura mater of preparation is improved with the shock-resistance of material in the reference example 7,8,9.Think that after deliberation the reason that this shock-resistance improves is that along with the importing of compound (c), the density of two keys appropriateness reduces, and along with hydroxyl imports, the loose crosslinking structure of being brought by hydrogen bond produces desirable influence.
And for by common difunctional epoxy resin deutero-comparative example 12-1,12-2, solidified nature significantly worsens, and shock-resistance is lower.
Reference example 10,11,12 and embodiment 13,14,15, comparative example 16: the preparation of dry-film type resist composition and cured article thereof
Add reference example 4,5,6 and embodiment 5,6,7, reactive polycarboxylic acid compound (B) 54.44g that obtains in the comparative example 8, HX-220 (trade(brand)name: the 3.54g diacrylate monomer that Nippon Kayaku K. K makes) as other reactive compounds (C), Irgacure907 (Ciba Specialty Chemicals manufacturing) 4.72g and Kayacure DETX-S (Nippon Kayaku K. K's manufacturing) 0.47g as Photoepolymerizationinitiater initiater, GTR-1800 (Nippon Kayaku K. K's manufacturing) 14.83g as cure component, as the trimeric cyanamide 1.05g of thermal curing catalyst and the methyl ethyl ketone 20.95g that adjusts solvent as concentration, it is mixing to utilize ball mill to carry out, make their homodisperse, obtain the resist resin combination.
Use the excellent spreader #20 of coiling; resultant composition is uniformly coated on the polyethylene terephthalate film as supporting film; make it pass through the hot-air drying stove of 70 ℃ of temperature; after forming the resin layer of thickness 20 μ m; on this resin layer, attach polyethylene film, obtain dry film as protective membrane.On one side the protective membrane of resulting dry film is peeled off, on one side the warming mill of 80 ℃ of use temperatures this resin layer is attached to the polyimide printed base plate (copper circuit is thick: 12 μ m, polyimide thickness: on the whole base plate face 25 μ m).
Need to prove that (A) that uses among reference example 10-5,11-6, the 12-5, (B) melange are the polycarboxylic acid compound (B) of the Resins, epoxy of the use correspondence for preparing among the sour modified carboxylic acid ester cpds (A) for preparing among reference example 1-1,2-1 or the 3-1 and reference example 4-1,5-1 or the 6-1 to be mixed in 50:50 (with solution weight) to obtain respectively.
Next, for the mask and the sensitivity of drawing circuit pattern being estimated ((strain) オ ー Network is made institute, model HMW-680GW), the optics step-wedge No.2 by Kodak makes shines 500mJ/cm to use ultraviolet exposure apparatus according 2Ultraviolet ray., peel off film dry film on, confirm to peel off state thereafter.Carry out spray development with 1% aqueous sodium carbonate then, remove the not resin of irradiation portion of ultraviolet ray.Behind the washing and drying, make printed base plate carry out the reaction that was heating and curing in 60 minutes, obtain cured film with 150 ℃ hot-air driers.
By evaluation method shown below, carry out the benchmark test (test example 5～10) of the dry-film type resist cured film that obtains in reference example 10,11,12 and embodiment 13,14,15, the comparative example 16.The evaluation test of each cured film the results are shown in table 5.
Test example 5: folding resistance evaluation
With the cured film side is the top, and the polyimide printed base plate that will be formed with the cured film of resist is upwards rolled over (mountain folding り), smoothes out with the fingers kink fully with finger.Kink is restored, observe resist film with magnifying glass.
Metewand: zero: do not have be full of cracks, △: observe be full of cracks slightly, *: peel off
Test example 6: cold-resistant thermal shocking evaluation
Polyimide printed base plate to the cured film that is formed with resist is implemented cold shock testing-65～120 ℃ scope.Test method is according to JIS C5012-9.1:1993.After the off-test, utilize scotch tape (セ ロ Ha ン テ ー プ) (registered trademark) to implement stripping test.
Metewand: zero: nothing is peeled off, △: observes slightly and peels off, *: peel off
Test example 7: the high temperature wet fastness is estimated
The polyimide printed base plate that will be formed with the cured film of resist is put into 120 ℃ autoclave 1 hour.Take out substrate, after room temperature makes it air-dry, utilize scotch tape (セ ロ Ha ン テ ー プ) (registered trademark) to implement stripping test.
Metewand: zero: nothing is peeled off, △: observes slightly and peels off, *: peel off
Test example 8: sensitivity evaluation
By investigating in the exposure portion that has seen through the optics step-wedge, the concentration part till which " section lattice " is remaining when developing, and judges sensitivity thus.The big person of " section lattice " number (value) is judged to be highly sensitive (unit: section) in the dense portion of optics step-wedge.
Test example 9: development evaluation
For development, with so-called presentation time (Block レ イ Network タ イ system) (this time is when the exposure portion that sees through pattern mask is developed, the time that is developed out fully until pattern form portion) as the evaluation of development (unit: second).
Test example 10: solidified nature evaluation
The pencil hardness of the cured film after the solidified nature evaluation finishes with 150 ℃ of heating is represented.Evaluation method is according to JISK5600-5-4:1999.
Table 5
Table 5 reference example 10,11,12 and embodiment 13,14,15, comparative example 16: the evaluation of dry film photoresist
Figure BDA00002935838600281
By above-mentioned result as can be known, the resist composition among the present invention can obtain having the cured article of higher hardness, has good development and sensitivity as resist.In addition, in the situation of reference example 10,11, has high folding resistance.And, in reference example 12, have high cold-resistant thermal shocking and high temperature wet fastness.The resist composition and the cured article thereof that are obtained by comparative example do not demonstrate good evaluation result in folding resistance, tolerance aspect impact, development and the sensitivity of thermal distortion generation, as the dry film photoresist material, performance is unsatisfactory.
Reference example 13 and embodiment 17, comparative example 18: flame retardant resin and relatively use the preparation of resin
The resist composition, the 0.5g phosphoric acid ester flame retardant (four countries change into SP-703H) that prepare among 9.5g reference example 10-2 and embodiment 13-1 and the comparative example 16-1 are mixed stirring, obtain curable resin composition.Use the excellent spreader #20 of coiling that composition is coated on the polyimide film of 25 microns of thickness, make its hot-air drying stove that passes through 70 ℃ of temperature, form the resin layer of the about 15 μ m of thickness.Use ultraviolet exposure apparatus according ((strain) オ ー Network is made institute, model HMW-680GW), irradiation 500mJ/cm 2Ultraviolet ray.After the irradiation, make printed base plate carry out the reaction that was heating and curing in 60 minutes, obtain cured film (being respectively reference example 13, embodiment 17, comparative example 18) with 150 ℃ hot-air driers.
Test example 11: the evaluation of flame retardant resistance
The cured film that obtains in reference example 13, embodiment 17, the comparative example 18 is cut into the strip of length 20cm, wide 2cm with the polyimide base material film.The film that downcuts is sling along lengthwise direction, utilized lighter for ignition to light a fire, estimate flame retardant resistance from the lower end.In order to carry out the comparison with folding resistance, as a reference, the folding resistance testing data of reference example 10-2, embodiment 13-1 and comparative example 16-1 is recorded in following table 6 in the lump.
Table 6
Table 6 test example 11; The evaluation of the flame retardant resistance of reference example 13 and embodiment 17, comparative example 18
Figure BDA00002935838600291
Flame retardant resistance metewand: zero: catch fire, but fire goes out before all burning up.*: all burn up.
By above result as can be known, the carbonate of reference example is the material that can have flame retardant resistance and folding resistance simultaneously.
Reference example 14,15,16 and embodiment 19,20,21, comparative example 22: be dispersed with the preparation of the resin of tinting pigment
With the reactive polycarboxylic acid compound (B) that obtains in 20g reference example 4,5,6 and embodiment 5,6,7, the comparative example 8,5.0g the acrylate monomer that Nippon Kayaku K. K makes), 10g mixes as the carbon black MA-100 of Mitsubishi of tinting pigment as the propylene glycol methyl ether acetate of organic solvent, 10g and stir as the DPHA of other reactive compounds (C) (trade(brand)name:.The granulated glass sphere that adds 35g therein carries out disperseing in 1 hour with the coating rocker.
Use the dispersion liquid after the excellent spreader #2 of coiling will disperse to finish to be coated on the polyethylene terephthalate film, utilize 80 ℃ hot air dryer to carry out 10 minutes dryings, respectively be dispersed with the sooty resin.
Test example 12: the evaluation relevant with pigment-dispersing
Use 60 ° of reflectance gloss meters (hole field make the IG-331 of institute glossmeter), the gloss of the film coated surface that is dispersed with the sooty resin that obtains in reference example 14,15,16 and embodiment 19,20,21, the comparative example 22 is measured, estimate dispersity of carbon black.At this moment, the high more person of gloss, the expression pigment-dispersing is good more.The results are shown in table 7.
Table 7
Table 7 reference example 14,15,16 and embodiment 19,20,21, comparative example 22: the evaluation of pigment-dispersing
Figure BDA00002935838600301
By above-mentioned result as can be known, pigment-dispersing is improved in the reactive polycarboxylic acid compound (B) of reference example.Think that after deliberation because different with the polycarboxylic acid of embodiment, this pigment-dispersing effect is the difference that comprises the effect that the interpolation of the Resins, epoxy of ad hoc structure and compound (c) brings in the molecule on basic framework.
Reference example 17 and embodiment 23, comparative example 24: be dispersed with the preparation of the resin of tinting pigment
With the reactive polycarboxylic acid compound (B) that obtains among 20g reference example 4-2 and embodiment 5-1, the comparative example 8-1,5.0g the acrylate monomer that Nippon Kayaku K. K makes), 10g mixes as the carbon black MA-100 of Mitsubishi of tinting pigment as the propylene glycol methyl ether acetate of organic solvent, 10g and stir as the DPHA of other reactive compounds (C) (trade(brand)name:.The granulated glass sphere that adds 35g therein carries out disperseing in 1 hour with the coating rocker.The resulting sooty resin liquid that is dispersed with is sampled to sample bottle, obtain the tinting pigment dispersion liquid.
Test example 13: the storage stability evaluation of tinting pigment dispersion liquid
The tinting pigment dispersion liquid of preparation leaves standstill 2 weeks, the state of this dispersion liquid of visual valuation preserved in 40 ℃ in reference example 17 and embodiment 23, the comparative example 24.The results are shown in table 8.
Table 8
The evaluation of the dispersible pigment dispersion storage stability of table 8 reference example 17 and embodiment 23, comparative example 24
Figure BDA00002935838600311
Estimation of stability benchmark: zero: uniform solution, △: the gradient dispersion, *: the pigment precipitation
By above-mentioned result as can be known, though the tinting pigment dispersion liquid of reference example in 40 ℃ through 2 weeks, also keeping state uniformly, dispersion liquid does not separate.On the other hand, for embodiment 23, can observe transparent layer (varnish come-up (ニ ス floats I)) on the upper strata, the dispersion state instability.In the comparative example 24, generate the precipitation of tinting pigment, even be in the state that also can't become homogeneous that stirs.
By above-mentioned result as can be known, by go up to import at the Resins, epoxy (a) that with the ad hoc structure is basic framework have concurrently in the molecule more than one can polymeric ethylenic unsaturated group and the compound (b) of an above carboxyl and molecule in have the compound (c) of an above hydroxyl and an above carboxyl concurrently, pigment-dispersing is improved in reactive polycarboxylic acid compound of the present invention (B), and the storage stability of its dispersible pigment dispersion is improved simultaneously.
Industrial applicibility
For active energy ray curable resin of the present invention, the material that has concurrently as solidified nature and flexibility, obdurability, flame retardant resistance, can enumerate the dura mater material, can alkaline development and be the purposes of the good pigment-dispersing of necessary anticorrosive additive material, performance with the flexibility, yet, can be used for chromatic photoresist, particularly black matrix layer etc. that LCD uses for example as the printing-ink of active energy ray curable, chromatic photoresist, particularly have the material of the suitable property of resists such as pigment-dispersing and development concurrently with being particularly suitable for.

Claims (14)

1. reactive epoxy carbonate, its make have concurrently in the Resins, epoxy (a) shown in the general formula (1) and a part more than one can polymeric ethylenic unsaturated group and compound (b) reaction of an above carboxyl obtain,
Figure FDA00002935838500011
In the general formula (1), R 1Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually; R 2The expression carbonatoms is that 7～16 divalent multi-ring alkyl or carbonatoms are 7～18 inferior aralkyl; M represents 1～4 integer; And n is in the positive number of mean value expression 1～10.
2. reactive epoxy carbonate as claimed in claim 1, wherein, Resins, epoxy (a) shown in general formula (2),
Figure FDA00002935838500012
In the general formula (2), R 3Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually; O represents 1～4 integer; And p is in the positive number of mean value expression 1～10.
3. reactive epoxy carbonate as claimed in claim 1, wherein, Resins, epoxy (a) shown in general formula (3),
Figure FDA00002935838500013
In the general formula (3), R 4Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually; Q represents 1～4 integer; And r is in the positive number of mean value expression 1～10.
4. reactive epoxy carbonate as claimed in claim 1, wherein, Resins, epoxy (a) shown in general formula (4),
In the general formula (4), R 5Identical or mutual difference represents that hydrogen atom, halogen atom or carbonatoms are 1～4 alkyl mutually; S represents 1～4 integer; And t is in the positive number of mean value expression 1～10.
5. reactive polycarboxylic acid compound, it makes each described reactive carbonate (A) reaction of multi-anhydride (d) and claim 1～4 and obtains.
6. an active energy ray-curable resin composition is characterized in that, described composition comprises each described reactive carbonate (A) of claim 1～4 and/or the described reactive polycarboxylic acid compound of claim 5 (B).
7. active energy ray-curable resin composition as claimed in claim 6 is characterized in that, described composition also comprises the reactive compounds (C) except that (A), (B).
8. as claim 6 or 7 described active energy ray-curable resin compositions, it is characterized in that described composition also contains tinting pigment.
9. as each described active energy ray-curable resin composition of claim 6～8, it is characterized in that described composition also comprises Photoepolymerizationinitiater initiater.
10. as each described active energy ray-curable resin composition of claim 6～9, wherein, described composition is a molding material.
11. as each described active energy ray-curable resin composition of claim 6～9, wherein, described composition is a tunicle formation material.
12. as each described active energy ray-curable resin composition of claim 6～9, wherein, described composition is the anticorrosive additive material composition.
13. a cured article, it is the cured article of each described active energy ray-curable resin composition of claim 6～9.
14. article, it has covered surperficial article for using each described active energy ray-curable resin composition of claim 6～9.
CN201310088076.XA 2007-08-21 2008-08-08 Reactive epoxy carboxylic acids's ester cpds, reactive polycarboxylic compounds, active energy ray-curable resin composition and article Active CN103224609B (en)

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CN101784578B (en) 2013-04-17
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WO2009025190A1 (en) 2009-02-26
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