CN105086605B - A kind of photocuring heat-curing composition ink, purposes and the wiring board containing it - Google Patents
A kind of photocuring heat-curing composition ink, purposes and the wiring board containing it Download PDFInfo
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Abstract
A kind of photocuring thermally curable resin composition ink, it includes：Photopolymerization resin 10 60% containing carboxyl and unsaturated double-bond in A molecules, B photopolymerization unsaturated double-bonds monomer 2 20%, C glycolylurea epoxide resins 0.5 20%, D epoxy resin 2 20%, E Epoxy curing accelerators 0.1 5%, F Photoepolymerizationinitiater initiaters 0.1 15%, G fillers 10 70%, H pigment 0 10%, I antifoaming agent 0.1 5%, also may include levelling agent, antioxidant, adhesion promoter, thixotropic agent, solvent.The insulation scolding tin that composition ink is applied to printed circuit is protected, and has the performances such as good scolding tin heat resistance, developability, adhesion, hardness, alkali resistance, acid resistance, solvent resistance.
Description
Technical field
The present invention relates to a kind of composition ink, its be used for the purposes of printed wiring board and comprising by the composition oil
The wiring board for the insulation heat-resisting protective soldermask coatings that ink is formed.
Background technology
It is in recent years, a large amount of in printed circuit board manufacture since electronic product is light, thin, thin and durable reliability requirement
Use photocuring heat-curing composition ink.Photocuring heat-curing composition ink can pass through silk-screen printing, roller coating, electrostatic
The modes such as painting, aerial spraying are coated on circuit board substrate, then in 70-80 DEG C of draughty condition drying, through contact or
Non-contacting selective ray irradiation.Then irradiated portion is cleaned up with dilute alkaline aqueous solution, the diluted alkaline water that can be used
The aqueous solution of solution commonly sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylphosphonihydroxide hydroxide base amine etc., irradiation portion code insurance stay in
On substrate.The composition for being retained in basic plate is heating and curing 30 minutes to 120 minutes at a temperature of 120 DEG C to 180 DEG C, last shape
At the insulation heat-resisting protective soldermask coatings on wiring board.For the heat resistance that composition coating film cured product thereof has obtained, need to be added
The multi-functional epoxy base epoxy for the heat cure that aqueous alkali cannot develop, the addition of this epoxy resin that cannot develop
Developability of the composition after prebake is caused to decline, metal pad can not develop totally.It is dried to obtain the development of composition ink
Dry wide operative weldability, China Patent No. 88108283.X, China Patent No. 93103607.0 disclose one kind and are slightly soluble in
In one molecule of the fine powder of composition containing there are two and more than two epoxy group epoxy resin, wherein TGIC (urinate by isocyanide
Sour three-glycidyl ester) it is representative resin, use the sl. sol. TGIC fine powders replacement part solubility in composition solvent
Multi-functional epoxy's base epoxy resin, to solve composition visualization problems.In recent years, due to the raising of environmental requirement,
TGIC is that compound is paid high attention in EU REACH Legislation, and the good epoxy resin of exploitation low toxic and environment-friendly composition process substitutes
TGIC epoxy resin becomes trend.Wherein Chinese Patent Application No.：201310723572.8 disclosing part (methyl) propionic ester
There are two containing in the molecule changed and although the epoxy resin of more than two epoxy groups, this composition meet European Union REACH
Laws and regulations requirement, but the aspect of the heat resistance improvement in need of developing process, solidify coating.
Invention content
The present inventor is by studying for a long period of time, repetition test, finds using one point with part aqueous glycolylurea structure
There are two containing in the epoxy resin and a molecule of epoxy group there are two containing in son and the epoxy resin of more than two epoxy groups mixes
Closing object can solve the above problems, and the ratio of glycolylurea epoxide resin and multi-functional epoxy base epoxy is 1:15 to 15:1,
Preferably 1:10 to 10:1, it so that composition is had the wide developing process that uses, and the solidfied material of composition ink
With excellent scolding tin heat resistance, the glycolylurea structural epoxy resins feature of environmental protection also complies with the REACH regulations of European Union, on solving
State problem.
Therefore, the present invention provides a kind of photocuring thermally curable resin composition ink, it includes
A. the photopolymerization resin containing carboxyl and unsaturated double-bond in molecule, 10-60%,
B. photopolymerization unsaturated monomer, 2-20%,
C. glycolylurea epoxide resin, 0.5-20%,
D. epoxy resin, 2-20%,
E. Epoxy curing accelerators, 0.1-5%,
F. Photoepolymerizationinitiater initiater, 0.1-15%,
G. filler, 10-70%,
H. pigment, 0-10%,
I. antifoaming agent, 0.1-5%,
And optional levelling agent, antioxidant, adhesion promoter, thixotropic agent, solvent；
Wherein, the glycolylurea epoxide resin refers to the epoxy resin containing glycolylurea structure in resin, glycolylurea epoxide resin and
The ratio of multi-functional epoxy base epoxy is 1:15 to 15:1, preferably 1:15 to 10:1,
Wherein, the total weight of the percentage composition of each composition component or ratio based on composition, each component content hundred
It is 100% to divide the sum of ratio.
On the other hand, the present invention provides use of the aforementioned photocuring thermally curable resin composition ink for printed wiring board
On the way.
In another aspect, the present invention also provides include the insulation heat-resisting protective soldermask coatings formed by the composition ink
Wiring board.
The composition is applied to the photosensitive solder resist ink of wiring board, with good scolding tin heat resistance, developability, attached
The performances such as the property, hardness, alkali resistance, acid resistance, solvent resistance.
Specific implementation mode
In the present invention, as without opposite explanation, then all operations are implemented in room temperature, normal pressure.
In the present invention, as without opposite explanation, then the percentage composition of each composition component or ratio are based on composition
Total weight, the sum of each component percentage composition are 100%.
The present invention provides a kind of photocuring thermally curable resin composition ink, it includes
A. the photopolymerization resin containing carboxyl and unsaturated double-bond in molecule, 10-60%,
B. photopolymerization unsaturated monomer, 2-20%,
C. glycolylurea epoxide resin, 0.5-20%,
D. epoxy resin, 2-20%,
E. Epoxy curing accelerators, 0.1-5%,
F. Photoepolymerizationinitiater initiater, 0.1-15%,
G. filler, 10-70%,
H. pigment, 0-10%,
I. antifoaming agent, 0.1-5%,
And optional levelling agent, antioxidant, adhesion promoter, thixotropic agent, solvent；
Wherein, the glycolylurea epoxide resin refers to the epoxy resin containing glycolylurea structure in resin, glycolylurea epoxide resin and
The ratio of multi-functional epoxy base epoxy is 1:15 to 15:1, preferably 1:15 to 10:1,
Wherein, the total weight of the percentage composition of each composition component or ratio based on composition, each component content hundred
It is 100% to divide the sum of ratio.
In the present invention, as without opposite explanation, then all operations are implemented in room temperature, normal pressure.
A kind of photocuring thermally curable resin composition ink includes the light containing carboxyl and unsaturated double-bond in molecule
Polymer resin A, the Resin A is the resin that can be obtained by following methods, and the content of the Resin A is 10-60%, preferably
15-60%：
1) in a molecule containing there are two and more than two epoxy group epoxy resin and single functionality unsaturated carboxylic acid it is anti-
The resin of hydroxyl should be obtained, then the resin obtained with anhydride reaction；
2) contain one in the compound containing epoxy group and single functionality unsaturated double-bond and a molecule in a molecule
The resin of the copolymer compound of a unsaturated double-bond, the resin are anti-with the monocarboxylic acid compound containing unsaturated double-bond in molecule again
It should obtain resin, the resin that the hydroxyl of gained resin is obtained with anhydride reaction again；
3) containing there are one the copolymer resins and a molecule of the compound of unsaturated double-bond in maleic anhydride and a molecule
Hydroxy compounds containing unsaturated double-bond resin obtained by the reaction；
4) (methyl) acrylic acid and the part carboxyl of the copolymer resins of single functionality unsaturated double-bond compound and one point
In son simultaneously the compound resin obtained by the reaction containing unsaturated double-bond and epoxy group；
5) the part carboxyl of the resin that method is obtained above-mentioned 1), 2), 3), 4) further in molecule containing unsaturated double
The compound of key and epoxy group resin obtained by the reaction.
The above resin can be used alone, can also two or more be used in mixed way.
In one embodiment of the invention, Resin A is the resin obtained by following methods：Contain two in one molecule
The epoxy resin of a and more than two epoxy groups is obtained by the reaction the resin of hydroxyl with single functionality unsaturated carboxylic acid, then with acid anhydrides
Resin obtained by the reaction.The epoxy resin refers to the asphalt mixtures modified by epoxy resin containing two or more epoxide functional groups in a molecule
Fat is not particularly limited in addition to this.Common epoxy resin has bisphenol A epoxide resin, double F types epoxy resin, phenolic aldehyde type ring
Oxygen resin, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F types epoxy resin, cycloaliphatic epoxy resin, o-cresol type asphalt mixtures modified by epoxy resin
Fat, glycolylurea epoxide resin, bisphenol-s epoxy resin, bisphenol fluorene base epoxy etc..Common multi-functional epoxy's base epoxy quotient
Product have：Taiwan South Asia resin：NPEL-127、NPEL-127E、NPEL-127H、NPEL-128、NPEL-128E、NPEL-128G、
NPEL-128R、NPEL-128S、NPEL-134、NPEL-136、NPEL-134、NPEL-23、NPEF-164X、NPEF-170、
NPEF-175, NPEF-176, NPEF-185, NPEF-187, NPEF-198, NPPN-631, NPPN-638, NPPN-638S etc.；South
Logical stars synthetic material Co., Ltd 0161,0161L, 0161E, 0164,0164E, 0164EA, 0164D, 0164C, 0174,
0174E, 0176E, 0177,0177E, 0179,0230,0235,0235E, 0235L, 0235C, 0248,0830,830 etc.；Wuxi
The epoxy resin 840L of blue star resin processing plant production, 840,850S, 850A, 850D, 860L, 860, N-740, N-740S, N-740G；
DOW Chemical production epoxy resin D.E.R.383, SD.E.R.331, D.E.R.331J D.E.R.337, D.E.N.438,
The epoxy resin such as D.E.N.439, D.E.R.354；Phoenix brand phenol aldehyde type epoxy resin F-51, F-50 of Wuxi resin processing plant production,
F-44, F-48 etc.；SQCN-704M, SQCN-704ML, SQCN051 etc. of Shandong holy well company；The U.S. magnificent chemical industry of jiangsu wuxi is limited
Company glycolylurea epoxide resin MHR-018, MHR-154, MHR070；ARACAST CY350；The HY238 that love jail reaches, Switzerland CIBA's
XB2793 etc..The above resin can individually can also two or more be used in mixed way.The carboxyl containing unsaturated double-bond
Compound is methacrylic acid, acrylic acid, cinnamic acid etc., can be used alone can also two kinds be used in mixed way.Described
Acid anhydrides is not particularly limited, and common acid anhydrides is specifiable to be had：Succinic anhydride, maleic anhydride, itaconicacid acid anhydride, phthalic acid
Acid anhydride, tetrahydrochysene benzene phthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl enlightening Nike acid anhydrides, partially
Benzenetricarboxylic anhydride, pyromellitic acid anhydride etc., the above acid anhydrides can be used alone, can also two or more be used in mixed way.
Catalyst and heat polymerization inhibitors can be added in the above reaction.
Compound in one molecule simultaneously containing epoxy group and unsaturated double-bond is specifiable to be had：Glycidyl methacrylate
Glyceride, glycidyl acrylate, allyl glycidyl ether, 4- vinylbenzyl glycidyl ethers, 3,4- epoxy basic rings
Hexyl methacrylate, 3,4- epoxycyclohexylmethyl methacrylates etc..
Monocarboxylic acid compound containing unsaturated double-bond refers to acrylic acid, methacrylic acid, cinnamic acid etc., can individually be made
With can also be used in mixed way.
In another embodiment of the present invention, Resin A is the resin obtained by following methods：Contain in one molecule
Containing there are one the copolymer compounds of unsaturated double-bond in epoxy group and the compound of single functionality unsaturated double-bond and a molecule
Resin, which is obtained by the reaction resin with the monocarboxylic acid compound containing unsaturated double-bond in molecule again, gained resin again with
Saturation or unsaturated acid anhydride resin obtained by the reaction.Change containing epoxy group and a unsaturated double-bond in a common molecule
Close that object is specifiable has：Glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 4- ethylene
Base benzyl glycidyl ether etc., can be used alone can also be used in mixed way.Containing there are one insatiable hungers in a common molecule
With the compound of double bond is specifiable has：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate,
(methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (first
Base) acrylic acid isopropyl piece ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester,
(methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, styrene etc..The above compound, which can be used alone, also may be used
It is used in mixed way with two or more.The monocarboxylic acid compound containing unsaturated double-bond is mainly third in a common molecule
Olefin(e) acid, methacrylic acid, cinnamic acid or their mixture.Carboxylic acid anhydride is not particularly limited.
In yet another embodiment of the present invention, Resin A is the resin obtained by following methods：Maleic anhydride and one
Containing there are one the hydroxy compounds that the copolymer resins of the compound of unsaturated double-bond and a molecule contain unsaturated double-bond in molecule
Object resin obtained by the reaction.The compound of unsaturated double-bond is specifiable there are one containing in a common molecule has：(methyl)
Methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid are different
Butyl ester, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid isopropyl piece ester, (methyl) acrylic acid gold
Rigid alkyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) Hydroxyethyl Acrylate, (methyl) propylene
Sour hydroxy propyl ester, styrene etc..The above compound can be used alone can also two or more be used in mixed way.It is preferred that horse
Come acid anhydrides and styrene copolymerized resin, specifiable commodity have：The SMA-1000P of Cray Willie (Guangzhou) Co., Ltd,
SMA-2000, SMA-3000, SMA-4000 etc.；The monohydroxy compound containing unsaturated double-bond can be enumerated in one molecule
Have：Hydroxyethyl methacrylate, hydroxy propyl methacrylate, Hydroxyethyl Acrylate, hydroxypropyl acrylate, can be with
But be used alone also two or more be used in mixed way.
According to the otherness of different situations, Resin A) number-average molecular weight be 500 to 50000 between, preferably 800 arrive
Between 45000, the heat resistance of the too small composition of molecular weight is bad, and the developability of the too big composition of molecular weight is bad, therefore not
It is preferred that.
As photopolymerization resin containing carboxyl, between acid value is 30 to 180, preferably 35 to 140, acid value is too low to be caused
The poor visualization of composition, acid value too Gao Zehui keep composition resin alkali solubility too big, and composition resolution is caused to decline.But make
The addition component of composition ink, acid value can be less than 30, as long as not influencing the developability of composition ink.
The photopolymerization unsaturated monomer B of the composition ink, is not particularly limited, and is examined from the speed angle of reaction
Consider, (methyl) acrylic ester monomer containing more than two unsaturated double-bonds in a preferably molecule.Specifiable commodity list
Body has：Duo Ma companies of the U.S. production SR399 (DPHA), SR350 (TMPTMA), CD9051, SR9012, SR9020 (GPTA),
SR454 (E03TMPTA), SR444 pentaerythritol triacrylates, SR368 tri- (2- ethoxys) isocyanuric acid triacrylate,
SR351, SR348, SR209, SR205, SR9003, SR833S, SR602, SR601, SR508, SR306, SR238, SR406 etc.；
TMPTA, NPGDA, TPGDA EO3-TMPTA, PHEA EO15-TMPTA, the EOEOEA PO2- of Tianjin proud son of heaven Chemical Co., Ltd.
NPGDA, IBOA PDDA, SMA, DPGDA, HDDA, BDDA, TMPTMA, EO4BPDA, PO3-GTA PETA (high viscosity), PETA
(low-viscosity), PEG (200) DA, TEGDMA, TEGDA PO3-TMPTA, PEA PEA-2, DITMP4A etc.；East Asia Synesis Company
M-225 (PPGDA) polypropyleneglycol diacrylate, M-305 (PETA) pentaerythritol triacrylate, three hydroxyls of M-309 (TMPTA)
Propane tri, M-350 (TMPEOTA) ethoxylated trimethylolpropane triacrylate, M-313 (THEIC)
Three (2- ethoxys) isocyanuric acid diacrylates and three (2- ethoxys) isocyanuric acid triacrylates, M-400 (DPHA)
Double pentaerythritol methacrylate, M-402 (DPHA) double pentaerythritol methacrylate, M-404 (DPHA) dipentaerythritol six
Acrylate etc.；EM210, EM211, EM70, EM231, EM223, EM221 of Taiwan Changxing Industries, Inc,
EM2380、EM2251、EM235(PET3A)、EM265(DPHA)；HEMA, HPMA etc. of Mitsubishi Corporation of Japan.Photocuring is unsaturated
Monomer can also be that the compound containing unsaturated group and epoxy group, specifiable compound have simultaneously in molecule：Methyl
Glycidyl, glycidyl acrylate, allyl glycidyl ether, 4- vinylbenzyl glycidyl ethers.It is above-mentioned
Compound can be used alone, but also two or more is used in mixed way.The content of the photopolymerization unsaturated monomer B is 2-
20%, preferably 3-18%.
The composition ink includes glycolylurea epoxide resin C, and the glycolylurea epoxide resin refers to containing glycolylurea knot in resin
The epoxy resin of structure, which is characterized in that in terms of 100 grams of compositions, the combined amount of glycolylurea epoxide resin is 1 to 20 grams, preferably 1.5
Gram to 15 grams.Too low, composition development latitude declines, and too high developability is very good, and the resolution of composition declines, therefore unexcellent
Choosing.Specifiable glycolylurea epoxide resin has：Glycolylurea epoxide resin MHR-018, MHR- of jiangsu wuxi Mei Hua Chemical Co., Ltd.s
154、MHR070；ARACAST CY350；The HY238 that love jail reaches；The XB2793 etc. of Switzerland CIBA；Glycolylurea epoxide resin can be with
It is the epoxy resin using dicarboxylic acids to glycolylurea epoxide resin chain extension, specifiable dicarboxylic acids has：Oxalic acid, malonic acid, fourth
Diacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tridecandioic acid, the tetradecane two
Acid, hexadecandioic acid (hexadecane diacid), cyclohexyl dicarboxylic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, adamantane two
Formic acid, adamantane oxalic acid etc., can be used alone, can also two or more be used in mixed way.Glycolylurea epoxide resin
It can also be that PART EPOXY base and the monocarboxylic acid containing unsaturated double-bond in a molecule of glycolylurea epoxide resin are obtained by the reaction
Resin.The monocarboxylic acid containing unsaturated double-bond is mainly acrylic acid, methacrylic acid, cinnamic acid, the above chemical combination in one molecule
Object may be used alone, can also be used in combination.
The composition ink includes epoxy resin D, the epoxy resin be in molecule containing there are two and two with
The epoxy resin of upper epoxy group, the combined amount of epoxy resin, opposite 100 grams of composition meters, epoxy resin is 1 gram to 25 grams, excellent
2 grams to 20 grams are selected as, too low composition scolding tin heat resistance is bad, and too high developability can decline, and craftsmanship is bad, therefore unexcellent
Choosing.Common epoxy resin has bisphenol A epoxide resin, double F types epoxy resin, phenol aldehyde type epoxy resin, hydrogenated bisphenol A type epoxy
Resin, A Hydrogenated Bisphenol A F types epoxy resin, cycloaliphatic epoxy resin, o-cresol type epoxy resin, isocyanuric acid three-glycidyl ester
Powder, bisphenol fluorene base epoxy, adamantane epoxy resin etc..The specifiable commodity of epoxy resin have：Taiwan South Asia resin：
NPEL-127、NPEL-127E、NPEL-127H、NPEL-128、NPEL-128E、NPEL-128G、NPEL-128R、NPEL-
128S、NPEL-134、NPEL-136、NPEL-134、NPEL-231、NPEF-164X、NPEF-170、NPEF-175、NPEF-
176, NPEF-185, NPEF-187, NPEF-198, NPPN-631, NPPN-638, NPPN-638S etc.；Nantong stars synthetic material
Co., Ltd 0161,0161L, 0161E, 0164,0164E, 0164EA, 0164D, 0164C, 0174,0174E, 0176E,
0177,0177E, 0179,0230,0235,0235E, 0235L, 0235C, 0248,0830,830 etc.；Wuxi blue star resin processing plant gives birth to
The epoxy resin 840L of production, 840,850S, 850A, 850D, 860L, 860, N-740, N-740S, N-740G；DOW Chemical produces
Epoxy resin D.E.R.383, SD.E.R.331, D.E.R.331J D.E.R.337, D.E.N.438, D.E.N.439,
The epoxy resin such as D.E.R.354；Phoenix brand epoxy resin F-51, F-50, F-44, F-48 etc. of Wuxi resin processing plant production；Nanjing
The TGIC powder that U.S.A launches company；The TGIC powder of Guangzhou Shen companies；The above resin can individually can also two kinds or two kinds with
On be used in mixed way.The content of the epoxy resin D is 2-20%, preferably 3-18%.
The composition includes also epoxy resin curing accelerator and/or epoxy curing agent E, is not limited particularly
System.Common commodity are specifiable to be had：Imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole, 2- phenyl miaows
The imidazole derivatives of azoles, 4- phenylimidazoles, 1-cyanoethyl-2-phenylimidazole, 1- (2- cyanoethyls) -2-ethyl-4-methylimidazole etc.
Object；Dicyandiamide, benzyldimethylamine, 2,4,4- (dimethylamino)-N, N- dimethyl benzyl amine, 4- methoxyl groups-N, N- dimethylbenzyl
The hydrazine compounds such as amine compounds, adipic dihydrazide, the sebacic dihydrazides such as base amine, 4- methyl-N, N- dimethyl benzyl amine；Three
Phosphorus compounds such as Phenylphosphine etc..In addition, the substance as commodity, can enumerate the dimethyl amine of four countries' chemical conversion industry corporation
Block isocyanate compound 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ；The U- of SAN-APRO, Ltd.
CAT3503N, U-CAT3502T (trade name), two ring type amidine compounds and its salt DBU, DBN, U-CATSA102, U-
CAT5002 etc..But it is not specially limited in these, as long as the thermal curing catalyst of epoxy resin or epoxy group can be promoted
Reacted with carboxyl, can individually or two or more be used in mixed way.In addition, guanamine, methyl can be used
Guanamines, benzo guanamine, melamine, 2,4- diamino -6- methacryloxyethyls-s-triazine, 2- vinyl -
2,4- diamino-s-triazine, 2- vinyl -4,6- diamino-s-triazine 〃 isocyanuric acid adducts, 2,4- diamino -6- methyl
Striazine derivatives such as acryloyl-oxyethyl-s-triazine 〃 isocyanuric acid adducts etc..Based on 100 grams of composition, E's
Content is 0.1 to 5 grams, preferably 0.3 to 3 grams.
The composition also contains Photoepolymerizationinitiater initiater F, is not particularly limited, as long as can be produced from after light irradiation
Unsaturated bond radical reaction is caused by base.Based on 100 grams of composition, the combined amount of F is 0.1 to 15 grams, excellent
It is selected as 0.3 to 13 grams.Common Photoepolymerizationinitiater initiater can enumerate styrax, styrax methyl ether, styrax ethylether, rest in peace
The styrax and styrax alkyl ether of fragrant propyl ether etc.；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethyls
The acetophenones of oxygroup -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, 1,1- dichloroacetophenones etc.；2- first
Base -1- [4- (methyl sulphur) phenyl] -2- morpholino propyl- 1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-fourth
The aminoacetophenone class of ketone -1 etc.；The Anthraquinones of 2-methylanthraquinone, 2- ethyl hydrazine, 2- tertiary butyls anthraquinone, 1- chloroanthraquinones etc.；2,
The thioxanthene ketone class of 4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, 2-chlorothioxanthone, 2,4- diisopropylthioxanthones etc.；Benzene
The ketal class of acetophenone dimethyl base ketal, benzyl dimethyl ketal etc.；The benzophenone of benzophenone etc.；Or xanthone class；
(2,6- Dimethoxybenzoyls) -2,4,4- amyls phosphine oxide, bis- (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides,
The oxidation of 2,4,6- trimethyl benzoyl diphenyl base phosphine oxides, ethyl -2,4,6- trimethylbenzoyl phenyl phosphine oxides etc.
Phosphine；Various peroxides, titanocenes class initiator etc., these Photoepolymerizationinitiater initiaters are acceptable and N, N- dimethylamino are pacified
The fragrant acetoacetic ester of breath, N, N- dimethylamino benzoic acids isopentyl ester, amyl -4- dimethyl aminobenzoates, triethylamine, three second
Light sensitizer uses simultaneously as the tertiary amines of hydramine etc..These Photoepolymerizationinitiater initiaters can be used alone or combine 2 kinds
Or two or more is used in mixed way.The content of the Photoepolymerizationinitiater initiater F is 0.1-15%, preferably 0.5-12%.
As the filler of the composition, the average grain diameter D50 of filler G is controlled at 30 microns hereinafter, preferred filler is average
Particle D50 is less than 25 microns；Filler can be that inorganic filler can also be organic filler.As inorganic filler, can individually or
It combines 2 kinds or two or more is used in mixed way, common inorganic filler, such as barium sulfate, barium titanate, silicon oxide powder, fine-powdered quartz
Powder, amorphous silica, talcum powder, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, mica, kaolin etc..Make
It is available to have PI powder and polytetrafluorethylepowder powder for organic filler.It is to reduce the solidification of film using these fillers
It shrinks, improve the characteristics such as adhesion, hardness.Their combined amount is preferably 10~70 weights relative to the composition of 100 parts by weight
Measure part.When combined amount is less than above range, the decline etc. of adhesive force, heat resistance occurs, on the other hand, when combined amount is more than upper
When stating range, decline or sensitivity decline of coating strength etc. occurs, either way not preferably.
As the pigment H of composition, be not particularly limited, it is specifiable have dark green, blue or green blue, carbon black, ultramarine,
Lithopone, permanent violet, permanent yellow, titanium dioxide etc., common commodity are specifiable to be had：The titanium dioxide R-706 of DuPont Corporation,
R-900、R-902、R-931、R-960、R-102、R-103、R-104、R-105、R-350；Japanese stone original titanium dioxide R-930, CR-
60-2、R-200、R-600、R-980、CR-50、CR-50-2、CR-58、CR-58-2、CR-93、CR-80、CR-80、CR-95、
CR-97 etc.；BASF L6480 is blue, BASF L3980 is red, green Green L8730, indigo plant Blue K7014LW, indigo plant Blue
K7090, indigo plant Blue K6907, indigo plant Blue D7079, indigo plant Blue K6912, indigo plant Blue L7080, green Green D9360/6G, indigo plant
Blue L7085, indigo plant Blue L6960F/BSNF, indigo plant Blue K7072, indigo plant Blue L7087/PG, indigo plant Blue K6902, indigo plant
Blue L6700F, indigo plant Blue K6911D, indigo plant Blue L6875F, green Green K8740, indigo plant Blue L6900, green Green
K9360, indigo plant Blue L6901F, indigo plant Blue K7096/GBP, indigo plant Blue L6920, green Green L9361, indigo plant Blue L6930,
Blue Blue L7101F, indigo plant Blue L6989F, green Green L8690P.G7 etc..
As needed, the composition, which also optionally uses, discloses common dyestuff, heat polymerization inhibitors, attachment promotion
Agent, antifoaming agent, dispersant, coupling agent, fire retardant, organic solvent etc..
Common heat polymerization inhibitors have：Hydroquinone, p-hydroxyanisole, quinhydrones, 264 anti-aging agents etc., can be single
It solely uses, but also two or more is used in mixed way.
Adhesion promoter has phosphoric acid ester (methyl) acrylate, common commodity to have：Sha Duoma companies of the U.S.
CD9051, Japanese chemical drug company PM2 etc., but not limited to this.
Antifoaming agent：Antifoaming agent can be organic silicon, and can also be esters of acrylic acid or the mixing of two class antifoaming agent makes
With.It common are the KS-66 of Japan XINYUE；German TEGO Di Gao companies antifoaming agent：Foamex N、Foamex 815N、
Foamex 825、Foamex 840、Foamex 842；This antifoaming agent of the modest hamming of moral：DEUCHEM 3200、DEUCHEM 3500、
DEUCHEM 5300、DEUCHEM 5400、DEUCHEM 5600、DEUCHEM 6500、DEUCHEM 6800；DEUCHEM 6600
Deng；The esters of acrylic acid antifoaming agent of German BYK companies：BYK-051, BYK-052, BYK-053, BYK-057 etc..
Solvent：It is characterized in that, the content of solvent, in terms of 100 parts of composition, the content of organic solvent is less than 40%, preferably
The content of organic solvent is less than 35%.Solvent content is too high, not environmentally, therefore not preferably.Consider from the required angle of technique, it is excellent
Solvent boiling point is selected to be more than 150 DEG C of organic solvent.Common organic solvent is specifiable to be had：Ketone, aromatic hydrocarbon, glycol ether
Class, sweet ether acetate, esters, alcohols, aliphatic hydrocarbon, oil series solvent etc..Specifically, methyl ethyl ketone, cyclohexanone, different Buddhist
The ketones such as your ketone, diacetone alcohol；Toluene, dimethylbenzene, trimethylbenzene, durol etc. are aromatic hydrocarbon；Ethyl cellulose, methyl are fine
Tie up element, butyl cellulose, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether,
The glycol ethers such as dipropylene glycol diethyl ether, Triethylene glycol ethyl ether；Ethyl acetate, butyl acetate, dipropylene glycol methyl ether second
The esters such as acid esters, methyl proxitol acetate, propylene glycol ethyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters；Ethyl alcohol, third
The alcohols such as alcohol, butanol, isopropanol, ethylene glycol, propylene glycol；The aliphatic hydrocarbons such as octane, hexamethylene；Petroleum ether, naphtha, hydrogenation stone
The oil series solvent such as cerebrol, solvent naphtha；Ethyl acetate, butyl acetate, dimethyl adipate, dimethyl succinate, penta 2
The esters solvents such as dimethyl phthalate, glycol dinitrate ester, ethylene glycol diacetate, propylene glycol dimethyl ester, propylene glycol diacetate.Have above
But solvent can be used alone also two or more be used in mixed way.
The composition of the present invention is formed by mixing each single component.Preferably, it is formed in each single ingredient of mixing
It is rapid to use after composition.
In addition, the present invention also provides the purposes that the photocuring thermally curable resin composition ink is used for printed wiring board.
The composition of the present invention is applied to printed circuit board as insulation welding resistance protection.Process conditions are commonly：Silk screen
The modes such as printing, roller coating, electrostatic spraying, aerial spraying are coated on circuit board substrate, are dried in 70-80 DEG C of draughty condition
It is dry, it is irradiated through contact or non-contacting selective ray, causes the polymerisation of composition, form the water-insoluble polymer of alkali,
Then, irradiated portion is cleaned up with dilute alkaline aqueous solution, the dilute alkaline aqueous solution that can be used commonly sodium carbonate, hydroxide
Sodium, potassium hydroxide, tetramethylphosphonihydroxide hydroxide base amine etc..Light irradiation group polymer portion is retained on substrate.It is retained in the group of basic plate
It closes object to be heating and curing 30 minutes to 120 minutes at a temperature of 120 DEG C to 180 DEG C, eventually forms the heat-resisting guarantor of insulation on wiring board
Soldermask coatings are protected, which has excellent development, scolding tin heat resistance, adhesion, hardness, solvent resistance, acid resistance, alkali resistance
Etc. performances.
In addition, the present invention also provides the circuits for including the insulation heat-resisting protective soldermask coatings formed by the composition ink
Plate.
Below by way of specific example, the present invention is further described：
Synthetic example 1
203 grams of o-cresol formaldehyde epoxy resin (Shandong holy well 704M, epoxide equivalent 203) is added in three-necked flask, to benzene
0.5 gram of diphenol, 180 grams of diethylene glycol ether acetate, 70 grams of durene, stirring are heated to 100 DEG C to 110 DEG C heat preservation dissolvings 1
Hour.Ensure after being completely dissolved, cool to 90 DEG C, is added dropwise 72 grams of acrylic acid and 3 grams of N, the solution of N- dimethyl benzylamines, three hours
It inside drips off, controls 90-100 DEG C of degree of temperature in the process.Temperature is raised to 105 DEG C of degree after dripping to react 12 hours to 110 degree, is surveyed
Determine acid value and be less than 10, material temperature is made to cool to 90 DEG C, 85 grams of tetrahydrophthalic anhydride is added, 90-95 DEG C keeps the temperature 3 hours.Use infrared spectrometer
Detection, 1780cm-1Peak disappears, and stops reaction, temperature is reduced to room temperature, obtains dark brown resin solution, resin viscosity is
260dpa.s/25 DEG C, solid content 60%, solid part acid value is 87.Resin number is A1.
Synthetic example 2
Kunshan South Asia o-cresol formaldehyde epoxy resin NPCN-704 (epoxide equivalent 210, softening point are added in three-necked flask
70-80 DEG C) 210 grams, 180 grams of diethylene glycol ether acetate, 70 grams of durene, stirring is heated to 100 DEG C to 110 DEG C heat preservations
Dissolving 1 hour.Ensure after being completely dissolved, cool to 90 DEG C, 72 grams of acrylic acid, 0.3 gram of hydroquinone, triphenylphosphine 1.8 is added
Gram, it is heated to 100-120 DEG C, is reacted 15 hours, acid value is less than 5,86 grams of tetrahydrophthalic anhydride is added, control temperature is at 90 to 100 DEG C
Reaction three hours, is detected, 1780cm with infrared spectrometer-1Peak disappears, and stops reaction, obtains resin pale yellow solution, viscosity is
300dpa.s/25 DEG C, solid content 60%, the resin of solid part acid value 87, resin number is A2.
Synthetic example 3
Be added in three-necked flask o-cresol formaldehyde epoxy resin 203 grams of (Shandong holy well SQCN704ML, epoxide equivalent 203),
0.5 gram of hydroquinone, 200 grams of diethylene glycol ether acetate, 80 grams of durene, stirring are heated to 100 DEG C to 110 DEG C heat preservations
Dissolving 1 hour.Ensure after being completely dissolved, cool to 90 DEG C, is added dropwise 72 grams of acrylic acid and 3 grams of N, the solution of N- dimethyl benzylamines,
It is dripped off in three hours, controls 90-100 DEG C of temperature in the process, temperature is raised to 105 DEG C of degree after dripping reacts 12 small to 110 degree
When, it measures acid value and is less than 10, material temperature cools to 90 DEG C, and 120 grams of tetrahydrophthalic anhydride is added, and 90-95 DEG C keeps the temperature 3 hours.Use infrared light
Spectrometer detects, 1780cm-1Peak disappears, and 20 grams of methyl propenoic acid glycidyl is added, and reacts 4 hours, temperature is reduced to room temperature,
Dark brown resin solution is obtained, it is 300dpa.s/25 DEG C to obtain viscosity, solid content 60%, solid part acid value 87.7, resin number
For A3.
Synthetic example 4
214g cresol novolak type epoxy resin is added in the four-neck flask equipped with blender and reflux condenser
EPICLON N-695 (big Japanese ink chemical industrial company production, epoxide equivalent 214), add 150 gram of 2 carbitol acetic acid
Ester, 100 grams of No. 150 weight aromatic solvents simultaneously dissolve by heating.After determining that resin is completely dissolved, pairs of the 0.2g as polymerization inhibitor is added
The triphenylphosphine of benzenediol and 1.8g as catalysts.The mixture is heated to 95~105 DEG C, 72g third is slowly added dropwise
Olefin(e) acid reacts 16 hours.Obtained reaction product is cooled to 90~95 DEG C, 91.2g tetrabydrophthalic anhydrides reaction 4 is added
Hour, it is taken out after cooling.Obtain the solution containing carboxy resin in this way, non-volatile content 60%, solid part acid value be
87.5mgKOH/g.The solution of the reaction product is referred to as A4.
Compare synthesis example 1
By 203 grams of o-cresol formaldehyde epoxy resin (Shandong holy well 704M, epoxide equivalent 203), 0.5 gram of hydroquinone, diethyl
30 grams of glycol ether acetate, 30 grams of durene are added in three-necked flask, stirring, are heated to 100 DEG C to 110 DEG C heat preservation dissolvings
1 hour.Ensure after being completely dissolved, cool to 90 DEG C, 36 grams of acrylic acid and 3 grams of N is added dropwise, the solution of N- dimethyl benzylamines, three is small
When it is interior drip off, in the process control 90-100 DEG C of temperature, after dripping by temperature be raised to 105 DEG C to 110 DEG C react 10 hours, measure
Acid value is less than 1, and material temperature cools to 60 DEG C of degree, obtains dark brown resin solution, and resin viscosity is 360dpa.s/25 DEG C, solid content
80%, solid part epoxide equivalent is 476.Resin number is A5.
Embodiment 1
By the material mixture ratio listed in 1 embodiment 1 of table, in precise a variety of materials to container, with high speed dispersor, with
500 rpms of speed is dispersed with stirring 15 minutes, then grinds three times composition three-roll grinder, make composition
Fineness is less than 15 microns.The viscosity for measuring combination of the above object is 200dPa.s/25 DEG C.
The developability of composition, scolding tin heat resistance, adhesion, hardness, solvent resistance, acid resistance, alkali resistance are commented
Valence.
Developability：Using the technique of silk-screen printing, 1 composition ink of embodiment is coated on by the nylon mesh of 43T
It has made on the clean three pieces circuit board substrate of conducting wire, has been respectively labeled as B11/B12/B13, made the dry film of coating
Thickness is 25-30 microns, in constant temperature oven, at a temperature of 75 DEG C, B11 drying 60 minutes, B12 is made to dry 70 minutes, B13 drying
80 minutes, then, use conventional circuit board developing method (developer solution for 1% Na2CO3Aqueous solution, developer temperatur 30
DEG C, the spray pressure of developer solution is 1.5kg/cm2Pressure) development 1 minute, model is cleaned up with deionized water, hot wind
Drying.Development effect after visual detection composition prebake, the method for evaluation are as follows：
It is totally excellent for developing completely on 80 minutes copper faces；It is totally good that 70 minutes copper faces, which have white spray, 60 minutes copper faces,；
It is poor that 60 minutes copper faces, which have the development of white haze shape not clean,.The results are shown in Table 2.
Embodiment 2, embodiment 3, embodiment 4, comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5 are used
Its developability is evaluated with 1 same method of embodiment, is as a result recorded in table 2.
Scolding tin heat resistance：
The composition ink full version of embodiment 1 is printed on the clean line for having certain line pattern with 43T blank silk screen
On the plate of road, dried 50 minutes in 75 DEG C of constant temperature ovens, it is cool to room temperature, with the energy that 21 lattice gray scale rulers are 10 lattice, to model into
Row exposure, the developing process using circuit board plant routine develops, then, by model to be carried out in 150 DEG C of 1 hour baking ovens
After cure, obtain evaluation model substrate.
Gained is evaluated and coats water-soluble flux on substrate cured coating film, static 10 minutes, is then immersed in and sets in advance
It is set in 288 DEG C of solder bath 10 seconds, repeats the above action three times, scaling powder is cleaned by 50 DEG C or so of hot water injection
Afterwards, the expansion of cured coating film evaluated by 50 times of magnifying glass visual detections, remove, whiten.Determinating reference is as follows.
It is excellent：Dipping three times after, do not observe coating have whiten, expand, peeling.
Difference：After impregnating three times, coating has any the phenomenon that whitening or expanding or remove.
The adhesion, hardness of solidfied material, alkali resistance, acidproof is made using method identical with scolding tin Evaluation of Heat Tolerance model
The evaluation model of the performances such as property, solvent resistance.
Adhesion：It, will on coating with cross-cut tester by the scratch experiment standard of GBT9286-1998 paint and varnish paint films
1cm2Coating is divided equally into 100 lattice 1mm2Small lattice, cut should draw antireflective coating layer, with No. 600 pressure sensitive adhesive tape patches of 1/2 inch wide 3M boards
Adhesive tape is firmly shut down at the power of an angle of 90 degrees, observes whether be stained with coating shedding on adhesive tape by tight coating surface by adhesive tape and coating
Or whether coating has layering or cracking, does not fall off completely, is layered, cracks, judgement coating adhesion is excellent, is otherwise difference.Record
In table 2.
Hardness：With pencil hardness method, it is excellent to be more than 5H with the hardness of 1 kilogram of load measurement film.
Alkali resistance：Model is steeped 30 points in the solution under conditions of 23-25 DEG C of temperature by 10% sodium hydrate aqueous solution respectively
Clock, washing is clean, hot-air seasoning, with cross-cut tester by 1cm on coating2Coating is divided equally into 100 lattice 1mm2Small lattice, cut are answered
Antireflective coating layer is drawn, coating surface is adjacent to 1/2 inch wide No. 600 pressure sensitive adhesive tapes of 3M boards, it will at the power of an angle of 90 degrees by adhesive tape and coating
Adhesive tape is firmly shut down, and observes whether be stained with whether coating shedding or coating have layering or cracking on adhesive tape, is not fallen off, is divided completely
Layer, cracking, discoloration, judgement solidify coating acid resistance is excellent, is otherwise difference, is as a result reported in Table 2 below.
Acid resistance：10% aqueous sulfuric acid is steeped model 30 minutes in the solution respectively under conditions of 23-25 DEG C of temperature,
Washing is clean, hot-air seasoning, with cross-cut tester by 1cm on coating2Coating is divided equally into 100 lattice 1mm2Small lattice, cut should be drawn
Coating is adjacent to coating surface with 1/2 inch wide No. 600 pressure sensitive adhesive tapes of 3M boards, by adhesive tape and coating at the power of an angle of 90 degrees by glue
Band is firmly shut down, and observes whether be stained with whether coating shedding or coating have layering or cracking on adhesive tape, is not fallen off, is divided completely
Layer, cracking, discoloration, judgement solidify coating acid resistance is excellent, is otherwise difference, is as a result reported in Table 2 below.
Solvent resistance：Model is steeped in dichloromethane solvent 30 minutes respectively under conditions of 23-25 DEG C of temperature, takes out and uses
Deionized water wash clean, hot-air seasoning, with cross-cut tester by 1cm on coating2Coating is divided equally into 100 lattice 1mm2Small lattice, cut
Antireflective coating layer should be drawn, coating surface is adjacent to 1/2 inch wide No. 600 pressure sensitive adhesive tapes of 3M boards, by adhesive tape and coating at an angle of 90 degrees
Power firmly shuts down adhesive tape, observes whether be stained with whether coating shedding or coating have layering or cracking on adhesive tape, completely without de-
It falls, be layered, crack, change colour, judgement coating solvent resistance is excellent, is otherwise difference, is as a result reported in Table 2 below.
Using with identical evaluation method and standard in embodiment 1.Result is recorded in table 2.
By 1 same method of embodiment, prepare manufacture embodiment 2, embodiment 3, embodiment 4, comparative example 1, comparative example 2,
The compositions ink such as comparative example 3, comparative example 4, comparative example 5.
By 1 same method of embodiment, evaluation criterion to embodiment 2, embodiment 3, embodiment 4, comparative example 1, comparative example
2, comparative example 3, comparative example 4, the developability of composition ink of comparative example 5, scolding tin heat resistance, adhesion, hardness, solvent resistant
Property, acid resistance, alkali resistance are evaluated.As a result it is listed in table 2.
Table 1
Note 1：The dipentaerythritol hexaacrylate of East Asia Synesis Company
Note 2：Zhejiang Yang Fan photosensitizer 2- methyl-1s-(4- methyl mercaptos phenyl) -2- morpholinyl -1- acetone
Note 3：The long day photosensitizer isopropyl thioxanthone anthraquinone in Tianjin
Note 4：The A1 blanc fixes of Guangzhou Ji Mei companies
Note 5：The fumed silica of German Di Gaosha
Note 6：The antifoaming agent of Japanese SHIN-ETSU HANTOTAI's chemistry
Note 7：The ultra-fine melamine that Nanjing U.S.A launches company
Note 8：The acrylic polyester class levelling agent of German BYK companies
Note 9：Shandong holy well phenol aldehyde type epoxy resin
Note 10：The MHR070 glycolylurea epoxide resins of Wuxi Mei Hua chemical companies
Note 11：The ultra-fine isocyanuric acid three-glycidyl ester that Nanjing U.S.A launches company
Evaluation result table 2
As can be known from the results of Table 2, method using the present invention, can obtain good developability, scolding tin heat resistance, adhesion,
The good printing ink composition of alkali resistance, acid resistance, solvent resistance.There is and use the group of TGIC (isocyanuric acid three-glycidyl ester)
The identical developing process of object ink and scolding tin heat resistance, adhesion, alkali resistance, acid resistance solvent resistance are closed, without the use of
The composition ink developability of TGIC or glycolylurea epoxide resin is poor because comparative example 1 and comparative example 2 use containing epoxy group
Resin is all unable to liquid alkali developing.
Claims (15)
1. a kind of photocuring thermally curable resin composition ink, it includes
A. the photopolymerization resin containing carboxyl and unsaturated double-bond in molecule, 10-60%,
B. photopolymerization unsaturated monomer, 2-20%,
C. glycolylurea epoxide resin, 0.5-4%,
D. epoxy resin, 2-20%,
E. Epoxy curing accelerators, 0.1-5%,
F. Photoepolymerizationinitiater initiater, 0.1-15%,
G. filler, 10-70%,
H. pigment, 0-10%,
I. antifoaming agent, 0.1-5%,
And optional levelling agent, antioxidant, adhesion promoter, thixotropic agent, solvent；
It is characterized in that, wherein, the glycolylurea epoxide resin refers to the epoxy resin containing glycolylurea structure in resin, hydantoin epoxy
The ratio of resin and multi-functional epoxy base epoxy is 1:15 to 15:1,
Wherein, the total weight of the percentage composition of each composition component or ratio based on composition, each component percentage composition
The sum of be 100%.
2. the photocuring thermally curable resin composition ink of claim 1, it is characterised in that the glycolylurea epoxide resin and more officials
The ratio of energy degree epoxy base epoxy is 1:15 to 10:1.
3. the photocuring thermally curable resin composition ink of claim 1, it is characterised in that the glycolylurea epoxide resin and more officials
The ratio of energy degree epoxy base epoxy is 1:10 to 10:1.
4. the photocuring thermally curable resin composition ink of claim 1, including the tree containing carboxyl and unsaturated group in molecule
Fat A, it is characterised in that the Resin A is the resin that can be obtained by following methods：
1) there are two containing in a molecule and the epoxy resin of more than two epoxy groups is reacted with single functionality unsaturated carboxylic acid
To the resin of hydroxyl, then the resin that is obtained with anhydride reaction；
2) in a molecule compound containing epoxy group and single functionality unsaturated double-bond in molecule containing there are one not
It is saturated the resin of the copolymer compound of double bond, which reacts with the monocarboxylic acid compound containing unsaturated double-bond in molecule again
To resin, resin that the hydroxyl of gained resin is obtained with anhydride reaction again；
3) maleic anhydride contains with the copolymer resins containing the compound there are one unsaturated double-bond in a molecule with a molecule
The hydroxy compounds resin obtained by the reaction of unsaturated double-bond；
4) in the part carboxyl and a molecule of (methyl) acrylic acid and the copolymer resins of single functionality unsaturated double-bond compound
Compound resin obtained by the reaction containing unsaturated double-bond and epoxy group simultaneously；
5) the part carboxyl of the resin that method is obtained above-mentioned 1), 2), 3), 4) further in molecule contain unsaturated double-bond and
The compound resin obtained by the reaction of epoxy group.
5. the photocuring thermally curable resin composition ink of claim 4, it is characterised in that the number-average molecular weight of the Resin A is
Between 500 to 50000.
6. the photocuring thermally curable resin composition ink of claim 4, it is characterised in that the number-average molecular weight of the Resin A is
Between 800 to 45000.
7. the photocuring thermally curable resin composition ink of claim 4, it is characterised in that the content of the Resin A is 15-
60%.
8. the photocuring thermally curable resin composition ink of claim 1, it is characterised in that the content of the unsaturated monomer B is
3-18%.
9. the photocuring thermally curable resin composition ink of claim 1, it is characterised in that the epoxy resin D refers to one point
In son containing there are two and more than two epoxy group the epoxy resin in addition to glycolylurea epoxide resin.
10. the photocuring thermally curable resin composition ink of claim 1, it is characterised in that the content of the epoxy resin D is
3-18%.
11. the photocuring thermally curable resin composition ink of claim 1, it is characterised in that the epoxy resin curing accelerator
The content of E is 0.3-4%.
12. the photocuring thermally curable resin composition ink of claim 1, it is characterised in that the content of the Photoepolymerizationinitiater initiater
For 0.5-12%.
13. the photocuring thermally curable resin composition ink of any one of claim 1-12 is used for the use of printed wiring board
On the way.
14. wiring board, the resin combination ink solidification object containing any one of claim 1-12.
15. glycolylurea epoxide resin is mixed for improving photocuring thermally curable resin composition with multi-functional epoxy base epoxy
The purposes of the developability of ink.
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| CN109988283B (en) * | 2017-12-29 | 2021-10-08 | 上海飞凯材料科技股份有限公司 | Epoxy acrylic resin and preparation method and application thereof |
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| CN1267688A (en) * | 1999-03-17 | 2000-09-27 | 互应化学工业株式会社 | Ultraviolet curing resin composition therewith and photoprotection welding ink |
| CN102164977A (en) * | 2008-10-27 | 2011-08-24 | 昭和电工株式会社 | Photosensitive resin composition and method for producing photosensitive resin used therein |
| CN103310878A (en) * | 2013-03-18 | 2013-09-18 | 滁州品创生物科技有限公司 | Carbon fiber composite material cable core |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267688A (en) * | 1999-03-17 | 2000-09-27 | 互应化学工业株式会社 | Ultraviolet curing resin composition therewith and photoprotection welding ink |
| CN102164977A (en) * | 2008-10-27 | 2011-08-24 | 昭和电工株式会社 | Photosensitive resin composition and method for producing photosensitive resin used therein |
| CN103310878A (en) * | 2013-03-18 | 2013-09-18 | 滁州品创生物科技有限公司 | Carbon fiber composite material cable core |
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