CN100569825C - Light solidifying/heat solidifying resin composition and cured article thereof - Google Patents

Light solidifying/heat solidifying resin composition and cured article thereof Download PDF

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CN100569825C
CN100569825C CNB2005800237251A CN200580023725A CN100569825C CN 100569825 C CN100569825 C CN 100569825C CN B2005800237251 A CNB2005800237251 A CN B2005800237251A CN 200580023725 A CN200580023725 A CN 200580023725A CN 100569825 C CN100569825 C CN 100569825C
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solidifying
resin composition
maleimide
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CN1984938A (en
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峰岸昌司
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13—Integrated optical circuits characterised by the manufacturing method
    • G02B6/138—Integrated optical circuits characterised by the manufacturing method by using polymerisation
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
    • H05K3/4676—Single layer compositions

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Structure Of Printed Boards (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a kind of light solidifying/heat solidifying resin composition that can develop by alkaline aqueous solution, it does not use Photoepolymerizationinitiater initiater or lacks than present usage quantity, thereby reduces volatile component, and can solidify with less ultraviolet irradiation amount.Said composition contains (A) and contains the compound that has 2 above epoxy group(ing) and/or oxetanyl in carboxyl photoresist, (B) maleimide derivatives, (C) a part, and (D) has the compound of the free redical polymerization of ring-type ether or morpholinyl (morpholino group).

Description

Light solidifying/heat solidifying resin composition and cured article thereof
Technical field
The present invention relates to light solidifying/heat solidifying resin composition and cured article thereof, the interlayer dielectic that is particularly related to various anticorrosive additive materials as printed circuit board (PCB), multilayer printed circuit board is useful, and as coating material, surface treatment agent, shaped material, tackiness agent, tackiness agent, printing-ink, tackiness agent etc., also to the light solidifying/heat solidifying resin composition that is formed with usefulness of laminated plate, optical waveguides etc.
In more detail, the present invention relates to not use Photoepolymerizationinitiater initiater or use still less than present usage quantity, thereby when solidifying or at high temperature or can reduce the new light solidifying/heat solidifying resin composition and the cured article thereof of evaporable composition when using under the decompression.
Background technology
Carry out the polymeric Photocurable resin composition by ultraviolet ray or visible light isoreactivity energy-ray, have the advantage of quick solidifying, be widely used in coating, welding resistance printing ink, printing-ink, tackiness agent, coating-forming agent etc.
This Photocurable resin composition, the active energy ray-curable resin that constitutes composition separately can not initiated polymerization, therefore be necessary to be used in combination with Photoepolymerizationinitiater initiater, but in order to carry out photocuring fast, the tendency that existence increases the addition of Photoepolymerizationinitiater initiater.
But, when the combined amount of Photoepolymerizationinitiater initiater increases, have following problem: the resolvent of the Photoepolymerizationinitiater initiater of remained unreacted or Photoepolymerizationinitiater initiater in cured article; When light or hotwork are used for this cured article, cause the cured article flavescence or produce stench from the volatile component of Photoepolymerizationinitiater initiater.
In addition, when the combined amount of Photoepolymerizationinitiater initiater increases, under humidified condition or liquid place under the situation of cured article in medium, exist unreacted Photoepolymerizationinitiater initiater etc. to ooze out or for example pollute the problem of plating bath.In addition, also there is the problem that causes electrical specification to reduce by the Photoepolymerizationinitiater initiater that oozes out in employed welding resistance printing ink in the precision optical machinery etc.
And then, use under the high temperature when soldering etc. or as situation about under reduced pressure using like that such as the printed circuit board (PCB) that uses in the outer space under, have unreacted Photoepolymerizationinitiater initiater volatilization, the pollution terminal causes loose contact, or the problem of pollution surrounding enviroment.
On the other hand, Photoepolymerizationinitiater initiater mostly is powder greatly, in composition, exist meal or again can't homodisperse situation under, exist in and produce particle in the cured coating film, cause the problem of bad order.
At these, in Japanese kokai publication hei 6-298817 number, proposed not contain the scheme of the Photocurable resin composition of Photoepolymerizationinitiater initiater.This Photocurable resin composition is what to adopt via the light polymerization process of charge transfer complex compound, wherein, the unsaturated compound that this charge transfer complex compound will have electron-donating group makes up and forms with the unsaturated compound with electron-accepting group, as having one of unsaturated compound of electron-accepting group, can maleimide derivatives be shown example.
Above-mentioned spy opens the flat 6-298817 number disclosed composition that contains maleimide derivatives can expect the minimizing of volatile component because of not containing Photoepolymerizationinitiater initiater.But, need a large amount of ultraviolet irradiation amounts, and the cured coating film of gained also can't obtain sufficient characteristic.
Summary of the invention
The problem that the invention desire solves
The object of the present invention is to provide a kind of light solidifying/heat solidifying resin composition of alkali developable, said composition contains maleimide derivatives, can reduce volatile component because of not using Photoepolymerizationinitiater initiater or lacking than present usage quantity, in addition, can solidify with less active energy beam irradiation dose.
The objective of the invention is to also provide a kind of printed circuit board (PCB), it forms the cured article that is made of such light solidifying/heat solidifying resin composition such as interlayer insulating film, solder mask layer, light waveguide-layer etc. and forms.
Solve the means of problem
For reaching described purpose, according to a first aspect of the invention, providing can be by the light solidifying/heat solidifying resin composition of alkaline aqueous solution development, it is characterized in that said composition contains (A) and contains the compound that has 2 above epoxy group(ing) and/or oxetanyl in carboxyl photoresist, (B) maleimide derivatives, (C) a part, and (D) has the compound of the free redical polymerization of ring-type ether or morpholinyl (morpholino group).
In addition, the blending ratio of described each composition is not limited to specified proportion, but with respect to 100 mass parts (as solids component, below identical) the described carboxyl photoresist (A) that contains, expectation maleimide derivatives (B) is 10～60 mass parts, be preferably the mixed of 30～50 mass parts, the compound (C) that has 2 above epoxy group(ing) and/or oxetanyl in a part is the mixed of 10～100 mass parts, the compound of free redical polymerization (D) is 5～50 mass parts, be preferably the mixed of 15～30 mass parts, and then when adding Photoepolymerizationinitiater initiater as required, can be with the mixed Photoepolymerizationinitiater initiater below 3 mass parts.
In addition, light solidifying/heat solidifying resin composition of the present invention, can directly use aqueous, the form that also can be used as dry film is used, can in various fields, effectively utilize, particularly at interlayer insulating film, the solder mask layer of printed circuit board (PCB), and constitute in the formation of sandwich layer, covering of optical waveguides and can effectively utilize.
Therefore, according to a second aspect of the invention, can provide by active energy beam irradiation and/or heating makes described light solidifying/heat solidifying resin composition solidify the cured article that obtains, as its preferred mode, can provide a kind of and form printed circuit board (PCB) that interlayer insulating film and/or solder mask layer form and form the printed circuit board (PCB) that light waveguide-layer forms by described light solidifying/heat solidifying resin composition by described light solidifying/heat solidifying resin composition.
The effect of invention
According to the light solidifying/heat solidifying resin composition that contains maleimide derivatives of the present invention, compound by in composition, containing the free redical polymerization with ring-type ether or morpholinyl (morpholino group) (below, only be called " compound of free redical polymerization "), even do not add Photoepolymerizationinitiater initiater, also can improve the light solidified of said composition.Its result does not lack than present usage quantity owing to do not use Photoepolymerizationinitiater initiater or use, can be provided at when solidifying or at high temperature or decompression use the time resin combination that reduced of institute's evaporable composition down.
In addition,, can obtain alkali-developable or to the adaptation excellence of base material according to light solidifying/heat solidifying resin composition of the present invention, and excellent cured articles such as anti-electroless plating, electric insulating quality.
Therefore, light solidifying/heat solidifying resin composition of the present invention is useful with material, optical waveguides with material etc. as coating, printing-ink, tackiness agent, various anticorrosive additive material, colour filter manufacturing, is particularly suitable in the purposes of interlayer insulating film, light waveguide-layer etc. of solder resist, the multilayer printed circuit board of printed circuit board (PCB).
Especially, need not the light solidifying/heat solidifying resin composition of the present invention that Photoepolymerizationinitiater initiater just can carry out photocuring, can suppress the loss of the light that light absorption caused of scattering of light that the Photoepolymerizationinitiater initiater particle causes, Photoepolymerizationinitiater initiater, be favourable to the formation of the optical waveguides of the propagated excellence of light.
Description of drawings
Fig. 1 is the fragmentary cross-sectional view of a routine multilayer printed circuit board.
Fig. 2 is the fragmentary cross-sectional view of a routine optical waveguides portion.
Nomenclature
1: circuit card, 2: conductor layer, 3: insulating resin layer, 4: via hole (via hole), 5: interlayer conduction hole, 6: conductor layer, 11: substrate, 12: following wrap, 13: sandwich layer, 14: upper clad layer
Embodiment
The inventor attentively studies in order to solve above-mentioned problem, found that by in containing the light solidifying/heat solidifying resin composition of maleimide derivatives, the compound (D) that contains free redical polymerization with ad hoc structure, even do not add the light solidified that Photoepolymerizationinitiater initiater also can improve said composition, promptly, even also can fully solidify with less active energy beam irradiation dose, so far finish the present invention.In addition, light solidifying/heat solidifying resin composition of the present invention contains the compound (D) of these maleimide derivatives (B) and free redical polymerization, and contain the compound (C) that has 2 above epoxy group(ing) and/or oxetanyl in carboxyl photoresist (A) and a part, therefore can develop with the diluted alkaline aqueous solution, its cured coating film also becomes excellent cured coating film such as adaptation, anti-electroless plating, electrical specification.
Below, describe with regard to each composition of light solidifying/heat solidifying resin composition of the present invention.
At first, just the carboxyl photoresist (A) that contains that uses among the present invention is illustrated.
As containing carboxyl photoresist (A), then just can use so long as have the resin of unsaturated group and carboxyl, be not limited to specific material, but be preferably resin as described below in them.
(1) at unsaturated carboxylic acid with have on the multipolymer of compound of unsaturated double-bond, the addition ethylenically unsaturated group is as side group, and what obtain thus contains the carboxyl photoresist.
(2) make compound with epoxy group(ing) and unsaturated double-bond and the multipolymer with compound of unsaturated double-bond, react with unsaturated carboxylic acid, the secondary hydroxyl that is generated is reacted with multi-anhydride, what obtain thus contains the carboxyl photoresist.
(3) make acid anhydrides with unsaturated double-bond and the multipolymer with compound of unsaturated double-bond, with the compound reaction with hydroxyl and unsaturated double-bond, what obtain thus contains the carboxyl photoresist.
(4) make the reaction of multi-group epoxy compound and unsaturated monocarboxylic acid, the secondary hydroxyl that generated and multi-anhydride are reacted, what obtain thus contains the carboxyl photoresist.
(5) reaction of hydroxyl polymer-containing and multi-anhydride obtains containing carboxy resin, make this resin again with the compound reaction with epoxy group(ing) and unsaturated double-bond, what obtain thus contains the carboxyl photoresist.
(6) make the reaction of polyfunctional group oxetane compound and unsaturated monocarboxylic acid, make then in the resulting modification oxetane resin primary hydroxyl again with multi-anhydride reaction, what obtain thus contains the carboxyl photoresist.
The above-mentioned carboxyl photoresist that contains can use separately or be used in combination more than 2 kinds.
Then, as the used maleimide derivatives of the present invention (B), have:
(B-1) simple function group aliphatics/alicyclic maleimide,
(B-2) simple function group aromatic series maleimide,
(B-3) polyfunctional group aliphatics/alicyclic maleimide,
(B-4) polyfunctional group aromatic series maleimide.
As simple function group aliphatics/alicyclic maleimide (B-1), can exemplify reactant of for example N-methyl maleimide, N-ethyl maleimide, Japanese kokai publication hei 11-302278 number disclosed maleimide carboxylic acid and tetrahydrofurfuryl alcohol etc.
As simple function group aromatic series maleimide (B-2), can exemplify for example N-phenylmaleimide, N-(2-aminomethyl phenyl) maleimide etc.
As polyfunctional group aliphatics/alicyclic maleimide (B-3), can exemplify for example N, N '-methylene-bis maleimide, N, N '-ethylenebis maleimide, three (hydroxyethyl) isocyanuric acid esters and aliphatics/alicyclic maleimide carboxylic acid dewaters esterification and obtains the maleimide ester cpds of isocyanuric acid ester skeleton, three (carbamate hexyl) isocyanuric acid esters and aliphatics/alicyclic maleimide alcohol carries out urethaneization and the isocyanuric acid ester skeleton poly maleimide class of maleimide urethane compound of the isocyanuric acid ester skeleton that obtains etc., the two urethanes of isophorone two (N-ethyl maleimide), triethylene glycol two (maleimide ethyl-carbonate), the esterification of dewatering of aliphatics/alicyclic maleimide carboxylic acid and various aliphatics/alicyclic polyol, or aliphatics/alicyclic maleimide carboxylicesters and various aliphatics/alicyclic polyol carry out transesterification reaction and aliphatics/alicyclic poly maleimide ester cpds class of obtaining, aliphatics/alicyclic maleimide carboxylic acid and various aliphatics/alicyclic polyepoxide carry out the ether ring-opening reaction and aliphatics/alicyclic poly maleimide ester cpds class of obtaining, pure aliphatics/alicyclic poly maleimide urethane compound the class of carrying out the urethane reaction with various aliphatics/alicyclic polyisocyanates and obtaining of aliphatics/alicyclic maleimide etc.
As polyfunctional group aromatic series maleimide (B-4), can exemplify for example N, N '-(4,4 '-ditan) bismaleimides, N, N '-(4,4 '-diphenyloxide) bismaleimides, N, N '-TOPOT 2,2 maleimide, N, N '-meta-phenylene bismaleimide, N, N '-2,4-toluene bismaleimides, N, N '-2,6-toluene bismaleimides, the esterification of dewatering of maleimide carboxylic acid and various aromatic polyol, or maleimide carboxylicesters and various aromatic polyol carry out transesterification reaction and the aromatic series poly maleimide ester cpds class that obtains, maleimide carboxylic acid and various aromatic series polyepoxide carry out the ether ring-opening reaction and the aromatic series poly maleimide ester cpds class that obtains, the pure aromatic series poly maleimide urethane compound class of carrying out the urethane reaction with various aromatic polyisocyanates and obtaining of maleimide etc.
For in above-mentioned maleimide derivatives (B), use is as simple function group aliphatics/alicyclic maleimide (B-1), the simple function group aromatic series maleimide (B-2) of simple function group maleimide, obtain cured article with low exposure, then must be used in combination the polyfunctional group as thinner described later (methyl) acrylate.In addition, in this manual, (methyl) acrylate is meant the meaning of acrylate and/or methacrylic ester, and other are similarly expressed too.
In addition, polyfunctional group aromatic series maleimide (B-4) is the polyfunctional group maleimide, but owing to have aromatic nucleus in the molecule, therefore the absorption that can produce active energy beam is difficult to use in the composition that needs ISO.
On the other hand, polyfunctional group aliphatics/alicyclic maleimide (B-3), because the solidified nature height, so the physical properties excellent of the postradiation cured coating film of active energy beam is preferred.Especially, to have carbonatoms and be 1～6 alkyl, the more preferably polytetramethylene glycol of the polypropylene glycol of the polyoxyethylene glycol of the maleimide alkyl carboxylic acid of straight chain shape alkyl or maleimide alkyl carboxylic acid ester and number-average molecular weight 100～1000 and/or number-average molecular weight 100～1000 and/or number-average molecular weight 100～1000 following general formula (1) and the represented aliphatics bismaleimide compound of general formula (2) that esterification or transesterification reaction obtain that dewater, because the solidified nature of resulting composition and the physical properties balance excellence of filming are therefore preferred especially.
The combined amount of this maleimide derivatives (B), containing carboxyl photoresist (A) with respect to above-mentioned 100 mass parts is 10～60 mass parts, is preferably the ratio of 30～50 mass parts.During combined amount less than 10 mass parts of maleimide derivatives (B), sufficient photoreactivity can't be obtained, pattern can not be formed.On the other hand, when surpassing 60 mass parts, the development deterioration of dry coating.
[changing 1]
Figure C20058002372500121
(in the formula, m is 1～6 integer, and n is 2～2 3 value, R 1Expression hydrogen atom or methyl.)
[changing 2]
Figure C20058002372500122
(in the formula, m represents 1～6 integer, and p represents 2～14 value)
In light solidifying/heat solidifying resin composition of the present invention, for obtaining sufficient cured coating film rerum natura, use the compound (C) that has 2 above epoxy group(ing) and/or oxetanyl in above-mentioned a part, that is, multi-group epoxy compound (C-1) and/or polyfunctional group oxetane compound (C-2).
As multi-group epoxy compound (C-1), particularly, can enumerate the Epikote828 that japan epoxy resin company makes, Epikote834, Epikote1001, Epikote1004, the Epiclon840 that big Japanese ink chemical industrial company makes, Epiclon850, Epiclon1050, Epiclon2055, Dongdu changes into the Epotote 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 Araldite6071 that Xiba Special Chemical Product Co.,Ltd makes, Araldite6084, AralditeGY250, Araldite GY260, the SumiepoxyESA-011 that Sumitomo Chemical Co. Ltd. makes, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade(brand)name) bisphenol A type epoxy resin; Epiclon152, Epiclon165 that the EpikoteYL903 that japan epoxy resin company makes, big Japanese ink chemical industrial company make, Dongdu changes into Epotote YDB-400, the YDB-500 that company makes, the D.E.R.542 that Dow Chemical makes, the Araldite8011 that Xiba Special Chemical Product Co.,Ltd makes, Sumiepoxy ESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. makes, (being trade(brand)name) brominated epoxy resins such as A.E.R.711, A.E.R.714 that industrial of Asahi Chemical Industry makes; The Epikote 152 that japan epoxy resin company makes, Epikote 154, the D.E.N.431 that Dow Chemical makes, D.E.N.438, the Epiclon N-730 that big Japanese ink chemical industrial company makes, Epiclon N-770, Epiclon N-865, Dongdu changes into the EpototeYDCN-701 that company makes, YDCN-704, the AralditeECN1235 that Xiba Special Chemical Product Co.,Ltd makes, Araldite ECN1273, Araldite ECN1299, AralditeXPY307, the EPPN-201 that Japan's chemical drug corporate system is made, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the Sumiepoxy ESCN-195X that Sumitomo Chemical Co. Ltd. makes, ESCN-220, the A.E.R.ECN-235 that industrial of Asahi Chemical Industry makes, ECN-299 etc. (being trade(brand)name) phenolic resin varnish type epoxy resin; The Epiclon830 that big Japanese ink chemical industrial company makes, the Epikote807 that japan epoxy resin company makes, Dongdu changes into EpototeYDF-170, YDF-175, the YDF-2004 that company makes, (being trade(brand)name) bisphenol f type epoxy resins such as Araldite XPY306 that Xiba Special Chemical Product Co.,Ltd makes; Dongdu changes into Epotote ST-2004, ST-2007, the ST-3000 bisphenol-A epoxy resins such as (trade(brand)names) that company makes; The Epikote604 that japan epoxy resin company makes, Dongdu changes into the Epotote YH-434 that company makes, the Araldite MY720 that Xiba Special Chemical Product Co.,Ltd makes, (being trade(brand)name) glycidyl amine type epoxy resins such as Sumiepoxy ELM-120 that Sumitomo Chemical Co. Ltd. makes; The Araldite CY-350 glycolylurea type Resins, epoxy such as (trade(brand)names) that Xiba Special Chemical Product Co.,Ltd makes; The Celoxide2021 that Daicel chemical industrial company makes, (being trade(brand)name) alicyclic epoxy resins such as Araldite CY175, CY179 that Xiba Special Chemical Product Co.,Ltd makes; The YL-933 that japan epoxy resin company makes, (being trade(brand)name) three hydroxyphenyl methane type Resins, epoxy such as T.E.N., the EPPN-501 that Dow Chemical makes, EPPN-502; YL-6056, YX-4000, YL-6121 di-cresylol type or united phenol-type epoxy resin or their mixtures such as (being trade(brand)name) that japan epoxy resin company makes; The EBPS-200 that Japan's chemical drug corporate system is made, the EPX-30 that Asahi Electro-Chemical Co. Ltd makes, the EXA-1514 bisphenol-s epoxy resins such as (trade(brand)names) that big Japanese ink chemical industrial company makes; The Epikote157S bisphenol-A phenolic varnish type Resins, epoxy such as (trade(brand)names) that japan epoxy resin company makes; The Epikote YL-931 that japan epoxy resin company makes, four hydroxyphenyl ethane type Resins, epoxy such as Araldite163 (being trade(brand)name) that Xiba Special Chemical Product Co.,Ltd makes; The Araldite PT810 that Xiba Special Chemical Product Co.,Ltd makes, (being trade(brand)name) hetero ring type Resins, epoxy such as TEPIC that daily output chemical industrial company makes; The o-phthalic acid diglycidyl ester resins such as Blemmer DGT that Nof Corp. makes; Dongdu changes into four glycidyl group dimethylbenzene acyl group ethane (the tetraglycidyl xylenoyl ethane) resins 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 Resins, epoxy of naphthyl; HP-7200, the HP-7200H etc. that big Japanese ink chemical industrial company makes have the Resins, epoxy of Dicyclopentadiene (DCPD) skeleton; The glycidyl methacrylate copolymerization based epoxy resins such as CP-50S, CP-50M that Nof Corp. makes; And then copolymerization Resins, epoxy of cyclohexyl maleimide and glycidyl methacrylate etc. is arranged, but be not limited to these materials.These Resins, epoxy can be used alone or in combination of two or more kinds.Preferred especially xenol type or di-toluene phenol-type epoxy resin or their mixture in these.
And then, as the typical example of polyfunctional group oxetane compound used in the present invention (C-2), can exemplify the compound shown in following general formula (3) or the following general formula (13).
[changing 3]
Figure C20058002372500151
(in the above-mentioned general formula (3), R 2For hydrogen atom or carbonatoms are 1～6 alkyl, P is that to be selected from carbonatoms be that 1～12 wire or a chain saturated hydrocarbons, carbonatoms are aromatic hydrocarbon based, the straight chain shape or the cyclic alkylene class that comprise carbonyl shown in formula (9) and (10) shown in 2～12 wire or a chain unsaturated hydrocarbons class, following formula (4), (5), (6), (7) and (8), comprise the base with divalent valence in carbonyl shown in formula (11) and (12) aromatic hydrocarbon based.)
[changing 4]
Figure C20058002372500152
(in the formula, R 3Expression hydrogen atom, carbonatoms are 1～12 alkyl, aryl or aralkyl, R 4Expression-O-,-S-,-CH 2-,-NH-,-SO 2-,-CH (CH 3)-,-C (CH 3) 2-or-C (CF 3) 2-, R 5Expression hydrogen atom or carbonatoms are 1～6 alkyl.
[changing 5]
Figure C20058002372500161
(in the formula, k represents 1～12 integer.)
[changing 6]
Figure C20058002372500162
[changing 7]
Figure C20058002372500163
(in the formula, R 6With above-mentioned R 2The carbonatoms that synonym, Q represent to comprise following formula (14), (15), (16) or (17) is aromatic hydrocarbon based shown in a chain alkylene base of 3～12, general formula (18), (19) and (20).In addition, l is the number of expression and residue Q bonded functional group, is the integer more than 3, is preferably 3～100 integer.)
[changing 8]
[changing 9]
(in the formula, R 7Expression hydrogen atom, carbonatoms are 1～6 alkyl or aryl.)
Except above-claimed cpd, also can use l with trimethylene oxide alcohol (oxetanealcohol) and the above-mentioned general formula (13) that obtains derived from (methyl) acrylic acid (methyl) acrylate carries out copolymerization is compound below 100.
Oxetane compound as described above (C-2) can be used alone or in combination of two or more kinds.
The compound (C) that has 2 above epoxy group(ing) and/or oxetanyl in a part as described above can improve the characteristic such as adaptation, thermotolerance of solder resist by thermofixation.With respect to the above-mentioned carboxyl photoresist (A) that contains of 100 mass parts, its combined amount is more than 10 mass parts, is fully below 100 mass parts, is preferably the ratio of 25～60 mass parts.Have in above-mentioned a part under the situation of combined amount less than 10 mass parts of compound (C) of 2 above epoxy group(ing) and/or oxetanyl, the cross-linking density of cured coating film reduces, and easily makes soldering thermotolerance or anti-electroless plating reduction.On the other hand, when surpassing 100 mass parts, can make the development deterioration of dry coating.In addition, for the thermofixation reaction of the compound (C) that promotes to have in above-mentioned a part 2 above epoxy group(ing) and/or oxetanyl, can add thermal curing catalyst described later.
As the thermal curing catalyst of the compound (C) that has 2 above epoxy group(ing) and/or oxetanyl in described a part, can exemplify for example 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; Dyhard RU 100, benzyldimethylamine, 4-(dimethylamino)-N, N-diformazan benzylamine, 4-methoxyl group-N, N-diformazan benzylamine, 4-methyl-N, amine compound such as N-diformazan benzylamine, hydrazine compounds such as adipic dihydrazide, sebacoyl hydrazine; Phosphorus compounds such as triphenylphosphine etc.In addition, as commercially available product, for example can exemplifying, four countries change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, the 2P4MHZ (being the trade(brand)name of glyoxaline compound) that industrial makes, U-CAT3503N, U-CAT3502T (being the trade(brand)name of the block isocyanate compound of dimethylamine) that SAN-APRO company makes, DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc.Be not particularly limited to these materials, so long as thermal curing catalyst or can promote epoxy group(ing) or the reaction of oxetanyl and carboxyl just passable, can use separately or mix more than 2 kinds and to use.In addition, also can use the guanamine, methyl guanamines, benzoguanamine, the trimeric cyanamide, 2 that also play the effect of adaptation imparting agent, 4-diamino-6-methylacryoyloxyethyl-s-triazine, 2-vinyl-4,6-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine isocyanuric acid affixture, 2,4-diamino-6-methylacryoyloxyethyl-s-triazine derivatives such as s-triazine isocyanuric acid affixture is preferably these compound and above-mentioned thermal curing catalysts that also plays the effect of adaptation imparting agent is used in combination.The combined amount of described thermal curing catalyst is just enough with the ratio of common amount, and for example described to contain carboxyl photoresist (A) be 0.1～20 mass parts with respect to 100 mass parts, is preferably the ratio of 0.5～15.0 mass parts.
Ring-type ether in the compound of free redical polymerization used in the present invention (D), can exemplify tetrahydrofuran (THF) ring, furan nucleus, amylene oxide ring, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane etc., wherein preferred tetrahydrofuran (THF) ring.
Therefore, the compound of free redical polymerization used in the present invention (D), be preferably the compound of free redical polymerization especially with tetrahydrofuran (THF) ring or morpholinyl (morpholino group), reason is unclear in detail, but uses its solidified nature of light solidifying/heat solidifying resin composition of these compounds very high.
In addition, the compound of the so-called free redical polymerization of the present invention is meant the compound of the group with free redical polymerization.At this; the group of free redical polymerization is meant the group that carries out radical chain reaction; particularly; (methyl) acryl, (methyl) acrylamido, (methyl) allyl group, vinyl, dimaleoyl imino, fumaric acid-based, methylene-succinic acid base, maleic etc. are arranged; especially (methyl) acryl solidified nature height is effective.In addition; in this specification sheets, (methyl) acryl, (methyl) acrylamido, (methyl) allyl group are meant the meaning of acryl and/or methacryloyl, acrylamido and/or methacryloyl amido, allyl group and/or methacrylic respectively.
So, by with containing carboxyl photoresist (A) and maleimide derivatives (B), use have the ring-type ether free redical polymerization compound or have the compound of the free redical polymerization of morpholinyl (morpholino group), thereby do not use Photoepolymerizationinitiater initiater or, just can obtain cured coating film with ultraviolet irradiation amount still less with excellent specific property with usage quantity than the Photoepolymerizationinitiater initiater that lacks at present.
Compound (D) as such free redical polymerization can exemplify out following commercially available product: the TC-110S (trade(brand)name) that makes as the Nippon Kayaku K. K of tetrahydrofurfuryl alcohol ε hexanolactam affixture acrylate, the Biscoat#150 (trade(brand)name) that makes as Osaka Organic Chemical Industry Co., Ltd. of tetrahydrofurfuryl acrylate etc.
Further, the compound of free redical polymerization (D) can be synthetic by the method (the 2nd method) that for example makes the method (the 1st method) that following (D-1)～(D-3) these three compositions react or following (D-1) and (D-4) compound are reacted.
(D-1) have the compound of ring-type ether or morpholinyl (morpholino group) and hydroxyl,
(D-2) organic multiple isocyanate,
(D-3) have the compound of the group of hydroxyl and free redical polymerization,
(D-4) has the compound of the group of isocyanate group and free redical polymerization.
At this, as the compound (D-1) with ring-type ether or morpholinyl (morpholino group) and hydroxyl, single 6-caprolactone affixture that can exemplify for example tetrahydrofurfuryl alcohol, tetrahydrofurfuryl alcohol etc. has the alcohols of tetrahydrofuran (THF) ring.
In addition, single 6-caprolactone affixture that can exemplify tetrahydropyrans-2-methyl alcohol, tetrahydropyrans-2-methyl alcohol etc. has the alcohols of amylene oxide ring.
Further, can exemplify 2, the condensation body, 2 of 2-dimethyl-3-oxygen propionic aldehyde (oxypropanal) and ethylene glycol, single 6-caprolactone affixture of the condensation body of 2-dimethyl-3-oxygen propionic aldehyde and ethylene glycol etc. has the alcohols of dioxolane.
In addition, further can exemplify morpholine ethanol, 3-morpholine-1, the oxy-compound that 2-propylene glycol etc. has alcohols of morpholinyl (morpholino group) etc., has the cyclic ether structure; Have the amine compound class of ring-type ethers such as tetrahydrofurfuryl amine etc., but be not limited to these.
As organic polyisocyanate compound (D-2), can exemplify for example aliphatic isocyanates classes such as trimethylene vulcabond, HDI; Between phenylene diisocyanate, to aromatic isocyanate classes such as phenylene diisocyanate; The trimer of 2,4 toluene diisocyanate, HDI trimer, modified polyisocyanate classes such as isophorone diisocyanate trimer; Polyvalent alcohols such as above-mentioned polyisocyanates and polyoxyethylene glycol, polytetramethylene glycol, TriMethylolPropane(TMP) carry out urethaneization and polyisocyanates of obtaining etc., but are not limited to these materials.
As the compound (D-3) of group, for example can exemplify (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate etc. with hydroxyl and free redical polymerization.
In addition, can exemplify mono-epoxy compounds and (methyl) acrylic acid reactant, for example (methyl) vinylformic acid 2-hydroxyl-3-octyloxy propyl ester, (methyl) vinylformic acid 2-hydroxyl-3-bay oxygen base propyl ester etc.
Further, the reactant of multi-group epoxy compound and (methyl) vinylformic acid or (methyl) acrylic acid dimer is (to 2 above epoxy group(ing) of multi-group epoxy compound, the compound that reacts (methyl) vinylformic acid or (methyl) acrylic acid dimer respectively and obtain, promptly, make 1 mole of multi-group epoxy compound and more than 2 moles (methyl) vinylformic acid or (methyl) acrylic acid dimer react and the compound that obtains), for example can exemplify, bisphenol A diglycidyl ether/(methyl) vinylformic acid=1/2 (mole) reactant, Bisphenol F diglycidylether/(methyl) vinylformic acid=1/2 (mole) reactant etc.Above-claimed cpd is (methyl) acrylic acid affixture, also can use (methyl) acrylic acid dimer is added to compound on the epoxy compounds.
In addition, have the compound (D-3) of the group of hydroxyl and free redical polymerization, also be not limited to the compound that exemplifies at this.
As the compound (D-4) of group, can exemplify 1: 1 addition reaction resultant etc. that for example methacrylic acid isocyanic ester, 2-methylacryoyloxyethyl isocyanic ester etc. and (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate etc. have (methyl) acrylate of hydroxyl with isocyanate group and free redical polymerization.
The composition that particularly contains the compound (D) of the free redical polymerization that use (methyl) acrylate compounds obtains, so the solidified nature height is preferred.
Compound (D-1) and organic multiple isocyanate (D-2) and reaction (the 1st method) with ring-type ether or morpholinyl (morpholino group) and hydroxyl with compound (D-3) of the group of hydroxyl and free redical polymerization, and above-claimed cpd (D-1) and reaction (the 2nd method) with compound (D-4) of the group of isocyanate group and free redical polymerization, be not particularly limited, can synthesize by known urethane reaction.
These reactions are under nitrogen atmosphere, and the temperature range in for example room temperature～90 ℃ is carried out, and preferably uses catalyzer.In above-mentioned the 1st method, isocyanate group 1 equivalent with respect to organic multiple isocyanate (D-2), have the compound (D-1) of ring-type ether or morpholinyl (morpholinogroup) and hydroxyl and have hydroxyl and the summation of the hydroxyl of the compound of the group of free redical polymerization (D-3) it is desirable to 0.9～1.2 equivalent, be preferably 1.0～1.1 equivalents.
In addition, in the 2nd method, isocyanate group 1 equivalent with respect to the compound (D-4) of group with isocyanate group and free redical polymerization, hydroxyl with compound (D-1) of ring-type ether or morpholinyl (morpholino group) and hydroxyl it is desirable to 0.9～1.2 equivalent, is preferably 1.0～1.1 equivalents.
As the employed catalyzer of the addition reaction of above-mentioned hydroxyl and isocyanic ester, can use for example organic titanic compounds such as tetrabutyl titanate, metatitanic acid orthocarbonate, tetraethyl titanate, organo-tin compounds such as stannous octoate, Dibutyltin oxide, dibutyl tin laurate, tin protoiodide etc.The addition of catalyzer with respect to whole inlet amounies preferably in the scope of 10～10000ppm.
In addition, reaction solvent can use the compound of the group with free redical polymerization of the active hydrogen of hydroxyl, amino, sulfydryl etc. not and/or not contain the organic solvent of the active hydrogen of hydroxyl, amino, sulfydryl etc.Organic solvent can exemplify that for example toluene, ethylbenzene, 1,2,3,4-tetralin, isopropyl benzene, dimethylbenzene etc. are aromatic hydrocarbon based; Ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone; Manthanoate, methyl acetate, ester classes such as ethyl acetate, n-butyl acetate, but be not limited to these.
In addition, in above-mentioned any reaction, the polymerization for the group that suppresses free redical polymerization it is desirable to use radical polymerization inhibitor.As radical polymerization inhibitor, can exemplify for example phenolic compounds such as quinhydrones, tertiary butylated hydroquinone, MEHQ hydroquinone monomethyl ether (methoquinone), 2,4 dimethyl 6 tert butyl phenol, catechol, tert-butyl catechol; Amines such as thiodiphenylamine, Ursol D, pentanoic; Methyl disulfide is for copper complexs such as amido Tubercuprose, diethyl-dithio amido Tubercuprose, dibutyl dithiocarbamate copper etc., and these stoppers can use separately, also can be used in combination more than 2 kinds.The addition of stopper is preferably the scope of 10～10000ppm with respect to whole inlet amounies.
Contain above-mentioned contain the compound (C) that has 2 above epoxy group(ing) and/or oxetanyl in carboxyl photoresist (A), maleimide derivatives (B), a part, and the compound (D) of free redical polymerization as in must the light solidifying/heat solidifying resin composition of the present invention of composition, not necessarily must add Photoepolymerizationinitiater initiater, but under need be with exposure solidified situation still less, in the scope of not damaging effect of the present invention, the mixed light polymerization starter is to improve light solidified as required.
As Photoepolymerizationinitiater initiater, can exemplify for example st-yrax and st-yrax alkyl ethers such as st-yrax, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether; Phenyl methyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, phenyl methyl ketone classes such as 1-Er Lvyixianben; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino amido-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, N, anthraquinone classes such as amido phenyl methyl ketone classes such as N-dimethylamino phenyl methyl ketone, 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthene ketones such as 4-di-isopropyl thioxanthone; Ketal classes such as phenyl methyl ketone dimethyl ketal, benzyl idol acyl dimethyl ketal; Organo-peroxide such as benzoyl peroxide, dicumyl peroxide; 2,4,5-triarylimidazoles dipolymer; Riboflavin Tetrabutyrate; Mercaptan compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-three-s-triazine; Organic halogen compounds such as tribromo-ethanol, trisbromomethyl phenyl sulfone; Benzophenone, 4,4 '-benzophenone or xanthene ketones such as two diethyl amido benzophenone; 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; Oximes such as 2-(acetoxyl group iminomethyl) thioxanthene-9-one etc.These known Photoepolymerizationinitiater initiaters commonly used can use separately or use as the mixture more than 2 kinds, and then can add the light trigger auxiliary agent, as N, N-dimethyl ethyl aminobenzoate, N, tertiary amines such as N-dimethylaminobenzoic acid isopentyl ester, amyl group-4-dimethylaminobenzoic acid ester, triethylamine, trolamine etc.In addition, in order to promote photoresponse, also can be added on visible region has CGI-784 cyclopentadiene titanium compounds such as (Xiba Special Chemical Product Co.,Ltd's manufacturings) of absorption etc.Particularly preferred Photoepolymerizationinitiater initiater is 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino amido-1-acetone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-(acetoxyl group iminomethyl) thioxanthene-9-one etc.; but be not particularly limited in these; so long as in UV-light or visible region absorb light; make unsaturated group generation radical polymerizations such as (methyl) acryl; just be not limited to Photoepolymerizationinitiater initiater, light trigger auxiliary agent, can use separately or a plurality of being used in combination.And then, state in the use under the situation of oximes Photoepolymerizationinitiater initiaters such as 2-(acetoxyl group iminomethyl) thioxanthene-9-one, because the light sensitivity height, so applicable laser direct imaging technology.
With respect to the described carboxyl photoresist (A) that contains of 100 mass parts, the combined amount of described Photoepolymerizationinitiater initiater (being their total amount when using the light trigger auxiliary agent) is preferably below 3 mass parts, more preferably the following ratio of 2 mass parts.Because the amount of blended Photoepolymerizationinitiater initiater than above-mentioned scope for a long time, the quantitative change of volatile component is many, can damage effect of the present invention.
In light solidifying/heat solidifying resin composition of the present invention, can mix the thinner that constitutes by photopolymerizable monomer and/or organic solvent as required.The application target of thinner is: under the situation of photopolymerizable monomer, dilution photosensitivity composition becomes the state that is easy to be coated with, and strengthens optical polymerism; On the other hand, under the situation of organic solvent, by dissolving and dilution photosensitivity composition, making aqueously becomes the state that is easy to be coated with, and makes film by drying, makes contact exposure become possibility.Therefore, can make photomask and the way of contact or any Exposure mode of noncontact mode of filming and being close to according to used thinner.
Further, as maleimide derivatives (B), under the situation of using simple function group aliphatics/alicyclic maleimide (B-1) or simple function group aromatic series maleimide (B-2), as mentioned above, have any problem because improve light sensitivity, therefore use photopolymerizable monomer as thinner.
As the representative substances of photopolymerizable monomer, but vinylformic acid hydroxyalkyl acrylate classes such as exemplified by acrylic 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate; The list or the diacrylate class of glycol such as ethylene glycol, methoxyl group TEG, polyoxyethylene glycol, propylene glycol; N,N-DMAA, N hydroxymethyl acrylamide, N, acrylic amides such as N-dimethylamino propyl acrylamide; Vinylformic acid N, N-dimethylaminoethyl, vinylformic acid N, vinylformic acid amido alkyl esters such as N-dimethylamino propyl ester; The multicomponent methacrylate class of polyvalent alcohols such as hexylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or these ethylene oxide adduct or propylene oxide adduct etc.; The esters of acrylic acid of phenoxy group acrylate, bisphenol a diacrylate, the ethylene oxide adduct that reaches these phenol or propylene oxide adduct etc.; The esters of acrylic acid of glycidyl ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; And trimeric cyanamide acrylate and/or corresponding to each methyl acrylic ester of aforesaid propylene acid esters etc.
As above-mentioned organic solvent, can exemplify ketones such as methylethylketone, pimelinketone; Toluene, dimethylbenzene, tetramethyl-benzene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methylcyclohexane, ethylene glycol butyl ether, Trivalin SF, methyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; Ester classes such as the acid esterification thing of ethyl acetate, butylacetate 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, petroleum naphtha, hydrogenated naphtha, solvent naphtha etc.
Such thinner can use separately or use as the mixture more than 2 kinds, under the situation of using photopolymerizable monomer, it is desirable to contain carboxyl photoresist (A) with respect to 100 mass parts, the appropriate scope of usage quantity is 10～60 mass parts, be preferably the ratio of 15～50 mass parts, under the situation of usage quantity more than this scope, so the touch dry variation of dry coating is not preferred.On the other hand, the usage quantity of organic solvent is not limited to specific ratio, but described to contain the scope of carboxyl photoresist (A) about 30～300 mass parts be suitable with respect to 100 mass parts, can suitably set according to selected coating process.
In addition, in light solidifying/heat solidifying resin composition of the present invention, according to purposes, for the specific inductivity that reduces its cured article and tangent of the dielectric loss angle and do not cause that their coating or all characteristics such as thermotolerance reduce, and can mix spherical porous matter weighting agent.As the material of spherical porous matter weighting agent, can exemplify out silicon-dioxide or cross-linked resin thing.
When in light solidifying/heat solidifying resin composition, mixing common weighting agent, be subjected to the specific inductivity of cured article, the domination of tangent of the dielectric loss angle, but when mixing spherical porous matter weighting agent, comprise air in its hole, therefore can reduce its dielectric characteristics.In order to comprise air like this, the median size that it is desirable to spherical porous matter weighting agent is 1～15 μ m, more preferably in the scope of 1～10 μ m, in addition, the oil number of spherical porous matter weighting agent it is desirable to about 100～500ml/100g, is preferably 150～300ml/100g.
The blending ratio of spherical porous matter weighting agent like this it is desirable to be more than 5 mass parts, below 100 mass parts, be preferably below 50 mass parts with respect to the above-mentioned carboxyl photoresist (A) that contains of 100 mass parts.
In light solidifying/heat solidifying resin composition of the present invention, in the scope of not damaging effect of the present invention, hybrid ring oxidation polyhutadiene, spherical urethane pearl as required.
Epoxidized polybutadiene is blended in order to give flexible and obdurability.As this epoxidized polybutadiene, EpoleadPB3600, the PB4700 etc. of for example Daicel chemical industrial company manufacturing are arranged, it is 5～50 mass parts that its combined amount it is desirable to respect to the above-mentioned carboxyl photoresist (A) that contains of 100 mass parts.
Spherical urethane pearl is to mix the material that median size is 1～15 μ m in order to give flexible and low warpage.It is 5～100 mass parts that the combined amount of this spherical urethane pearl it is desirable to respect to the above-mentioned carboxyl photoresist (A) that contains of 100 mass parts.
In light solidifying/heat solidifying resin composition of the present invention, also can be as required, mix separately or make up known inorganic fillers commonly used such as mixing barium sulfate, barium titanate, silica powder, micro mist shape silicon oxide, soft silica, crystalline silica, fused silica, spherical silicon dioxide, talcum, clay, magnesiumcarbonate, lime carbonate, aluminum oxide, aluminium hydroxide, mica more than 2 kinds.These inorganic fillers are for the cure shrinkage that suppresses to film, and improve characteristics such as adaptation, hardness and use.With respect to the above-mentioned carboxyl photoresist (A) that contains of 100 mass parts, the combined amount of inorganic filler is 10～300 mass parts, is preferably 30～200 mass parts.
Light solidifying/heat solidifying resin composition of the present invention, also can mix known additive kind commonly used as required, as phthalocyanine blue, phthalocyanine green, iodine is green, dual-azo yellow, Viola crystallina, titanium oxide, carbon black, known tinting materials commonly used such as naphthalene is black, quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, known hot stopper commonly used such as thiodiphenylamine, fine particle silica, organobentonite, known thickening material commonly used such as montmorillonite, silicone, the fluorine class, the defoamer and/or the flow agent of high score subclass etc., imidazoles, thiazoles, the silane coupling agent of triazole species etc. etc.
Light solidifying/heat solidifying resin composition of the present invention, by with above-mentioned each mixing element, preferably with described mixed, with roller mill etc. mix equably, dissolving, dispersion etc., can obtain thus.This resin combination is generally aqueous, also can make dry film.
When making dry film, can obtain by following operation: for example use roller coating machine or scraper, line bar mode, dip-coating mode, spin coating mode, intaglio printing mode and scraper mode etc., after being applied to described light solidifying/heat solidifying resin composition of the present invention on the basement membrane (mould release film), dry in being set at about 60～100 ℃ drying oven, and stick mould release film etc. as required.At this moment, the thickness of epilamellar dry coating is adjusted into 5～160 μ m, is preferably 10～60 μ m.As above-mentioned basement membrane, can suit to use the film of polyethylene terephthalate, polypropylene etc.
Has the light solidifying/heat solidifying resin composition of as above forming of the present invention, dilute as required, be adjusted into the viscosity that is suitable for coating process, by suitable method such as silk screen print method, curtain formula curtain coating, spraying method, rolling method, spin-coating method, it is applied on the printed circuit board (PCB) that is formed with circuit, under for example about 60～100 ℃ temperature, make organic solvent volatile dry contained in the composition, film thereby can form.Thereafter, see through and form figuratum photomask, utilize active energy beam to carry out the selectivity exposure, unexposed portion is developed with the diluted alkaline aqueous solution and formation photoresist pattern, and then, by solidifying at irradiation active energy beam post-heating or, or, can form the curing overlay film (solder resist overlay film) of adaptation, anti-electroless plating, electrical specification excellence by only finally solidifying (formal curing) to be heating and curing by the back irradiation active energy beam that is heating and curing.
As above-mentioned alkaline aqueous solution, can use the alkaline aqueous solution of potassium hydroxide, sodium hydroxide, yellow soda ash, salt of wormwood, sodium phosphate, water glass, ammonia, amine etc.
In addition, as the radiation source that is used for photocuring, suitable is Cooper-Hewitt lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, xenon lamp or metal halide lamp etc.In addition, laser beam etc. also can be used as active energy beam.
In addition, use light solidifying/heat solidifying resin composition of the present invention to form under the situation of interlaminar insulating resin layer of multilayer printed circuit board, be adjusted into the viscosity that is fit to coating process as required, by above-mentioned present known method, for example as shown in Figure 1, it is coated on the conductor layer 2 of the circuit card 1 that is pre-formed circuit, dry and form set to touch filming under for example about 60～100 ℃ temperature as required, utilize active energy beam optionally to expose by the negative film that is formed with the lightproof part of deceiving circle isotactic setting shape then, unexposed portion is developed by for example alkaline aqueous solution as described above, form the via hole 4 of the black circle that is equivalent to negative film.Thereafter, the punching of interlayer conduction hole 5 grades of stipulating as required, utilizing alligatoring agent such as oxygenant, alkaline aqueous solution, organic solvent to carry out surface coarsening then handles, on insulating resin layer 3 surfaces of surface coarsening, cover conductor layers by electroless plating, plating etc., carry out heat treated then, improve the cross-linking density of above-mentioned insulating resin layer 3, and carry out stress and relax.By being heated to for example about 140～180 ℃ temperature it is solidified, can form the interlaminar insulating resin layer 3 of all excellents such as adaptation, anti-electroless plating, electrical specification., according to ordinary method, the conductor layer on insulating resin layer 3 surfaces carried out etching and form the circuit pattern of regulation, form the conductor layer 6 that has formed circuit thereafter.In addition, also can repeat these operations as requested successively, make the conductor layer of insulating resin layer and specified circuit pattern replace lamination (build up) formation.
In addition, light solidifying/heat solidifying resin composition of the present invention, not only as utilizing the insulating resin layer of the multi-layer circuit board fabrication process of lamination method (build up method) as mentioned above, also can in the manufacturing of the multilayer printed circuit board that for example utilizes attached resin copper foil layer platen press, be used to form insulating resin layer or the insualtion resin composition used as used prepreg in the lamination pressing etc.
On the other hand, light solidifying/heat solidifying resin composition of the present invention can be used in the formation of the sandwich layer of optical waveguides or covering.
Just use an example of the method for manufacturing optical waveguide of light solidifying/heat solidifying resin composition of the present invention, describe with reference to accompanying drawing.
Fig. 2 is the sectional view of a routine optical waveguides portion.For example the light solidifying/heat solidifying resin composition that covering is used is adjusted into the viscosity that is suitable for coating process as required, utilize present known method to be coated on the substrates 11 such as silicon chip, dry under for example about 60～100 ℃ temperature as required, make the organic solvent volatilization, expose from top irradiation active energy beam then, then in about 140～180 ℃ heated air circulation type drying oven, be heating and curing, form the following wrap 12 that optical waveguides is used thus.Thereon, the light solidifying/heat solidifying resin composition that the sandwich layer of coating refractive index ratio aforesaid combination object height is used, dry under about 60～100 ℃ temperature, make the organic solvent volatilization, the side carries out the selectivity exposure through negative film irradiation active energy beam from it then, then unexposed portion is developed, in about 140～180 ℃ heated air circulation type drying oven, carry out thermofixation then, form sandwich layer 13 thus with alkaline aqueous solution.Thereafter, the light solidifying/heat solidifying resin composition that the described covering of coating is used on sandwich layer 13, dry under about 60～100 ℃ temperature, make the organic solvent volatilization, quadrature is penetrated active energy beam and is exposed from it then, then in about 140～180 ℃ heated air circulation type drying oven, carry out thermofixation, form upper clad layer 14 thus.Operation can be made the multi-model optical waveguides like this.
The specific refractory power of above-mentioned sandwich layer 13 and covering 12,14, sandwich layer is used and the specific refractory power of the light solidifying/heat solidifying resin composition that covering is used is adjusted by adjusting.The specific refractory power of light solidifying/heat solidifying resin composition also can be utilized to change reaction system and by the method for adjusting in conjunction with the segmental polarization or change the structure of compound and adjusted by the specific refractory power of molecule.In as light solidifying/heat solidifying resin composition of the present invention, containing the system of carboxyl photoresist (A) as necessary composition, compare with the means of the amount of adjusting reactive group, it is more easy utilizing main framing that changes resin or the means that blending ratio is adjusted to adjust specific refractory power, the validity height.
In order to improve the specific refractory power of organic compound, increasing molar refraction or reducing molecular volume is effectively, particularly, import phenyl ring equiconjugate structure, sulphur ,-COO-,-COOH, SO 2, the halogen atom beyond the CS, defluorination is effectively, and considers that from the carrying capacity of environment aspect importing of bromine or chlorine is unfavorable.On the other hand, in order to reduce the specific refractory power of organic compound, reducing molar refraction or increasing molecular volume is effectively, particularly, import carbonatoms and be 3～6 cycloaliphatic ring ,-OH ,-O-,-C=C-, NH 2, fluorine is effectively, but the polymkeric substance that contains fluorine has problems in waste treatment, and the cost of materials cost is risen, so the importing of fluorine is less-than-ideal.
But in overmoded waveguide, the difference of the specific refractory power between the width of core wide more or sandwich layer and covering is big more, and then modulus is many more, and the propagation of light improves more.Usually the difference of specific refractory power by ( n1-n 0)/n 1* 100 (%) (wherein, n 1The specific refractory power of expression sandwich layer, n 0The specific refractory power of expression covering.) try to achieve, in overmoded waveguide, this refringence is preferably more than 0.5%, more preferably more than 1.0%.
In addition, the size of sandwich layer changes according to the difference of the specific refractory power of sandwich layer and covering and desired modulus, but uses near the communication wavelengths the 0.85 μ m optical waveguides to be used under the situation of multimode, and the sandwich layer size it is desirable in the scope of about 20～80 μ m.In addition, when having big particle in the sandwich layer,, therefore not preferred owing to can produce the scattering of light loss, preferably do not contain the above particle of 1 μ m of having an appointment usually.
About having formed the printed circuit board (PCB) of optical waveguides, be recorded in for example Japanese kokai publication hei 6-258537 number or international open WO2004/095093A1, quote and comprise these inspiration content in this manual.
Embodiment
Below provide embodiment and comparative example is specifically described the present invention, but the present invention is not limited to following embodiment certainly.In addition, following " part " and " % " are quality criteria not having under the special statement.
Contain the synthetic of carboxyl photoresist (A-1):
With 330 parts of cresols phenolic resin varnish type epoxy resin (Epiclon N-695, big Japanese ink chemical industrial company makes, epoxy equivalent (weight) 220) pack into possess gas introduction tube, in the flask of whipping appts, cooling tube and thermometer, add 400 parts of Trivalin SF acetic ester, heating for dissolving is added 0.46 part of quinhydrones and 1.38 parts of triphenylphosphines.With this mixture heating up to 95～105 ℃, slowly drip 108 parts of vinylformic acid, reacted 16 hours.This resultant of reaction is cooled to 80～90 ℃, adds 163 parts of Tetra Hydro Phthalic Anhydrides, reacted 8 hours.Reaction is acid number, the total acid value that utilizes potential difference titration determination reaction solution, follows the trail of the markup percentage of gained, with reactivity more than 95% as terminal point.So the resulting nonvolatile component that contains the carboxyl photoresist of operation is 60%, and the acid number of solid matter is 100mgKOH/g.Below, this reaction soln is called varnish A-1.
Contain the synthetic of carboxyl photoresist (A-2):
With 322 parts of phenol novolak type epoxy resin (EPPN-201, Japan's chemical drug corporate system is made, epoxy equivalent (weight) 190), pack into possess gas introduction tube, in the flask of whipping appts, cooling tube and thermometer, add 400 parts of Trivalin SF acetic ester, heating for dissolving is added 0.46 part of quinhydrones and 1.38 parts of triphenylphosphines.With this mixture heating up to 95～105 ℃, slowly drip 122 parts of vinylformic acid, reacted 16 hours.This resultant of reaction is cooled to 80～90 ℃, adds 156 parts of Tetra Hydro Phthalic Anhydrides, reacted 8 hours.Reaction is acid number, the total acid value that utilizes potential difference titration determination reaction solution, follows the trail of the markup percentage of gained, with reactivity more than 95% as terminal point.So the resulting nonvolatile component that contains the carboxyl photoresist of operation is 60%, and the acid number of solid matter is 96mgKOH/g.Below, this reaction soln is called varnish A-2.
Contain the synthetic of carboxyl photoresist (A-3):
(japan epoxy resin (strain) is made with 350 parts of bisphenol A type epoxy resins, Epikote1004, epoxy equivalent (weight): 917) and after 925 parts of epoxy chloropropane are dissolved in 463 parts of dimethyl sulfoxide (DMSO), under agitation, in 70 ℃ of sodium hydroxide that in 100 minutes, add 61 part 99%.Again 70 ℃ of reactions 3 hours, reaction finishes back 250 parts of water of interpolation and washes after the interpolation.After separating oil content, under reduced pressure, reclaim more than half dimethyl sulfoxide (DMSO) and superfluous unreacted epoxy chloropropane from the oil reservoir fractionation, the resultant of reaction that will comprise residual by-product salt and dimethyl sulfoxide (DMSO) is dissolved in 750 parts of methyl iso-butyl ketone (MIBK), the NaOH that adds 10 part 30% again was in 70 ℃ of reactions 2 hours.After reaction is finished, with 200 parts of water washing 2 times and carry out oil content and separate, reclaim methyl iso-butyl ketone (MIBK) from the oil reservoir fractionation then, the acquisition epoxy equivalent (weight) is 318 Resins, epoxy.The Resins, epoxy of gained, if calculate by epoxy equivalent (weight), in 5.3 alcoholic extract hydroxyl groups in the initial substance bisphenol A type epoxy resin 4.8 by epoxidation.Pack in flask 318 parts of these Resins, epoxy and 351 parts of Trivalin SF acetic ester, heated and stirred to 90 ℃ makes it dissolving.Add 0.4 part of toluhydroquinone, 72 parts of vinylformic acid and 4 parts of triphenylphosphines in this solution, reacted 36 hours down at 90～95 ℃, obtaining acid number is the resultant of reaction of 2.2mgKOH/g.After this reaction soln is cooled to room temperature, add 137 parts of Tetra Hydro Phthalic Anhydrides, be heated to 85 ℃ and react.So the resulting nonvolatile component that contains the carboxyl photoresist of operation is 60%, and the solids component acid number is 96mgKOH/g.Below this reaction soln is called varnish A-3.
Embodiment 1～4 and comparative example 1～3
With mixing element shown in the table 1 of the above-mentioned synthetic gained varnish A-1 of use, A-2, A-3, mixing with the three-roller type roller mill, obtain light solidifying/heat solidifying resin composition.The characteristic value of each composition is as shown in table 2.
Table 1
Figure C20058002372500331
Table 2
Figure C20058002372500332
In addition, the method for the performance test in the above-mentioned table 2 is as follows.
(1) light sensitivity
On glass epoxy substrate, be coated with the composition of the various embodiments described above and comparative example with silk screen printing comprehensively, drying is 20 minutes under 80 ℃, after placement is cooled to room temperature, the stage phototimer No.2 (21 sections) that uses the Kodak manufacturing is as photomask, the exposure apparatus (metal halide lamp 7KW2 lamp) of making manufacturing with Oak under reduced pressure, with ultraviolet accumulative total quantorecorder 500,700 or the 900mJ/cm of 365nm 2Expose, press under the condition of 0.2MPa 1%Na in spray with 30 ℃ 2CO 3The aqueous solution developed for 60 seconds, the gloss hop count of Visual Confirmation cured coating film.In addition, the big more expression light sensitivity of numerical value is high more.
(2) electric insulating quality
On the comb-type electrode of L/S=50 μ m, the roller coating machine that uses Pilot Seiko (strain) to make is coated with the composition of the various embodiments described above and comparative example comprehensively, then in the heated air circulation type drying oven in 80 ℃ of dryings 30 minutes.After it was cooled to room temperature, embodiment 1～4 was 700mJ/cm in exposure 2Condition under expose, comparative example 1～3 is 900,900 in exposure respectively, 500mJ/cm 2Condition under expose, in the heated air circulation type drying oven, solidified 60 minutes in 150 ℃, obtain assess sample.This comb-type electrode is added the bias voltage of DC5.5V, and in humidity 85%, temperature is placed after 150 hours for 130 ℃ and is measured insulating resistance value.
(3) anti-electroless gold plating
On printed circuit board (PCB), with the composition of silk screen print method coating the various embodiments described above and comparative example, then in the heated air circulation type drying oven in 80 ℃ of dryings 30 minutes.After it was cooled to room temperature, embodiment 1～4 was 700mJ/cm in exposure 2Condition under expose, comparative example 1～3 is 900,900 in exposure respectively, 500mJ/cm 2Condition under expose, in the heated air circulation type drying oven, solidified 60 minutes in 150 ℃, obtain assess sample.(Japanese Mac Diarmid makes at 30 ℃ acid degreasing fluids, the 20vol% aqueous solution of METEX L-5B) in the assess sample dipping of gained was washed after 3 minutes, then at room temperature in the 14.4wt% ammonium persulfate aqueous solution, flooded 3 minutes, at room temperature in the 10vol% aqueous sulfuric acid, flooded 1 minute again after the washing.Then, (Meltex Inc company makes at 30 ℃ catalyst solutions, the 10vol% aqueous solution of metal plate activator 350) should estimate the substrate dipping in washed after 5 minutes, (Meltex Inc company makes at 85 ℃ nickel plating baths, the 20vol% aqueous solution of Melplate Ni-865M, pH=4.6) middle dipping is 30 minutes, implements nickel plating thus, at room temperature in the 10vol% aqueous sulfuric acid, flooded 1 minute then, wash.Then, (Meltex Inc company makes at 95 ℃ golden plating baths, the 15vol% of Aurorectroles UP and the potassium auric cyanide 3vol% aqueous solution, pH=6) in the assess sample substrate was flooded 30 minutes, after implementing electroless gold plating thus, wash, in 60 ℃ warm water, flooded 3 minutes again, use flowing water to wash.At resulting adhesion glassine paper adhesive tape on the gold-plated assess sample, the state of the cured coating film when confirming to peel off implemented.Determinating reference is as follows.
Zero: cured coating film is not unusual fully.
△: cured coating film produces some peeling off.
*: cured coating film is peeled off.
By the result of table 2 illustrated embodiment 1～4 as can be known, cured article by light solidifying/heat solidifying resin composition gained of the present invention, do not use Photoepolymerizationinitiater initiater just to show good light sensitivity, electric insulation resistance, anti-electroless gold plating also have excellent characteristic.
Relative therewith, comparative example 1,2 can't obtain sufficient light sensitivity, the electric insulation resistance of the cured article of gained, anti-electroless gold plating deterioration.In addition, use the comparative example 3 of Photoepolymerizationinitiater initiater, can be observed the reduction of the insulation resistance that causes by oozing out of Photoepolymerizationinitiater initiater.
Utilize the field on the industry
Light solidifying/heat solidifying resin composition of the present invention is as various being coated with such as coating Cover material material, printing-ink, surface conditioning agent, moulding material, adhesive, sticker, Adhesive, various anticorrosive additive material, colour filter manufacturing with material, fiber waveguide with material etc. Useful, especially at the solder resist of printed circuit board (PCB) or the layer of multilayer board Between be useful in the formation of insulating barrier, light waveguide-layer etc.

Claims (8)

1. light solidifying/heat solidifying resin composition that can develop by alkaline aqueous solution; it is characterized in that; what said composition contained that (A) have unsaturated group and a carboxyl contains the carboxyl photoresist; (B) be selected from (B-1) simple function group aliphatics/alicyclic maleimide; (B-2) simple function group aromatic series maleimide; (B-3) polyfunctional group aliphatics/alicyclic maleimide; (B-4) maleimide derivatives in the group formed of polyfunctional group aromatic series maleimide; (C) has the compound of 2 above epoxy group(ing) and/or oxetanyl in a part; reach the acryl or the methacryloyl based compound that (D) have ring-type ether or morpholinyl
The described carboxyl photoresist (A) that contains with respect to as solids component being 100 mass parts contains the compound (C), the described acryl of 5～50 mass parts or the methacryloyl based compound (D) that have 2 above epoxy group(ing) and/or oxetanyl in the described maleimide derivatives of 10～60 mass parts (B), the described a part of 10～100 mass parts.
2. light solidifying/heat solidifying resin composition according to claim 1, wherein said have the acryl of ring-type ether or morpholinyl or the ring-type ether of methacryloyl based compound (D) is the tetrahydrofuran (THF) ring.
3. light solidifying/heat solidifying resin composition according to claim 1, wherein said contain carboxyl photoresist (A) for be selected from the group that following (1)～(6) are formed more than a kind or 2 kinds:
(1) at unsaturated carboxylic acid with have on the multipolymer of compound of unsaturated double-bond, the addition ethylenically unsaturated group is as side group, and what obtain thus contains the carboxyl photoresist;
(2) make compound with epoxy group(ing) and unsaturated double-bond and the multipolymer with compound of unsaturated double-bond, react with unsaturated carboxylic acid, the secondary hydroxyl that is generated is reacted with multi-anhydride, what obtain thus contains the carboxyl photoresist;
(3) make acid anhydrides with unsaturated double-bond and the multipolymer with compound of unsaturated double-bond, with the compound reaction with hydroxyl and unsaturated double-bond, what obtain thus contains the carboxyl photoresist;
(4) make the reaction of multi-group epoxy compound and unsaturated monocarboxylic acid, the secondary hydroxyl that generated and multi-anhydride are reacted, what obtain thus contains the carboxyl photoresist;
(5) reaction of hydroxyl polymer-containing and multi-anhydride obtains containing carboxy resin, make this resin again with the compound reaction with epoxy group(ing) and unsaturated double-bond, what obtain thus contains the carboxyl photoresist;
(6) make the reaction of polyfunctional group oxetane compound and unsaturated monocarboxylic acid, make then in the resulting modification oxetane resin primary hydroxyl again with multi-anhydride reaction, what obtain thus contains the carboxyl photoresist.
4. light solidifying/heat solidifying resin composition according to claim 1, wherein said maleimide derivatives (B) are following general formula (1) or the represented aliphatics bismaleimide compound of general formula (2),
Figure C2005800237250003C1
In the formula, m is 1～6 integer, and n is 2～23 value, R 1Expression hydrogen atom or methyl,
Figure C2005800237250003C2
In the formula, m represents 1～6 integer, and p represents 2～14 value.
5. light solidifying/heat solidifying resin composition according to claim 1; ring-type ether in wherein said acryl or the methacryloyl based compound (D) is tetrahydrofuran (THF) ring, furan nucleus, amylene oxide ring, 1; 3-dioxolane, 1; 3-dioxane or 1, the 4-dioxane.
6. cured article, it is by active energy beam irradiation and/or heating, each described light solidifying/heat solidifying resin composition of described claim 1～5 is solidified and obtains.
7. printed circuit board (PCB), it forms interlayer insulating film by each described light solidifying/heat solidifying resin composition of claim 1～5 and/or solder mask layer forms.
8. printed circuit board (PCB), it forms light waveguide-layer by each described light solidifying/heat solidifying resin composition of claim 1～5 and forms.
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