CN1945434B - Photohardenable and thermosetting resin compositions, their hardened product, and printing circuit boards using the same - Google Patents

Photohardenable and thermosetting resin compositions, their hardened product, and printing circuit boards using the same Download PDF

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Publication number
CN1945434B
CN1945434B CN2006101404506A CN200610140450A CN1945434B CN 1945434 B CN1945434 B CN 1945434B CN 2006101404506 A CN2006101404506 A CN 2006101404506A CN 200610140450 A CN200610140450 A CN 200610140450A CN 1945434 B CN1945434 B CN 1945434B
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solidifying
resin
resin composition
carboxylic acid
heat
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CN1945434A (en
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伊藤信人
有马圣夫
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Provided is a photosetting/thermosetting resin composition, useful as a solder resist used in production of a printed wiring board and as insulating resin layers of various electronic components, having high sensitivity, and adaptable even to a laser direct imaging method, without deteriorating the coating characteristics or the dry-to-touch properties, and to provide a cured product of the same and a printed wiring board with a pattern formed that uses the same. The photosetting/thermosetting resin composition comprises (A) an unsaturated group-containing carboxylic acid resin, obtained by reacting (A1) a carboxylic acid-containing resin with (A2) a compound having one isocyanate group and two or more ethylenically unsaturated groups inside a single molecule, (B) a photopolymerization initiator, (C) a compound having two or more ethylenically unsaturated groups in one molecule, (D) a filler and (E) a thermosetting component having two or more cyclic ether groups and/or cyclic thio-ether groups inside a single molecule.

Description

Light solidifying/heat solidifying resin composition, its solidfied material and the printed circuit board (PCB) that uses it to make
Technical field
The present invention relates to printed circuit board (PCB) that needs solder resist etc., as the useful light solidifying/heat solidifying resin composition of the insulating resin layer of various electronic units, its solidfied material and the printed circuit board (PCB) that uses it to make, say in further detail, relate to a kind of ISO and can adapt to light solidifying/heat solidifying resin composition, its solidfied material of laser direct imaging technology and the printed circuit board (PCB) that uses it to make.
Background technology
Because the fast development of nearest semiconductor device, e-machine trends towards miniaturization and, high performance, multifunction, and in order to follow these, printed circuit board (PCB) constantly carries out densification.The employed solder resist of such printed circuit board (PCB), usual way was by silk screen print method heat-curable composition or Photocurable composition to be formed pattern in the past, and make the method for transfer section heat curing or photocuring, but densification corresponding to printed circuit board (PCB), the developable solder flux becomes main flow (for example, referring to Patent Document 1).
Such developable solder flux needs following operation: the painting process that passes through whole painting erosion resistant agents such as silk screen print method, curtain formula curtain coating, spraying process, rolling method on tellite, for can contact exposure and make the predrying operation of solvent evaporates, cooling and the exposure process that carries out contact exposure, remove the developing procedure of unexposed portion by developing, be used to obtain the heat curing operation of sufficient coating characteristic.In these operations, exposure process is a very loaded down with trivial details operation as described below: the kind according to printed circuit board (PCB) changes negative film (nega film), makes after the aligned in position, vacuumizes, and exposes.Therefore, in order to boost productivity, reduce price, shortening exposure process is key factor, and in addition, in order to shorten exposure process, the ISOization of solder resist has very big contribution.Hence one can see that, and for employed solder resist in normally used e-machine, the demand of ISOization uprises.Usually, for ISOization, can consider to add in a large number polyfunctional group (methyl) acrylate compounds.But, if increase the amount of low-molecular-weight polyfunctional group (methyl) acrylate compounds, light sensitivity is to have risen, however the problem that cured coating film characteristics such as the significantly decline of the dry to touch (tack-free property, tack free) of needs, plating tolerance also reduce when having contact exposure.
On the other hand, for the manufacturing of employed printed circuit board (PCB) in the limited-production types such as analytical instrument or as the manufacturing of the printed circuit board (PCB) of trial production product, require the solder resist corresponding with the laser direct imaging technology, described laser direct imaging technology is by deriving from the CAD (computer-aided design (CAD) of computing machine, Computer Aided Design) data are directly carried out image scanning with laser to printed circuit board (PCB).Employed laser in such laser direct imaging technology, its beam diameter are 5～15 μ m, and output power is about several watts.Such laser is carried out switch and scan with the width of 5～15 μ m, thus rendering image, and the time that therefore forms pattern on 1 printed circuit board (PCB) depends on the light sensitivity of solder resist greatly.According to this situation,, require the higher ISOization (for example, patent documentation 2) of light sensitivity than the developable solder flux of employing contact exposure commonly used for the solder resist that uses in the laser direct imaging technology.
Light source that the laser direct imaging technology is used and wavelength, purposes according to employed Photocurable resin composition changes, but light source roughly can be divided into the type of using gases ion laser and the type of use Solid State Laser. use argon gas in the gaseous ion laser usually, in Solid State Laser, use semiconductor laser and YAG laser usually. in addition, if Wavelength of Laser territorial classification to be radiated, then can be divided into ultraviolet region type and visibility region type, usually use 365nm, 405nm, 488nm. still, the Photocurable resin composition of sensitization under the 488nm of visible region, owing to must in the particular surroundings under the red light, use, thereby be desirably in the Photocurable resin composition of the ISO of sensitization under 350nm～420nm.
Patent documentation 1: Japanese kokai publication sho 61-243869 communique (claims)
Patent documentation 2: international open WO02/096969 communique (claims)
Summary of the invention
Invent problem to be solved
The present invention carries out in order to solve above-mentioned prior art problems, its fundamental purpose is, a kind of light solidifying/heat solidifying resin composition and solidfied material thereof are provided and use it to form the printed circuit board (PCB) of pattern, described light solidifying/heat solidifying resin composition is as the insulating resin layer of solder resist that is used to make printed circuit board (PCB) or various electronic units and useful, ISO and can not make coating characteristic or dry to touch reduction can adapt to the laser direct imaging technology.
The method of dealing with problems
The inventor studies intensively in order to achieve the above object, found that a kind of light solidifying/heat solidifying resin composition that can develop by dilute alkaline soln, and it comprises:
(A) make contain compound (A2) reaction that has 1 isocyanate group and 2 above ethylenically unsaturated groups in carboxylic acid resin (A 1) and 1 molecule and the carboxylic acid resin of containing unsaturated group,
(B) Photoepolymerizationinitiater initiater,
(C) have in the molecule 2 above ethylenically unsaturated groups compound,
(D) filler and
(E) has the Thermocurable composition of 2 above ring-type ethers and/or cyclic thioether base in the molecule, said composition can be brought into play high photopolymerization ability and can obtain sufficient deep curing performance and then coating characteristic excellence such as plating tolerance, thereby has finished the present invention.
As the form that provides of light solidifying/heat solidifying resin composition of the present invention, can be liquid form, also can be the form of photosensitive dry film in addition.
In addition, according to the present invention, the solidfied material of light solidifying/heat solidifying resin composition of the present invention can be provided and form the printed circuit board (PCB) that the pattern of this solidfied material forms.
The invention effect
Light solidifying/heat solidifying resin composition of the present invention because ISO and can not make coating characteristic or dry to touch reduction, thereby can improve operability when making printed circuit board (PCB), can provide fiduciary level high printed circuit board (PCB) at an easy rate.
And then, owing to can be cured by the laser generation light source of 350nm～420nm, need under the inferior particular surroundings of ruddiness, not use, just can use the laser direct imaging technology, and do not need the negative-appearing image pattern, can help the raising and the cost degradation of initial production rate.
Embodiment
Light solidifying/heat solidifying resin composition of the present invention, it comprises:
(A) make contain compound (A2) reaction that has 1 isocyanate group and 2 above ethylenically unsaturated groups in carboxylic acid resin (A 1) and 1 molecule and the carboxylic acid resin of containing unsaturated group,
(B) Photoepolymerizationinitiater initiater,
(C) have in the molecule 2 above ethylenically unsaturated groups compound,
(D) filler and
(E) have the Thermocurable composition of 2 above ring-type ethers and/or cyclic thioether base in the molecule,
As the carboxylic acid resin of containing unsaturated group (A) on basis used will contain compound (A2) reaction that has 1 isocyanate group and 2 above ethylenically unsaturated groups in carboxylic acid resin (A1) and 1 molecule and the photoresist of ISO, it is characterized in that on this point.
Below, each constituent of light solidifying/heat solidifying resin composition of the present invention is elaborated.
The carboxylic acid resin of containing unsaturated group (A) who is comprised in the light solidifying/heat solidifying resin composition of the present invention be make contain compound (A2) reaction that has 1 isocyanate group and 2 above ethylenically unsaturated groups in carboxylic acid resin (A1) and 1 molecule and contain carboxy resin.
The above-mentioned carboxylic acid resin of containing (A1) can use the carboxy resin that contains known commonly used that contains carboxyl in the molecule.
Specifically, can list as following enumerate contain carboxylic acid resin (A1).
(1) make polyfunctional epoxy resin (a) and the reaction of saturated or unsaturated monocarboxylic acid (b) after, again with multi-anhydride (c) reaction contain carboxy resin;
(2) make the reaction of difunctional epoxy resin (d) and difunctional phenol (e) and/or dicarboxylic acid (f) after, again with multi-anhydride (c) reaction contain carboxy resin;
(3) make compound (h) reaction that has an epoxy radicals in multifunctional phenolic resin (g) and the molecule after, again with multi-anhydride (c) reaction contain carboxy resin;
(4) make the compound (i) that has 2 above alcohol hydroxyl groups in the molecule react the carboxy resin that contains that forms with multi-anhydride (c);
(5) carboxy resin that contains by unsaturated carboxylic acid such as (methyl) acrylic acid and the compound copolymerization that has unsaturated double-bond more than a kind except that it are obtained; And
(6) on the multipolymer of unsaturated carboxylic acid such as (methyl) acrylic acid and the compound that has unsaturated double-bond more than a kind except that it, utilize (methyl) glycidyl acrylate or 3,4-epoxycyclohexyl methyl (methyl) acrylate etc. has the compound of epoxy radicals and unsaturated double-bond or (methyl) acryloyl chloride etc., the addition ethylenically unsaturated group is as side group, and what obtain thus contains the carboxylic acid resin; Make the reaction of multi-group epoxy compound and unsaturated monocarboxylic acid, make the hydroxyl that generated again with saturated or unsaturated multi-anhydride reaction contain carboxy resin etc., but be not limited to these.
In these illustrations preferably above-mentioned (1), (2), (3) and (4) contain carboxy resin, from photo-curable, cured coating film characteristic aspect, particularly preferably be the carboxy resin that contains of above-mentioned (1).
In addition, in this manual, (methyl) acrylate is the word of general name acrylate, methacrylate and their potpourri, all is same meanings about other similar performances.
Can use all epoxy resin as the polyfunctional epoxy resin (a) that is used for the synthetic above-mentioned carboxylic acid resin of containing (A1). the example as representative can list bisphenol A-type, the hydrogenated bisphenol A type, the Bisphenol F type, the bisphenol S type, the phenol phenolic varnish type, the cresols phenolic varnish type, the phenolic varnish type of bisphenol-A, biphenyl type, di-cresols type, known epoxy compounds commonly used such as N-diglycidyl type, as commercially available product suitable be the EHPE-3150 etc. of Daicel corporate system. can also enumerate epihalohydrin reactions such as the hydroxyl of bisphenol-type epoxy resin of the solid of sening as an envoy to and chloropropylene oxide, carry out afterwards multiple functionalized and polyfunctional group bisphenol-type epoxy resin etc. in these, especially preferably use epoxy radicals many and be the phenol phenolic varnish type of solid, the cresols phenolic resin varnish type epoxy resin, the polyfunctional group bisphenol-type epoxy resin. these polyfunctional epoxy resins (a) can be used alone or in combination of two or more kinds.
In addition, as saturated or unsaturated monocarboxylic acid (b), can list saturated monocarboxylic acids such as formic acid, acetate, propionic acid, butyric acid, lactic acid, dihydromethyl propionic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, alpha-cyano cinnamic acid, β-styrene acrylic, β-unsaturated monocarboxylic acids such as furfuryl group acrylic acid, these can be used alone or in combination of two or more kinds.
On the other hand, as multi-anhydride (c), can list succinic anhydride, maleic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, itaconic anhydride, methyl-carbic anhydride, trihemellitic acid acid anhydride, PMA etc., these can be used alone or in combination of two or more kinds.
As the employed difunctional epoxy resin (b) in carboxy resin synthetic that contains in above-mentioned (2), can list bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, united phenol-type epoxy resin, di-toluene phenol-type epoxy resin, terephthalic acid (TPA) diglycidyl ether, 1,6-hexanediol diglycidyl ether etc., these can be used alone or in combination of two or more kinds.
As with the difunctional phenol (e) of above-mentioned difunctional epoxy resin reaction, for example can list, 1,4-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, 2,7-dihydroxy naphthlene, 2, dihydroxy naphthlene derivants such as 8-dihydroxy naphthlene, 2,2 '-biphenol derivatives such as di-cresols, xenol, bisphenol-A, Bisphenol F, bisphenol S, alkyl replace bisphenol derivatives such as bis-phenol, hydroquinone derivatives such as quinhydrones, methylnaphthohydroquinone, trimethylhydroquinone etc.
In addition, dicarboxylic acid compound (f) as same and above-mentioned difunctional epoxy resin reaction, for example can list, 1, the 4-cyclohexyl dicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, six hydrogen m-phthalic acids, six hydrogen terephthalic acid (TPA)s, phthalic acid, m-phthalic acid, terephthalic acid (TPA), succinic acid, hexane diacid, muconic acid, suberic acid, decanedioic acid, the addition product of 2-hydroxy-2-methyl succinic acid and phthalic anhydride etc., but from ultraviolet permeability, giving the aspect of flexibility sets out, preferred especially 1, the 4-cyclohexyl dicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, six hydrogen m-phthalic acids, six hydrogen terephthalic acid (TPA)s, hexane diacid, muconic acid, suberic acid, the dicarboxylic acid compound of aliphatics such as decanedioic acid or ester ring type.
These above-mentioned difunctional phenol (e) and above-mentioned dicarboxylic acid compound (f) can be used alone or in combination of two or more kinds respectively.
In addition, as the employed multifunctional phenolic resin (g) in carboxy resin synthetic that contains in (3), can list catechol, resorcinol, quinhydrones, orcin, the naphthalene glycol, tert-butyl catechol, tertiary butylated hydroquinone, 1,2,3,-thrihydroxy-benzene, phloroglucin, bisphenol-A, Bisphenol F, bisphenol S, 4,4 '-dihydroxy benaophenonel, 4,4 '-dihydroxy diphenyl ether, phenolphthalein, phenolic varnish type phenolics, phenol and condensation product with aromatic aldehyde of phenol hydroxyl, poly--para hydroxybenzene ethene, the condensation product of 1-naphthols or beta naphthal and aldehydes etc. (being the naphthol type novolac resin), 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 2,3-, 2,6-, 2, the condensation product of 7-dihydroxy naphthlene and aldehydes, the condensation product of monobasic naphthols and above-mentioned dihydroxy naphthlene and aldehydes, the condensation product of monobasic or dihydroxy naphthlene and xylylene glycols, the addition product of monobasic or dihydroxy naphthlene and diolefin compound etc., but be not limited to these.These compounds that contain the phenol hydroxyl can use separately or mix more than 2 kinds and use.
As with the molecule of above-mentioned multifunctional phenolic resin (g) reaction in have 1 epoxy radicals compound (h), can list butyl glycidyl ether, acryloyl glycidol ether, phenyl glycidyl ether, (methyl) glycidyl acrylate, diglycidyl, 1,2-epoxy radicals-vinyl cyclohexane, 3,4-epoxycyclohexyl methyl (methyl) acrylate, styrene oxide, oxidation australene etc., these can use separately or be used in combination more than 2 kinds.
In addition, as the compound (i) that has 2 above alcohol hydroxyl groups in carboxy resin synthetic in the employed molecule that contains in (4), can use known polyol compound commonly used, for example can list, polyvinyl alcohol (PVA), polyvinyl acetal resin, polyvinyl butyral resin, styrene-allyl alcohol copolymer, celluosic resin, methoxylation celluosic resin, polyester polyalcohols resin etc., these can use separately or be used in combination more than 2 kinds.
As with above-mentioned 1 molecule that contains carboxylic acid resin (A1) reaction that obtains like this in have the compound (A2) of 1 isocyanate group and 2 above ethylenically unsaturated groups, can list 1,1-(two acryloyl-oxy ylmethyl) ethyl isocyanate, 1,1-(two methacryloxy methyl) ethyl isocyanate; And 1 half urethanes that has diisocyanate such as the compound of 1 hydroxyl and 2 above ethylenically unsaturated groups and isoflurane chalcone diisocyanate, toluene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate in the molecule.
In half such urethanes,, the reaction capacity difference of preferred especially 2 isocyanate group, do not have the isoflurane chalcone diisocyanate derivant of the aromatic rings that the light transmission of making reduces from throughput rate, photo-curable aspect.
In addition, as the compound that has 1 hydroxyl and 2 above ethylenically unsaturated groups in employed 1 molecule in above-mentioned half urethanes synthetic, can list pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, dipentaerythritol five acrylate, (methyl) esters of acrylic acid of polyvalent alcohols such as dipentaerythritol pentamethyl acrylate, on the polyvalent alcohol of the raw material that becomes them addition (methyl) esters of acrylic acid of polyvalent alcohol of oxirane (abbreviating EO as) or epoxypropane (abbreviating PO as), also has (methyl) glycidyl acrylate or 3,4-epoxycyclohexyl methyl (methyl) acrylate etc. contains (methyl) esters of acrylic acid of the simple function group monomer of epoxy radicals, and these can use separately or be used in combination more than 2 kinds.
In the compound (A2) that in 1 molecule, has 1 isocyanate group and 2 above ethylenically unsaturated groups like this, can list 1 as preferred compound, 1-(two acryloyl-oxy ylmethyl) ethyl isocyanate and isoflurane chalcone diisocyanate derivant, particularly have an isoflurane chalcone diisocyanate derivant of 3 ethylenically unsaturated groups.
The carboxylic acid resin's who contains unsaturated group (A) who obtains as described above acid number is in the scope of 40～200mg KOH/g, more preferably in the scope of 45～120mg KOH/g.If carboxylic acid resin's (A) the acid number that contains unsaturated group is not enough 40mg KOH/g, then the alkali development becomes difficult, on the other hand, if surpass 200mg KOH/g, the dissolving of the exposed portion that developer solution causes then can take place, so live width is thinner than needed, or according to circumstances causes exposed portion and unexposed portion indistinguishably to be developed the liquid dissolving peeling off, becoming is difficult to describe normal corrosion-resisting pattern, thereby not preferred.
In addition, the above-mentioned weight-average molecular weight that contains the carboxylic acid resin (A) of unsaturated group, because of resin matrix different, but usually preferably in 2000～150000 scope, further preferred in 5000～100000 scope.If weight-average molecular weight is less than 2000, then dry to touch can variation, the moisture-proof variation of filming after the exposure and when developing, produce the film loss, resolution deteriorates significantly.On the other hand, if weight-average molecular weight surpasses 150000, then have the situation that development significantly worsens, storage-stable worsens.
The carboxylic acid resin's who contains unsaturated group (A) like this combined amount is 20～60 weight % in whole compositions, be preferably 30～50 weight %.Under situation about lacking than above-mentioned scope, coating strength etc. can reduce, so not preferred.On the other hand, under the situation of Duoing than above-mentioned scope, viscosity uprises or reduction such as coating performance, so not preferred.
As employed Photoepolymerizationinitiater initiater (B) among the present invention, for example can list stupid acyloin and benzoin alkylether classes such as stupid acyloin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 1-[4-(4-benzoyl phenyl sulfinyl)-2-methyl-2-(4-aminomethyl phenyl sulfinyl) propane-acetophenones such as 1-ketone; 2-methyl isophthalic acid-[4 (methyl mercapto) phenyl]-2-morpholino amino-1-acetone, 2-benzyl-2-dimethylamino-(4-morpholino phenyl)-aminoacetophenone classes such as 1-butanone; Anthraquinone classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthene ketones such as 4-diisopropyl thioxanthones; Ketal classes such as acetophenone dimethyl ketal, benzil dimethyl ketal; Benzophenones such as benzophenone or or the xanthene ketone; And the oxime ester class Photoepolymerizationinitiater initiater that contains oxime ester base shown in the following general formula (I).
In the formula, R 1Expression hydrogen atom, carbon number are 1～7 alkyl or phenyl, R 2The expression carbon number is 1～7 alkyl or phenyl.
In these, Photoepolymerizationinitiater initiater shown in the following formula (II) is 2-(acetoxyl group iminomethyl) thioxanthene-9-one (the イ Le ガ キ ユ ア one that Xiba Special Chemical Product Co.,Ltd makes, be designated hereinafter simply as CGI-325), Photoepolymerizationinitiater initiater shown in the following formula (III) (イ Le ガ キ ユ ア one OXE01 that Xiba Special Chemical Product Co.,Ltd makes), and the Photoepolymerizationinitiater initiater shown in the following formula (IV) (イ Le ガ キ ユ ア one OXE02 that Xiba Special Chemical Product Co.,Ltd makes), owing to be insoluble in organic solvent thereby dry to touch excellence, and 350nm useful in the printed circuit board (PCB) manufacturing～420n m ultraviolet ray is carried out photopolymerization just can produce free radical effectively on a small quantity, and it is can not cause when photopolymerization is sent out agent and is not easy because of heat curing or situation that the heat during laser explosure distils, thereby preferred especially.
Figure G2006101404506D00111
These known Photoepolymerizationinitiater initiaters commonly used can use separately or be used in combination more than 2 kinds. and the blending ratio of these Photoepolymerizationinitiater initiaters (B) is, the above-mentioned carboxylic acid resin (A) who contains unsaturated group is suitably for 0.01～30 weight portion with respect to 100 weight portions, but when the time for above-mentioned oxime ester class Photoepolymerizationinitiater initiater, be suitably for 0.01～20 weight portion, be preferably 0.01～5 weight portion. when the use amount of Photoepolymerizationinitiater initiater than above-mentioned scope after a little while, the photo-curable variation, on the other hand, for a long time than above-mentioned scope, characteristic as solder resist reduces, so not preferred.
In addition, light solidifying/heat solidifying resin composition of the present invention as light-initiated auxiliary agent, can contain uncle's ammoniate or benzophenone cpd.As such uncle's Ammonia, can list the ethanol Ammonia, 4,4 '-dimethylamino benzophenone (Japanese Cao Da corporate system ニ Star ソ キ ユ ア one MABP), 4-dimethylamino ethyl benzoate (Japanese chemical drug カ ヤ キ ユ ア one EPA of company), 2-dimethylamino ethyl benzoate (the Quantacure DMB that イ Application タ one Na シ ヨ Na Le バ イ オ one シ Application セ エ テ イ Star Network ス company makes), 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (the Quantacure BEA that イ Application タ one Na シ ヨ Na Le バ イ オ one シ Application セ エ テ イ Star Network ス company makes), to dimethylamino benzoic acid isopentyl ethyl ester (Japanese chemical drug corporate system カ ヤ キ ユ ア one DMBI), 4-dimethylamino benzoic acid-2-Octyl Nitrite (Van Dyk corporate system Esolol 507), 4,4 '-diethylamino benzophenone (protecting the native ケ paddy system EAB of chemical company) etc.These known uncle's ammoniates commonly used can use or use the potpourri more than 2 kinds separately.Particularly preferred uncle's ammoniate is 4,4 '-diethylamino benzophenone, but be not defined in these especially, as long as absorbing light and in the zone of wavelength 350nm～420nm by being used in combination the material of bringing into play the sensitizing effect with the hydrogen-abstraction Photoepolymerizationinitiater initiater, just be not limited to Photoepolymerizationinitiater initiater, photopolymerization auxiliary agent, can use separately or a plurality of being used in combination.
The compound (C) that in light solidifying/heat solidifying resin composition of the present invention, has 2 above ethylenically unsaturated groups in the employed molecule, by irradiation active energy beam generation photocuring, thereby the above-mentioned carboxylic acid resin (A) of containing unsaturated group is not dissolved in alkaline aqueous solution or help it in alkaline aqueous solution, not dissolve.As such compound, can list the diacrylate class of glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; The multicomponent methacrylate class of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, trihydroxy ethyl isocyanuric acid ester or these ethylene oxide adduct or these propylene oxide adduct etc.; The multicomponent methacrylate class of the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenols or propylene oxide adduct etc.; The multicomponent methacrylate class of glycidol ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; And melamine acrylate and/or each methyl acrylic ester corresponding etc. with the aforesaid propylene acid esters.
Further can enumerate the reaction of polyfunctional epoxy resins such as making the cresols phenolic resin varnish type epoxy resin and acrylic acid and Epocryl or the hydroxyl of this Epocryl further with the half urethanes reaction of diisocyanate such as hydroxy acrylate such as pentaerythritol triacrylate and isophorone diisocyanate epoxy urethane acrylate compound etc.Such epoxy acrylic esters resin can not make the dry to touch reduction, can improve photo-curable.
The combined amount that has the compound (C) of 2 above ethylenically unsaturated groups in such molecule, the above-mentioned carboxylic acid resin (A) who contains unsaturated group is 5～100 weight portions with respect to 100 weight portions, more preferably the ratio of 10～70 weight portions.During above-mentioned combined amount less than 5 weight portions, photo-curable reduces, is difficult to develop by the alkali behind the irradiation active energy beam and forms pattern, and is therefore not preferred.On the other hand, surpassing under the situation of 100 weight portions, becoming fragile owing to the dissolubility to alkaline aqueous solution reduces or films, thus not preferred yet.
As the filler that uses among the present invention (D), can use known inorganic or organic filler commonly used, but especially preferably use barium sulphate, spherical silicon dioxide. in addition, NANOCRYL (trade name) XP0396 that can also use the Hanse-Chemie company that in above-mentioned compound (C) with 2 above ethylenically unsaturated groups or polyfunctional epoxy resin described later (E-1), disperseed nano silicon oxide to make, XP0596, XP0733, XP0746, XP0765, XP0768, XP0953, XP0954, XP1045 (being the product type name all), or NANOPOX (trade name) XP0516 of Hanse-Chemie company manufacturing, XP0525, XP0314 (being the product type name all).
These can use separately or mix more than 2 kinds and use.The cure shrinkage that these fillers suppress to film, fundamental characteristics such as adhesion, hardness are improved is certain, also is used to suppress when the reflection of light of active energy beam during by Photocurable resin composition inside or the obstruction of refraction etc.
The combined amount of these fillers (D) is 0.1～300 weight portion, the ratio of 0.1～150 weight portion more preferably with respect to the above-mentioned carboxylic acid resin (A) who contains unsaturated group of 100 weight portions.During combined amount less than 0.1 weight portion of above-mentioned filler (D), cured coating film characteristics such as scolding tin thermotolerance, plating tolerance reduce, and are therefore not preferred.On the other hand, when the combined amount of above-mentioned filler (D) surpassed 300 weight portions, the viscosity of composition uprised, printing reduces or solidfied material becomes fragile, and is therefore not preferred.
The employed Thermocurable composition that in molecule, has 2 above ring-type ethers and/or a cyclic thioether base among the present invention (below, abbreviate ring-type (sulphur) ether compound as.) (E) be the compound that has the ring-type ether of 3,4 or 5 yuan of rings more than 2 or any one or two kinds of groups in the cyclic thioether base in the molecule, can enumerate the compound that has at least 2 above epoxy radicals in the molecule for example and be the compound that has at least 2 above oxetanyls in multi-group epoxy compound (E-1), the molecule and be the compound that has 2 above thioether groups in polyfunctional group oxetane compound (E-2), the molecule is episulfide resin etc.
As above-mentioned multi-group epoxy compound (E-1), for example can enumerate, bisphenol A type epoxy resin, エ ピ コ one ト 828 as the manufacturing of japan epoxy resin company, エ ピ コ one ト 834, エ ピ コ one ト 1001, エ ピ コ one ト 1004, the エ ピ Network ロ Application 840 that big Japanese ink chemical industrial company makes, エ ピ Network ロ Application 850, エ ピ Network ロ Application 1050, エ ピ Network ロ Application 2055, Dongdu changes into the エ Port ト one ト YD-011 that company makes, YD-013, YD-127, YD-128, the D.E.R.317 that Dow Chemical makes, D.E.R.331, D.E.R.661, D.E.R.664, the ア ラ Le ダ イ De 6071 that Xiba Special Chemical Product Co.,Ltd makes, ア ラ Le ダ イ De 6084, ア ラ Le ダ イ De GY250, ア ラ Le ダ イ De GY260, the ス ミ one エ Port キ シ ESA-011 that Sumitomo Chemical Co. Ltd. makes, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial group of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, A.E.R.664 etc. (all being trade name); Brominated epoxy resin, エ ピ コ one ト YL903 as the manufacturing of japan epoxy resin company, エ ピ Network ロ Application 152, エ ピ Network ロ Application 165 that big Japanese ink chemical industrial company makes, Dongdu changes into エ Port ト one ト YDB-400, the YDB-500 that company makes, the D.E.R.542 that Dow Chemical makes, the ア ラ Le ダ イ De 8011 that Xiba Special Chemical Product Co.,Ltd makes, ス ミ one エ Port キ シ ESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. makes, (all being trade name) such as A.E.R.711, A.E.R.714 that industrial group of Asahi Chemical Industry makes; Phenolic resin varnish type epoxy resin, エ ピ コ one ト 152 as the manufacturing of japan epoxy resin company, エ ピ コ one ト 154, the D.E.N.431 that Dow Chemical makes, D.E.N.438, the エ ピ Network ロ Application N-730 that big Japanese ink chemical industrial company makes, エ ピ Network ロ Application N-770, エ ピ Network ロ Application N-865, Dongdu changes into the エ Port ト one ト YDCN-701 that company makes, YDCN-704, the ア ラ Le ダ イ De ECN1235 that Xiba Special Chemical Product Co.,Ltd makes, ア ラ Le ダ イ De ECN1273, ア ラ Le ダ イ De ECN1299, ア ラ Le ダ イ De XPY307, the EPPN-201 that Japan's chemical drug corporate system is made, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the ス ミ one エ Port キ シ ESCN-195X that Sumitomo Chemical Co. Ltd. makes, ESCN-220, the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry makes, ECN-299 etc. (all being trade name); Bisphenol f type epoxy resin, the エ ピ Network ロ Application of making as big Japanese ink chemical industrial company 830, エ ピ コ one ト 807 that japan epoxy resin company makes, Dongdu changes into エ Port ト one ト YDF-170, YDF-175, the YDF-2004 that company makes, (all being trade names) such as ア ラ Le ダ イ De XPY306 that Xiba Special Chemical Product Co.,Ltd makes; Bisphenol-A epoxy resin changes into エ Port ト one ト ST-2004, ST-2007, the ST-3000 (trade name) etc. that company makes as Dongdu; Glycidyl amine type epoxy resin, エ ピ コ one ト 604 as the manufacturing of japan epoxy resin company, Dongdu changes into the エ Port ト one ト YH-434 that company makes, the ア ラ Le ダ イ De MY720 that Xiba Special Chemical Product Co.,Ltd makes, (all being trade name) such as ス ミ one エ Port キ シ ELM-120 that Sumitomo Chemical Co. Ltd. makes; The ア ラ Le ダ イ De CY-350 hydantoins type epoxy resin such as (trade names) that Xiba Special Chemical Product Co.,Ltd makes; The セ ロ キ サ イ De 2021 that Daicel chemical industrial company makes, (all being trade name) alicyclic epoxy resins such as ア ラ Le ダ イ De CY175, CY179 that Xiba Special Chemical Product Co.,Ltd makes; The YL-933 that japan epoxy resin company makes, (all being trade name) trihydroxy benzene methylmethane type epoxy resin such as T.E.N.EPPN-501, EPPN502 that Dow Chemical makes; (all being trade name) di-cresols type or united phenol-type epoxy resin or their potpourris such as YL-6056, the YX-4000 that japan epoxy resin company makes, YL-6121; The EBPS-200 that Japan's chemical drug corporate system is made, the EXA-1514 bisphenol-s epoxy resins such as (trade names) that the EPX-30 that Asahi Electro-Chemical Co. Ltd makes, big Japanese ink chemical industrial company make; The エ ピ コ one ト 157S bisphenol-A phenolic varnish type epoxy resin such as (trade names) that japan epoxy resin company makes; (all being trade name) four phenolic hydroxyl group ethane type epoxy resin such as ア ラ Le ダ イ De 163 that the エ ピ コ one ト YL-931 that japan epoxy resin company makes, Xiba Special Chemical Product Co.,Ltd make; (all being trade name) hetero ring type epoxy resin such as TEPIC that the ア ラ Le ダ イ De PT810 that Xiba Special Chemical Product Co.,Ltd makes, daily output chemical industrial company make; The o-phthalic acid diglycidyl ester resins such as Block レ Application マ one DGT that Nof Corp. makes; Dongdu changes into the four glycidyl group xylenols ethane resin such as ZX-1063 that company makes; ESN-190, ESN-360 that chemical company of Nippon Steel makes, HP-4032, the EXA-4750 that big Japanese ink chemical industrial company makes, EXA-4700 etc. contain the epoxy resin of naphthyl; HP-7200, the HP-7200H etc. that big Japanese ink chemical industrial company makes have the epoxy resin of bicyclopentadiene skeleton; The glycidyl methacrylate copolymerization based epoxy resins such as CP-50S, CP-50M that Nof Corp. makes; Further can enumerate the copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; The epoxy resin (for example Dongdu changes into YR-102, the YR-450 etc. that company makes) of epoxide modified polybutadiene rubber derivant (for example the PB-3600 that makes of Daicel chemical industry etc.), CTBN modification etc., but be not limited to these materials. these epoxy resin can be used alone or in combination of two or more kinds. preferred especially phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their potpourri in the middle of these.
As above-mentioned polyfunctional group oxetane compound (E-2), can enumerate two [(3-methyl-3-oxetanes ylmethoxy) methyl] ethers, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, 1, two [(3-methyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters and polyfunctional group oxetanes classes such as their oligomer or multipolymer, in addition, also have oxetanes and novolac resin, poly-(para hydroxybenzene ethene), cardo type bisphenols, calixarene kind, resorcinol calixarenes (calixresorcinarene) class, or silsesquioxane (silsesquioxane) etc. has the etherate etc. of the resin of hydroxyl.Other example can also be enumerated unsaturated monomer with oxetanes ring and multipolymer of alkyl (methyl) acrylate etc.
As the compound that has 2 above cyclic thioether bases in the above-mentioned molecule, for example can enumerate the bisphenol A-type episulfide resin YL7000 that japan epoxy resin company makes etc.In addition, also can use with same synthetic method the oxygen atom of the epoxy radicals in the phenolic resin varnish type epoxy resin is replaced to the resulting episulfide resin of sulphur atom etc.
The combined amount of such ring-type (sulphur) ether (E), be 0.6～2.0 equivalent, be preferably the scope of 0.8～1.5 equivalent with respect to above-mentioned carboxyl 1 equivalent that contains the carboxylic acid resin of unsaturated group. the combined amount of ring-type (sulphur) ether (E) than above-mentioned scope situation still less under, carboxyl can be residual, make declines such as thermotolerance, alkali resistance, electrical insulating property, therefore not preferred. on the other hand, surpassing under the situation of above-mentioned scope, because low-molecular-weight ring-type (sulphur) ether (E) can be residual, cause the reductions such as intensity of filming, therefore not preferred.
State in the use under the situation of ring-type (sulphur) ether compound (E), preferably contain thermal curing catalyst.As such thermal curing catalyst, imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole are for example arranged; Dicyandiamide, benzyl dimethyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, amines such as N-dimethyl benzyl amine; Hydrazide compounds such as hexane diacid hydrazides, decanedioic acid hydrazides; Phosphorus compounds such as triphenylphosphine etc.; And there are four countries for example to change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of glyoxaline compound all) that industrial group makes as commercially available product, U-CAT3503X, U-CAT3502X (being the trade name of the block isocyanate compound of dimethyl amine all) etc. that サ Application ア プ ロ company makes, DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof all) etc.Be not particularly limited in above-claimed cpd, so long as the thermal curing catalyst of epoxy resin or oxetane compound, maybe can promote that the material of reaction of epoxy radicals and/or oxetanyl and carboxyl is just passable, can use separately or mix more than 2 kinds and use.In addition, also can use the guanamine that also has as the function of tackifiers, acetyl guanamine, stupid and guanamine, melamine, 2,4-diamido-6-methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamido-S-triazine, 2-vinyl-4,6-diamido-S-triazine isocyanuric acid addition product, 2,4-diamido-6-methacryloxyethyl-S-pyrrolotriazine derivatives such as S-triazine isocyanuric acid addition product, the compound that preferably these is also played the tackifiers effect is used in combination with above-mentioned thermal curing catalyst.
The combined amount of these thermal curing catalysts is just enough with the ratio of common amount, be 0.1～20 weight portion for example, be preferably the ratio of 0.5～15.0 weight portion with respect to carboxylic acid resin who contains unsaturated group (A) or ring-type (sulphur) ether compound (E) 100 weight portions.
Further, in the light solidifying/heat solidifying resin composition of the present invention, regulate viscosity for the synthetic above-mentioned carboxylic acid resin (A) who contains unsaturated group or modulation group compound or for it being applied on substrate or the carrier film, can be with an organic solvent.
As such organic solvent, can enumerate ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, petroleum-type solvent etc.More particularly be ketones such as MEK, cyclohexanone; First is stupid, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; Glycol ethers acetate esters such as dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters; Ester classes such as the acid esterification thing of ethyl acetate, butyl acetate and above-mentioned glycol ethers; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Petroleum-type solvents such as sherwood oil, naphtha, hydrotreated naphtha, solvent naphtha etc.
Such organic solvent can use separately or use as the potpourri more than 2 kinds.
Light solidifying/heat solidifying resin composition of the present invention, can also mix phthalocyanine blue as required, phthalocyanine green, iodine is green, permanent yellow, crystal violet, titanium dioxide, carbon black, known colorants commonly used such as naphthalene is black, quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, known hot polymerization inhibitor commonly used such as phenothiazine, fine particle silica, organobentonite, known thickening agent commonly used such as polynite, silicone, the fluorine class, the defoamer and/or the levelling agent of high score subclass etc., imidazoles, thiazoles, known additive kinds commonly used such as the silane coupling agent of triazole type etc.
Light solidifying/heat solidifying resin composition of the present invention, for example adjust to the viscosity that is suitable for coating process with above-mentioned organic solvent, pass through dip coating, flow coat method, rolling method, rod is coated with method, silk screen print method, methods such as curtain coating method are applied on the base material, and under about 60～100 ℃ temperature, make organic solvent volatile dry contained in the composition (temporary transient dry), can form filming of dry to touch thus. in addition, be applied to above-mentioned composition on the carrier film and make it dry and make film and reel, then it is adhered on the base material, can form resin insulating barrier thus. afterwards, with contact (or noncontact mode) by forming figuratum photomask and utilizing active energy beam to make the exposure of its selectivity, non-exposed portion is developed with dilute alkaline aqueous solution (for example 0.3～3% aqueous sodium carbonate) and the formation corrosion-resisting pattern. further, for example can make its heat curing by heating under about 140～180 ℃ temperature, have Thermocurable composition (E) reaction of 2 above ring-type ethers and/or cyclic thioether base thereby make in the above-mentioned carboxylic acid resin's (A) who contains unsaturated group carboxyl and the molecule, thereby can form thermotolerance, chemical proofing, anti-hydroscopicity, cohesive, the cured coating film of all excellents such as electrical specification.
As above-mentioned base material, can enumerate the high-frequency circuit that uses paper phenolics, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/nonwoven fabrics epoxy resin, glass cloth/paper epoxy resin, synthon epoxy resin, fluoro-tygon-PPO-cyanate etc. copper clad laminate with all models (FR-4 etc.) of materials such as copper clad laminate, and polyimide film, PET film, glass substrate, ceramic substrate, wafer board etc.
Be coated with the volatile dry that carries out after the light solidifying/heat solidifying resin composition of the present invention, can use heated air circulation type drying oven, IR stove, heating plate, convection oven etc. (being provided with the device of thermal source that carries out the mode of air heat with steam by use makes hot blast in the dryer carry out the method for convection current contact and blow to mode on the supporter by nozzle) to carry out.
As described below with behind Photocurable resin composition coating of the present invention and the volatile dry, to expose (the irradiation active energy beam) of filming that obtains thus.In filming, its exposed portion (part of being shone by active energy beam) solidifies.
As the exposure machine that is used to shine above-mentioned active energy beam, can use direct drawing apparatus (for example directly using the laser image forming apparatus of laser scanning image) as described above by the cad data of computer.As active energy beam,, no matter be that gas laser or Solid State Laser can as long as use the laser of maximum wavelength in 350～420nm scope.In addition, its exposure is according to thickness etc. and different, but can be made as 2～100mJ/cm usually 2, preferably be made as 5～60mJ/cm 2, further preferably be made as 10～30mJ/cm 2Scope in.As above-mentioned direct drawing apparatus, can use the device of ペ Application タ Star Network ス company manufacturing, the device that the PVC ア メ カ ニ of Hitachi Network ス company makes, the device that ボ one Le セ ミ コ Application ダ Network タ one company makes etc., can use device arbitrarily.
As above-mentioned developing method, infusion process, spray process, gunite, brushing method etc. are arranged, can use the alkaline aqueous solution of potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc. as developer solution.
Embodiment
Below, provide embodiment and comparative example and come the present invention is specifically described, but should be understood that the present invention is not limited to following embodiment.
＜contain carboxylic acid resin synthetic of unsaturated group 〉
Synthesis example 1
In having 1 liter removable flask of stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, add cresols phenolic resin varnish type epoxy resin (エ ピ Network ロ Application N-680,78 ℃ of softening points, epoxide equivalent 215 that big Japanese ink chemical industrial company makes) 215g and the carbitol acetic acid esters 112.3g after dehydrating, be heated to 90 ℃ and stirring, make it dissolving.Then, temporarily be cooled to 60 ℃, add acrylic acid 72g, triphenylphosphine 1.0g, methylnaphthohydroquinone 0.2g, under 95 ℃, make it to react 16 hours, obtain the reaction product that acid number is 0.2mg KOH/g. add tetrabydrophthalic anhydride 91.2g therein, be heated to 85 ℃ and make it to react 8 hours.
The イ プ ゾ one Le #150 of 112.3g bright dipping petrochemistry corporate system is joined in this reaction solution, and maintain about 60 ℃.Further, the foaming that marginal not meaning decarbonate causes, the limit will make pentaerythrite 1 mole of (298g) and isophorone diisocyanate 1 mole (222g) react the half polyurethane 15.6g that gets by usual way in advance with about 1 hour and slowly drip and make it reaction.And then, be heated to 80 ℃, make it to react 1 hour, with its taking-up.
The carboxylic acid resin's who contains unsaturated group (A) who obtains thus solution, its varnish acid number are that 52.1mg KOH/g, two key equivalent (solid constituent scaled value) are 358, nonvolatile component is 63.6 weight %.Below, this resin solution is called (A-1) varnish.
＜contain carboxylic acid resin synthetic of unsaturated group 〉
Synthesis example 2
In having 2 liters removable flask of stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, add cresols phenolic resin varnish type epoxy resin (エ ピ Network ロ Application N-680,78 ℃ of softening points, epoxide equivalent 215 that big Japanese ink chemical industrial company makes) 215g and the carbitol acetic acid esters 128.1g after dehydrating, be heated to 90 ℃ and stirring, make it dissolving.Then, temporarily be cooled to 60 ℃, add acrylic acid 72g, triphenylphosphine 1.0g, methylnaphthohydroquinone 0.2g, under 95 ℃, make it to react 16 hours, obtain the reaction product that acid number is 0.2mg KOH/g.Add tetrabydrophthalic anhydride 91.2g therein, be heated to 85 ℃ and make it to react 8 hours.
The イ プ ゾ one Le #150 of 128.1g bright dipping petrochemistry corporate system is joined in this reaction solution, and maintain about 60 ℃.Further, the foaming that decarbonate causes is observed on the limit, and the limit slowly dripped in advance with about 1 hour and makes pentaerythrite 1 mole of (298g) and isophorone diisocyanate 1 mole (222g) react the half polyurethane 31.2g that gets and make it reaction by usual way.And then, be heated to 80 ℃, make it to react 1 hour, take out.
The carboxylic acid resin's who contains unsaturated group (A) who obtains thus solution, its varnish acid number are that 51.2mg KOH/g, two key equivalent (solid constituent scaled value) are 347, nonvolatile component is 61.5 weight %.Below, this resin solution is called (A-2) varnish.
＜contain carboxylic acid resin synthetic of unsaturated group 〉
Synthesis example 3
In having 2 liters removable flask of stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, add cresols phenolic resin varnish type epoxy resin (エ ピ Network ロ Application N-680,78 ℃ of softening points, epoxide equivalent 215 that big Japanese ink chemical industrial company makes) 215g and the carbitol acetic acid esters 126.3g after dehydrating, be heated to 90 ℃ and stirring, make it dissolving.Then, temporarily be cooled to 60 ℃, add acrylic acid 72g, triphenylphosphine 1.0g, methylnaphthohydroquinone 0.2g, under 95 ℃, make it to react 16 hours, obtain the reaction product that acid number is 0.2mg KOH/g.Add tetrabydrophthalic anhydride 101.3g therein, be heated to 85 ℃ and make it to react 8 hours.
The イ プ ゾ one Le #150 of 126.3g bright dipping petrochemistry corporate system is joined in this reaction solution, and maintain about 60 ℃.Further, the foaming that decarbonate causes is observed on the limit, the limit with the カ レ Application ズ BEI (1,1-(two acryloyl-oxy ylmethyl) ethyl isocyanate) that slowly dripped the clear and electrician's corporate system of 23.9g in about 1 hour, make it to react.And then, be heated to 80 ℃, make it to react 1 hour, take out.
The carboxylic acid resin who contains unsaturated group (A) solution that obtains thus, its varnish acid number are that 47.8m g KO H/g, two key equivalent (solid constituent scaled value) are 343.5, nonvolatile component is 62.0 weight %.Below, this resin solution is called (A-3) varnish.
Compound synthetic that has 2 above ethylenically unsaturated groups in the＜molecule 〉
Synthesis example 4
Add 215 parts of cresols phenolic resin varnish type epoxy resin エ ピ Network ロ Application N-680 (big Japanese ink chemical industry (strain) manufacturing, epoxide equivalent=215g/ equivalent), 266.5 parts of carbitol acetic acid esters in having 2 liters removable flask of stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, heating makes it dissolving.In this resin solution, add 0.05 part of quinhydrones as polymerization inhibitor, add 1.0 parts of triphenylphosphines as catalysts.With this mixture heated to 85～95 ℃, slowly drip 72 parts of acrylic acid again, make it to react 24 hours.In this epoxy acrylate, slowly drip in advance with 208 parts of 1: 1 mole of half polyurethane that isophorone diisocyanate and pentaerythritol triacrylate is reacted obtain, and under 60～70 ℃, make it to react 4 hours.Obtain epoxy polyurethane acrylate varnish (nonvolatile component=65 weight %) thus as the compound that has 2 above ethylenically unsaturated groups in the molecule (C), below, be referred to as (C-1) varnish.
Compare synthesis example 1
Add 215 parts of cresols phenolic resin varnish type epoxy resin エ ピ Network ロ Application N-680 (big Japanese ink chemical industry (strain) manufacturing, epoxide equivalent=215), 110.3 parts of carbitol acetic acid esters in having 2 liters removable flask of stirrer, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, heating makes it dissolving.In this resin solution, add 0.05 part of quinhydrones as polymerization inhibitor, add 1.0 parts of triphenylphosphines as catalysts.With this mixture heated to 85～95 ℃, slowly drip 72 parts of acrylic acid again, make it to react 24 hours, obtain the reaction product that acid number is 0.2mg KOH/g.Add tetrabydrophthalic anhydride 91.2g therein, be heated to 85 ℃ and make it to react 8 hours.In this solution, add the イ プ ゾ one Le #150 of 110.3g bright dipping petrochemistry corporate system, take out.
The carboxylic acid resin's solution that contains unsaturated group that obtains thus, its varnish acid number are that 57.9mg KOH/g, two key equivalent are 378, nonvolatile component is 65.0 weight %.Below, this resin solution is called (R-1) varnish.
＜i ray the modulation of light solidifying/heat solidifying resin composition 〉
Use the resin solution of above-mentioned synthesis example 1～4 and comparison synthesis example 1 to mix with the ratio shown in the table 1 (weight portion) with the various compositions shown in the table 1, after using the stirring machine premixed, use 3 roll-type three-stage roll mill mixing, the light solidifying/heat solidifying resin composition that modulation i ray is used.Here, measure the dispersion degree that granularity is estimated the light solidifying/heat solidifying resin composition of gained with the particle size analyzer that エ リ Network セ Application company makes, the result is below the 15 μ m.
＜i ray light solidifying/heat solidifying resin composition 〉
Table 1
＜h ray the modulation of light solidifying/heat solidifying resin composition 〉
Use the resin solution of above-mentioned synthesis example 1～4 and comparison synthesis example 1 to mix with the ratio shown in the table 2 (weight portion) with the various compositions shown in the table 2, after using the stirring machine premixed, use 3 roll-type three-stage roll mill mixing, the light solidifying/heat solidifying resin composition that modulation h ray is used.Here, measure the dispersion degree that granularity is estimated the light solidifying/heat solidifying resin composition of gained with the particle size analyzer that エ リ Network セ Application company makes, the result is below the 15 μ m.
＜h ray light solidifying/heat solidifying resin composition 〉
Table 2
Figure G2006101404506D00261
＜metal halide lamp the modulation of light solidifying/heat solidifying resin composition 〉
Use the resin solution of above-mentioned synthesis example 1～4 and comparison synthesis example 1 to mix with the ratio shown in the table 3 (weight portion) with the various compositions shown in the table 3, after using the stirring machine premixed, use 3 roll-type three-stage roll mill mixing, the light solidifying/heat solidifying resin composition that the modulation metal halide lamp is used. here, measure the dispersion degree that granularity is estimated the light solidifying/heat solidifying resin composition of gained with the particle size analyzer that エ リ Network セ Application company makes, the result is below the 15 μ m.
＜metal halide lamp light solidifying/heat solidifying resin composition 〉
Table 3
Performance evaluation:
＜light sensitivity 〉
Adopt silk screen print method, with the embodiment 1～11 that obtains of modulation and the whole face of light solidifying/heat solidifying resin composition of comparative example 1～3 are applied on etching (etching out) substrate of the Copper Foil of having removed copper clad laminate FR-4 fully like this, and make dry film thickness become about 20 μ m, drying is 15 minutes under 80 ℃, obtains filming of dry to touch.
Paste the stage metraster of the No.2 of Kodak on light solidifying/heat solidifying resin composition and dried substrate at the i ray of coating embodiment 1～4 and comparative example 1, the i ray that uses the manufacturing of オ Le ボ テ Star Network company is with laser direct imaging device (Paragon8000), with accumulation light quantity 50mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3Aqueous solution presses 0.2MP a to carry out 1 minute development with spray, then, by the hop count that is obtained by stage metraster light sensitivity is estimated.Table 4 provides this result.
Paste the stage metraster of the No.2 of Kodak on light solidifying/heat solidifying resin composition and dried substrate at the h ray of coating embodiment 5～8 and comparative example 2, the h ray that uses the manufacturing of ペ Application タ Star Network ス company is with laser direct imaging device (DI-μ 10), with accumulation light quantity 50mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3Aqueous solution presses 0.2MPa to carry out 1 minute development with spray, then, by the hop count that is obtained by stage metraster light sensitivity is estimated.Table 5 provides this result.
Paste the stage metraster of the No.2 of Kodak on light solidifying/heat solidifying resin composition and dried substrate at the metal halide lamp ray of coating embodiment 9～11 and comparative example 3, use オ one Network to make the exposure machine (GW-680) that company of institute makes, with accumulation light quantity 150mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3Aqueous solution presses 0.2MPa to carry out 1 minute development with spray, then, by the hop count that is obtained by stage metraster light sensitivity is estimated.Table 6 provides this result.
＜resolution 〉
With similarly above-mentioned, pass through silk screen print method, the whole face of light solidifying/heat solidifying resin composition of embodiment 1～11 and comparative example 1～3 is applied on etching (etching out) substrate of the Copper Foil of having removed copper clad laminate FR-4 fully, and make dry film thickness become about 20 μ m, drying is 15 minutes under 80 ℃, obtains filming of dry to touch.
Paste at the i ray of coating embodiment 1～4 and comparative example 1 and to have described the photomask that line/interval is respectively the pattern of 30,40,50,60,70,80,90,100 μ m with light solidifying/heat solidifying resin composition and dried substrate, the i ray that uses the manufacturing of オ Le ボ テ Star Network company is with laser direct imaging device (Paragon 8000), with accumulation light quantity 50mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3After aqueous solution presses 0.2MPa to develop 1 minute with spray, with the minimum feature of visual valuation image retention.Table 4 provides this result.
Paste at the h ray of coating embodiment 5～8 and comparative example 2 and to have described the photomask that line/interval is respectively the pattern of 30,40,50,60,70,80,90,100 μ m with light solidifying/heat solidifying resin composition and dried substrate, the h ray that uses the manufacturing of ペ Application タ Star Network ス company is with laser direct imaging device (DI-μ 10), with accumulation light quantity 50mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3After aqueous solution presses 0.2MPa to develop 1 minute with spray, with the minimum feature of visual valuation image retention.Table 5 provides this result.
Paste at the metal halide lamp ray of coating embodiment 9～11 and comparative example 3 and to have described the photomask that line/interval is respectively the pattern of 30,40,50,60,70,80,90,100 μ m with light solidifying/heat solidifying resin composition and dried substrate, use オ one Network to make the exposure machine (GW-680) that company of institute makes, with accumulation light quantity 150mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3After aqueous solution presses 0.2MPa to develop 1 minute with spray, with the minimum feature of visual valuation image retention.Table 6 provides this result.
＜coating characteristic is estimated the manufacturing of substrate 〉
Adopt silk screen print method, the whole face of light solidifying/heat solidifying resin composition of embodiment 1～11 and comparative example 1～3 is applied on the copper clad laminate FR-4 that forms circuit, and making dry film thickness become about 20 μ m, drying is 15 minutes under 80 ℃, obtains filming of dry to touch.
Paste the photomask of the circuit pattern of having described expectation on light solidifying/heat solidifying resin composition and dried substrate at the i ray of coating embodiment 1～4 and comparative example 1, the i ray that uses the manufacturing of オ Le ボ テ Star Network company is with laser direct imaging device (Paragon 8000), with accumulation light quantity 50mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3Aqueous solution presses 0.2MPa to develop 1 minute with spray, has made coating characteristic evaluation substrate.
Similarly paste the photomask of the circuit pattern of having described expectation on light solidifying/heat solidifying resin composition and dried substrate at the h ray of coating embodiment 5～8 and comparative example 2, the h ray that uses the manufacturing of ペ Application タ Star Network ス company is with laser direct imaging device (DI-μ 10), with accumulation light quantity 50mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3Aqueous solution presses 0.2MPa to develop 1 minute with spray, has made coating characteristic evaluation substrate.
Paste the photomask of the circuit pattern of having described expectation on light solidifying/heat solidifying resin composition and dried substrate at the metal halide lamp ray of coating embodiment 9～11 and comparative example 3, use オ one Network to make the exposure machine (GW-680) that company of institute makes, with accumulation light quantity 150mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3Aqueous solution presses 0.2MPa to develop 1 minute with spray, has made coating characteristic evaluation substrate.
＜scolding tin thermotolerance 〉
The rosin based solder flux is applied to above-mentioned each that makes estimates with on the substrate, 30 seconds of dipping in being heated to 260 ℃ weld groove in advance, wash solder flux off with propylene glycol monomethyl ether after, the swelling of visual valuation resist layer, peel off, variable color.Its result is shown in table 4, table 5 and table 6 respectively.
Zero: confirm not change fully
△: only take place a bit to change
*: the swelling of having filmed, peel off
＜electroless plating metal tolerance 〉
With above-mentioned respectively estimating in the acid degreaser that substrate is immersed in 30 ℃ (Japanese マ Network ダ one ミ Star De company makes, the 20vol% aqueous solution of Metex L-5B) 3 minutes dipping being washed in 3 minutes in flowing water then to carry out degreasing of obtaining.Should estimate substrate and be immersed under room temperature in the 14.3wt% ammonium persulfate aqueous solution, and carry out soft etching (soft etching), then, dipping was washed in 3 minutes in flowing water.To estimate substrate and be immersed in the 10vol% aqueous sulfuric acid after 1 minute under room temperature, dipping 30 second～1 minute are washed in flowing water.This evaluation substrate is immersed in 30 ℃ the catalyzer liquid (メ Le テ Star Network ス company makes, the 10vol% aqueous solution of メ タ Le プ レ one ト ア Network チ ベ one タ 1) 7 minutes, gives after the catalyzer, dipping was washed in 3 minutes in flowing water.With giving in the nickel plating bath that evaluation substrate behind the catalyzer is immersed in 85 ℃ (メ Le テ Star Network is made, 20vol% aqueous solution, the pH4.6 of メ Le プ レ one ト Ni-865M) 20 minutes, carry out electroless nickel plating.To estimate substrate and be immersed in the 10vol% aqueous sulfuric acid after 1 minute under room temperature, dipping 30 second～1 minute are washed in flowing water.To estimate in the metal plating liquid (aqueous solution, the p H6 of メ Le テ Star Network ス corporate system, オ ウ ロ レ Network ト ロ レ ス UP 15vol% and potassium auricyanide 3vol%) that substrate is immersed in 95 ℃ 10 minutes then, carry out after the electroless plating metal, dipping was washed in 3 minutes in flowing water, and then dipping carried out hot wash in 3 minutes in 60 ℃ warm water.Fully after the washing, fully dewater and carry out drying, obtained applying the evaluation substrate of electroless plating metal.Use the evaluation substrate that has applied the electroless plating metal obtain thus, utilize cellophane tape to carry out disbonded test, peeling off of filming, variable color are estimated according to following benchmark.Its result is shown in table 4, table 5 and table 6 respectively.
Zero: confirm not change fully
△: confirming to film only has any to be stripped from or some variable colors is only arranged.
*: confirming has filmed peels off
＜electrical insulating property 〉
With similarly above-mentioned, adopt silk screen print method, the whole face of light solidifying/heat solidifying resin composition of embodiment 1～11 and comparative example 1～3 is applied on the copper clad laminate FR-4 that has formed IPC B-25 comb-type electrode B print (coupon), and make dry film thickness become about 20 μ m, drying is 15 minutes under 80 ℃, obtains filming of dry to touch.
Paste the photomask of the circuit pattern of having described expectation on light solidifying/heat solidifying resin composition and dried substrate at the i ray of coating embodiment 1～4 and comparative example 1, the i ray that uses the manufacturing of オ Le ボ テ Star Network company is with laser direct imaging device (Paragon 8000), with accumulation light quantity 50mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3Aqueous solution presses 0.2MPa to develop 1 minute with spray, has made electrical insulating property evaluation substrate.
Similarly paste the photomask of the circuit pattern of having described expectation on light solidifying/heat solidifying resin composition and dried substrate at the h ray of coating embodiment 5～8 and comparative example 2, the h ray that uses the manufacturing of ペ Application タ Star Network ス company is with laser direct imaging device (DI-μ 10), with accumulation light quantity 50mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3Aqueous solution presses 0.2MPa to develop 1 minute with spray, has made electrical insulating property evaluation substrate.
Paste the photomask of the circuit pattern of having described expectation on light solidifying/heat solidifying resin composition and dried substrate at the metal halide lamp ray of coating embodiment 9～11 and comparative example 3, use オ one Network to make the exposure machine (GW-680) that company of institute makes, with accumulation light quantity 150mJ/cm 2Carry out whole exposure, utilize the Na of 1wt% 2CO 3Aqueous solution presses 0.2MP a to develop 1 minute with spray, has made electrical insulating property evaluation substrate.
The comb-type electrode of the evaluation substrate that obtains is thus applied the bias voltage of DC5.5V, be determined at humidity 85%, 130 ℃ of insulating resistance values of placing down after 150 hours of temperature.Its result is shown in table 4, table 5 and table 6 respectively.
Table 4
Figure G2006101404506D00321
Table 5
Figure G2006101404506D00331
Table 6
Figure G2006101404506D00332
From the result shown in above-mentioned table 4, table 5 and the table 6 as can be known, use of the present invention contains the carboxylic acid resin's of unsaturated group light solidifying/heat solidifying resin composition, different with existing resin, be ISO and resolution, scolding tin thermotolerance, electroless plating metal tolerance excellence.
In addition, light solidifying/heat solidifying resin composition of the present invention as can be known can be by changing the composition of Photoepolymerizationinitiater initiater, also can tackle to monochromatic light such as i ray, h ray or to ultraviolet light sources such as metal halide lamps.

Claims (18)

1. light solidifying/heat solidifying resin composition that can develop by dilute alkaline soln, it comprises:
(A) make contain compound (A2) reaction that has 1 isocyanate group and 2 above ethylenically unsaturated groups in carboxylic acid resin (A1) and 1 molecule and the carboxylic acid resin of containing unsaturated group, its acid number is 20～60 weight % in 2000～150000 scope, combined amount in the scope of 40～200mg KOH/g, weight-average molecular weight in whole compositions;
(B) Photoepolymerizationinitiater initiater, its blending ratio are to be 0.01～30 weight portion with respect to the above-mentioned carboxylic acid resin (A) of containing unsaturated group of 100 weight portions;
(C) have the compound of 2 above ethylenically unsaturated groups in the molecule, its combined amount is 5～100 weight portions with respect to the above-mentioned carboxylic acid resin (A) of containing unsaturated group of 100 weight portions;
(D) filler, its combined amount is 0.1～300 weight portion with respect to the above-mentioned carboxylic acid resin (A) of containing unsaturated group of 100 weight portions; And
(E) have the Thermocurable composition of 2 above ring-type ethers and/or cyclic thioether base in the molecule, its combined amount is 0.6～2.0 equivalent with respect to above-mentioned carboxyl 1 equivalent that contains the carboxylic acid resin (A) of unsaturated group.
2. light solidifying/heat solidifying resin composition according to claim 1, it is characterized in that, the described carboxylic acid resin of containing (A 1) be make after the reaction of polyfunctional epoxy resin (a) and saturated or undersaturated monocarboxylic acid (b) again with multi-anhydride (c) reaction contain carboxy resin.
3. light solidifying/heat solidifying resin composition according to claim 1, it is characterized in that the described carboxylic acid resin of containing (A1) is the carboxy resin that contains that gets with multi-anhydride (c) reaction again after difunctional epoxy resin (d) and difunctional phenol (e) and/or dicarboxylic acid (f) are reacted.
4. light solidifying/heat solidifying resin composition according to claim 1, it is characterized in that the described carboxylic acid resin of containing (A1) is the carboxy resin that contains that gets with multi-anhydride (c) reaction again after the compound (h) that has 1 epoxy radicals in multifunctional phenolic resin (g) and the molecule is reacted.
5. light solidifying/heat solidifying resin composition according to claim 1 is characterized in that, the described carboxylic acid resin of containing (A1) makes the compound (i) that has 2 above alcohol hydroxyl groups in the molecule react the carboxy resin that contains that forms with multi-anhydride (c).
6. according to any described light solidifying/heat solidifying resin composition in the claim 1～5, it is characterized in that the compound (A2) that has 1 isocyanate group and 2 above ethylenically unsaturated groups in described 1 molecule is the isoflurane chalcone diisocyanate derivant.
7. according to any described light solidifying/heat solidifying resin composition in the claim 1～5, it is characterized in that the compound (A2) that has 1 isocyanate group and 2 above ethylenically unsaturated groups in described 1 molecule is the compound with 3 ethylenically unsaturated groups.
8. according to any described light solidifying/heat solidifying resin composition in the claim 1～5, it is characterized in that, the compound (A2) that has 1 isocyanate group and 2 above ethylenically unsaturated groups in described 1 molecule is 1,1-(two acryloyl-oxy ylmethyl) ethyl isocyanate.
9. according to any described light solidifying/heat solidifying resin composition in the claim 1～5, it is characterized in that described Photoepolymerizationinitiater initiater (B) is to contain the oxime ester class Photoepolymerizationinitiater initiater that contains oxime ester base shown in the following general formula (I),
Figure F2006101404506C00021
In the formula, R 1Expression hydrogen atom, carbon number are 1～7 alkyl or phenyl, R 2The expression carbon number is 1～7 alkyl or phenyl.
10. light solidifying/heat solidifying resin composition according to claim 9 is characterized in that, described oxime ester class Photoepolymerizationinitiater initiater (B) is the Photoepolymerizationinitiater initiater shown in the following formula (II).
11. according to any described light solidifying/heat solidifying resin composition in the claim 1～5, it can be the laser generation light source curing of 350nm～420nm by maximum wavelength.
12. the dry film of a Photosetting and thermosetting, it is applied to any described light solidifying/heat solidifying resin composition in the claim 1～5 on the carrier film and makes it dry and obtain.
13. a solidfied material, it makes any described light solidifying/heat solidifying resin composition photocuring in the claim 1～5 and obtains on copper.
14. a solidfied material, it makes the described dry film photocuring of claim 12 and obtains on copper.
15. a solidfied material, it makes by the laser generation light source, and any described light solidifying/heat solidifying resin composition photocuring obtains in the claim 1～5.
16. a solidfied material, it obtains the described dry film photocuring of claim 12 by the laser generation light source.
17. a printed circuit board (PCB), it is to be that the laser of 350nm～420nm makes in the claim 1～5 that heat curing obtains behind any described light solidifying/heat solidifying resin composition photocuring by wavelength.
18. a printed circuit board (PCB), it is to be that heat curing obtained after the laser of 350nm～420nm made the described dry film photocuring of claim 12 by wavelength.
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Patentee after: Taiyo Holding Co., Ltd.

Address before: Tokyo, Japan, Japan

Patentee before: Taiyo Ink Manufacturing Co., Ltd.

EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20070411

Assignee: Taiyo Ink Mfg.Co., Ltd.

Assignor: Taiyo Holding Co., Ltd.

Contract record no.: 2011990000116

Denomination of invention: Photohardenable and thermosetting resin compositions, their hardened product, and printing circuit boards using the same

Granted publication date: 20100512

License type: Common License

Record date: 20110302

LICC Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model