CN102944977B - Photosensitive solder resist composite, application thereof and printed circuit board (PCB) containing same - Google Patents
Photosensitive solder resist composite, application thereof and printed circuit board (PCB) containing same Download PDFInfo
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- CN102944977B CN102944977B CN201210499734.XA CN201210499734A CN102944977B CN 102944977 B CN102944977 B CN 102944977B CN 201210499734 A CN201210499734 A CN 201210499734A CN 102944977 B CN102944977 B CN 102944977B
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Abstract
The invention relates to a photosensitive solder resist composite. The photosensitive solder resist composite comprises (A) 100 parts by weight of alkali-soluble photosensitive resin with a triazine ring structure in molecule and the following components in parts by weight based on the 100 parts by weight of alkali-soluble photosensitive resin: (B) 5 to 70 parts of epoxy resin free of aromatic rings in molecule, (C) 1 to 30 parts of photoinitiator containing at least one type of acylphosphine oxide photoinitiators, (D) 30 to 200 parts of titanium dioxide, and (E) 3 to 100 parts of organic solvent and/or 50 parts or less of photopolymerizable monomer as diluent. The photosensitive solder resist composite provided by the invention has excellent thermal resistance, hardness and photoaging resistance. In addition, the invention also relates to the application of the photosensitive solder resist composite in a PCB, and the PCB containing the solder resist composite.
Description
Technical field
The present invention relates to a kind of photosensitive solder resist composition, its purposes for printed circuit board (PCB), and comprise described photosensitive solder resist composition as the printed-wiring board (PWB) of the permanent soldering-resistance layer of one deck.
Technical background
Photosensitive solder resist composition is to cover the outer field protection group compound of printed wiring board; one of its effect is welding resistance; prevent that unnecessary scolding tin is attached on printed wiring board; even if the wiring board plate face that printed wiring board covers is not adhered to by tin in spray tin, Reflow Soldering and wave-soldering technique thereafter; thereby effectively prevent the short circuit between circuit, realize the increasingly automated of production run.
In addition, print circuit board surface at application LED light source is used the soldering-resistance layer of being prepared by photosensitive solder resist composition, can utilize efficiently LED light source, effectively reduces energy consumption, this requires soldering-resistance layer to have high reflectance, and can in long-term use procedure, keep its high reflectance.In addition, also require this soldering-resistance layer can meet the stable on heating requirement of printed circuit board in element equipment process.
In order to solve the problem of above soldering-resistance layer requirement high reflectance, in Chinese patent application 200710151485.4 and 200710108405.7, proposed (methyl) acrylic acid and (methyl) acrylate of not containing phenyl ring to carry out copolymerization, obtain a kind of resin; With the compound that contains thiazolinyl and epoxy radicals in molecule simultaneously, the carboxyl of this resin is carried out to partial esterification again, obtain in molecule not only containing carboxyl but also containing the resin of thiazolinyl; Then take this resin as main body is equipped with epoxy resin and other compositions, form white light heat of solidification hardening composition.It has solved the problem of the desired high reflectance of soldering-resistance layer of being prepared by said composition preferably, and the soldering-resistance layer problem that reflectivity declines in long-term use procedure.But there is the bad problem of thermotolerance in it.
Summary of the invention
The invention provides a kind of photosensitive solder resist composition, it comprises
(A) in 100 weight portion molecules, there is the alkali solubility photosensitive resin of triazine ring structure;
And the following component based on alkali solubility photosensitive resin meter described in 100 weight portions:
(B) in 5-70 weight portion molecule, do not contain the epoxy resin of aromatic rings;
(C) light trigger that 1-30 weight portion contains at least one acylphosphine oxide type light trigger;
(D) 30-200 parts by weight of titanium dioxide; And
(E) 3-100 weight portion organic solvent and/or the photopolymerization monomer that is up to 50 weight portions are as thinning agent.
In a preferred embodiment, above-mentioned photosensitive solder resist composition comprises
(A) in 100 weight portion molecules, there is the alkali solubility photosensitive resin of triazine ring structure;
And the following component based on alkali solubility photosensitive resin meter described in 100 weight portions:
(B) in 10-30 weight portion molecule, do not contain the epoxy resin of phenyl ring;
(C) light trigger that 3-20 weight portion contains at least one acylphosphine oxide type light trigger;
(D) 50-100 parts by weight of titanium dioxide; And
(E) 5-30 weight portion organic solvent and/or the photopolymerization monomer that is up to 30 weight portions are as thinning agent.
On the other hand, the present invention also provides the purposes of described photosensitive solder resist composition for the preparation of printed wiring board.
On the one hand, the present invention also provides a kind of printed wiring board again, and it contains described photosensitive solder resist composition as soldering-resistance layer.
Photosensitive solder resist composition of the present invention has good thermotolerance after photocuring, has in addition good hardness and light fastness aging.
Embodiment
The invention provides a kind of photosensitive solder resist composition, it comprises
(A) in 100 weight portion molecules, there is the alkali solubility photosensitive resin of triazine ring structure;
And the following component based on alkali solubility photosensitive resin meter described in 100 weight portions:
(B) in 5-70 weight portion molecule, do not contain the epoxy resin of aromatic rings;
(C) light trigger that 1-30 weight portion contains at least one acylphosphine oxide type light trigger;
(D) 30-200 parts by weight of titanium dioxide; And
(E) 3-100 weight portion organic solvent and/or the photopolymerization monomer that is up to 50 weight portions are as thinning agent.
In a preferred embodiment, above-mentioned photosensitive solder resist composition comprises
(A) in 100 weight portion molecules, there is the alkali solubility photosensitive resin of triazine ring structure;
And the following component based on alkali solubility photosensitive resin meter described in 100 weight portions:
(B) in 10-30 weight portion molecule, do not contain the epoxy resin of phenyl ring;
(C) light trigger that 3-20 weight portion contains at least one acylphosphine oxide type light trigger;
(D) 50-100 parts by weight of titanium dioxide; And
(E) 5-30 weight portion organic solvent and/or the photopolymerization monomer that is up to 30 weight portions are as thinning agent.
Alkali solubility photosensitive resin of the present invention (A) is the reactant of triglycidyl isocyanurate (also claiming TGIC), unsaturated monocarboxylic and multi-anhydride, is preferably the reactant of TGIC, acrylic acid and tetrabydrophthalic anhydride.
In one embodiment of the invention, described alkali solubility photosensitive resin (A) obtains by being prepared as follows: by first the TGIC of following formula being dissolved with (a) solvent, optionally heat, then add (b) polymerization inhibitor and (c) catalyzer, and add (d) unsaturated monocarboxylic to carry out esterification under the temperature of 90-110 ℃ and normal pressure, reaction time is different and different according to catalyzer, is generally 10-16 hour; The carboxylate obtaining (its hydroxyl) is partially or completely reacted under normal pressure with (e) multi-anhydride, the reaction time is according to the difference of reactant and difference is generally 4-6 hour again:
The TGIC selecting in said method is the mixture (both ratios have no particular limits) of α type TGIC and β type TGIC.Its epoxide equivalent should be less than 115, is preferably less than 110.When the epoxide equivalent of TGIC is greater than 115, the thermotolerance of gained photosensitive solder resist composition is bad.
The example of (a) solvent using in said method comprises: ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol single-butyl ether acetic acid esters, DPGME acetic acid esters, dihydroxypropane single-ethyl ether acetic acid esters, dipropylene glycol single-butyl ether acetic acid esters, toluene, dimethylbenzene, durene etc.These solvents can be used alone or two or more mixing is used.Preferably, the solvent of use is ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, toluene, dimethylbenzene, durene, or its potpourri.More preferably use ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetic acid esters, toluene, dimethylbenzene, or its potpourri.
The example of (b) polymerization inhibitor using in said method comprises: p-dihydroxy-benzene, 1,4-benzoquinone, methylnaphthohydroquinone, MEHQ, 2-TBHQ, 2,5-di-tert-butyl hydroquinone etc.These polymerization inhibitors can be used alone or two or more mixing is used.Its consumption, based on total resin weight meter, is 5/10000ths to 5/1000ths, preferably ten thousand/and to per mille.
The example of (c) catalyzer using in said method comprises: tertiary amine compounds, and as triethylamine, N, N-dimethyl benzylamine, DMA, pyridine and substitutive derivative, glyoxaline compound etc.; Non-proton quaternary ammonium salt, as tetramethyl bromine (chlorine) is changed amine, trimethyl benzyl bromine (chlorine) is changed amine etc.; Triphenylphosphine, the slaine of triphenylarsine, carboxylic acid, Organotransitionmetal complex etc.Its consumption, based on total resin weight meter, is 5/10000ths to 5 percent, preferably per mille to percent two.
The example of (d) unsaturated monocarboxylic using in said method comprises: acrylic acid, acrylic acid dipolymer, methacrylic acid, β-styrene acrylic, β-furfuryl group acrylic acid, butenoic acid, alpha-cyano cinnamic acid, cinnamic acid, and reactant half lipid of the reactant of (methyl) acrylics that contains a carboxyl in full and/or unsaturated dicarboxylic acid anhydride and molecule or full and/or unsaturated dibasic acid and unsaturated single diglycidyl compound.Consider photo-curable, in these unsaturated monocarboxylics, preferably use acrylic acid and/or methacrylic acid.The epoxy molar equivalent meter of its consumption based on TGIC, is 90%-110%, preferably 98%-102%.
The example of (e) multi-anhydride using in said method comprises: the dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, the adjacent dicarboxylic acid anhydride of six hydrogen, the adjacent benzoic anhydride of methyl six hydrogen, Jia Qiao-Nei-tetrabydrophthalic anhydride, methyl first bridge-Nei-tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride; The aromatic polycarboxylic acid acid anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetrabasic carboxylic acid dicarboxylic anhydride; And 5-(2,5-dioxy tetrahydrofuran base)-3-methyl-3-cyclic ethylene-1,2-dicarboxylic anhydride, and similarly polybasic acid anhydride derivant, these are full and/or undersaturated multi-anhydride can be independent or two or more mixing use.Preferably, the consumption of described (e) multi-anhydride is 50-150mg KOH/g for making the acid number of resultant of reaction (alkali solubility photosensitive resin (A)), when the not enough 50mg KOH/g of acid number, alkali dissolubility is not good enough, the development difficulty of filming in diluted alkaline water of the composition obtaining, and when acid number surpasses 150mg KOH/g, the performances such as anti-developability, alkali resistance and the electrical characteristics of the cured coating film being obtained by described composition reduce, and sometimes even can not make soldering-resistance layer.Described acid number can pass through conventional determination of acid-basetitration.
Meanwhile, consider the weatherability of cured coating film, preferably use the multi-anhydride that does not contain aromatic rings, as tetrabydrophthalic anhydride, hexahydrophthalic anhydride and succinic anhydride etc.
Described alkali solubility photosensitive resin (A) is owing to having a plurality of free carboxyls on polymer lateral chain, the composition that contains this alkali solubility photosensitive resin (A) in a molecule, contains three unsaturated double-bonds, so can carry out development and the photocuring of dilute alkaline aqueous solution simultaneously; In addition, owing to thering is highly stable triazine ring structure in molecule, by said composition being exposed, developed and being heating and curing to filming, can obtain the soldering-resistance layer of the characteristic goods such as preliminary drying drying property, developability, thermotolerance, solvent resistance, adhesion, hardness, light fastness aging, resistance to acids and bases; Owing to not containing aromatic rings in this alkali solubility photosensitive resin molecular structure, therefore there is the characteristic that good ultraviolet resistance is aging simultaneously.
In photosensitive solder resist composition of the present invention, described (B) epoxy resin is not contain the epoxy resin of aromatic rings, such as bisphenol-A epoxy resin, aliphatic epoxy resin, triglycidyl isocyanurate (TGIC) etc., these epoxy resin can be used alone and also can mix use.
Preferably described (B) epoxy resin is not contain the epoxy resin compound of phenyl ring, the more preferably multipolymer of glycidyl methacrylate and simple function (methyl) acrylate.Simple function (methyl) acrylate containing phenyl ring does not have no particular limits.Conventional has: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) isobornyl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate etc.
Described (B) epoxy resin can be used separately, also can containing the epoxy resin of phenyl ring, not mix use with other.Owing to not containing the easy xanthochromia groups such as phenyl ring in composition, the light aging resisting property of the cured coating film of photosensitive solder resist composition of the present invention is outstanding.
In photosensitive solder resist composition of the present invention, in alkali solubility photosensitive resin (A) described in 100 weight portions, the consumption of described epoxy compound (B) is 5-70 weight portion, preferably 10-30 weight portion, more preferably 15-25 weight portion.When consumption surpasses 70 weight portion, alkaline-based developer will decline to the being partly dissolved property without exposure reaction, easily produces the unclean phenomenon of developing, thereby can not apply in practice.On the other hand, when with quantity not sufficient 5 weight portion, a part of carboxyl due in alkali solubility photosensitive resin (A), can not fully be reacted, and easily causes the deficiencies such as the thermotolerance of the soldering-resistance layer after solidifying, resistance to electrical resistance, chemical solvent resistance.
In one embodiment, composition of the present invention is mixture preparation form, comprises by photoresist (A) as the host of major component and epoxy compound (B) as hardening agent.All the other components are optionally present in host or hardening agent.Preferably, light trigger is present in host.During use, host is mixed with hardening agent.
The light trigger (C) that the present invention uses contains at least one acylphosphine oxide type light trigger; for example 2; 4; 6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide, 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide (commodity are called Irgacure TPO), two (2; 4; 6-trimethylbenzoyl) phenyl phosphine oxide, 2; 4; the acylphosphine oxide type light triggers such as 6-trimethylbenzene formyl diethyl phosphonate, two (2,6-dimethylbenzoyls)-(4 ˊ, 4 ˊ-dimethyl octyl group-2) phenyl phosphine oxide.For light trigger used in the present invention (C); can only use acylphosphine oxide type light trigger; also can be used in combination with the light trigger of one or more other types; in the situation that being used in combination, the content of described acylphosphine oxide type light trigger in light trigger (C) is 50-100 % by weight.In the present invention, the other types light trigger that can be used in combination together with acylphosphine oxide type light trigger has, for example: benzoin, benzoin and the benzoin alkyl ethers such as benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, the acetophenones such as 1-dichloroacetophenone; 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl 1-acetone (commodity are called Irgacure907), 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone, N, the aminoacetophenone classes such as N-dimethylamino benzoylformaldoxime; The Anthraquinones such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, isopropyl thioxanthone (ITX); 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2, the thioxanthene ketones such as 4-diisopropyl thioxanthones; The ketal classes such as acetophenone dimethyl ketal, benzyl dimethyl ketal; The organic peroxides such as this formyl of peroxidating, dicumyl peroxide base; The mercaptan compounds such as hibon, 2-sulfenyl benzimidazole, 2-sulfenyl benzoxazole, 2-sulfurio benzo thiazole; 2,4,6-, tri--S-triazine; 2,2,2-ethobrom; Trisbromomethyl phenyl ketone organohalogen compounds; Benzophenone, 4, the 4 '-Benzophenones such as bis-ethylamino benzophenone or thioxanthene ketone etc.; Various superoxide etc.; Luxuriant titanium is light trigger etc.In addition, in described light trigger (C), also can add light-initiated auxiliary agent, N for example, N-dimethylamino benzoic acid ethyl ester, N, the tertiary amines such as N-dimethylamino benzoic acid isopentyl ester, amyl group-4-dimethylaminobenzoic acid ester, triethylamine, triethanolamine.
In photosensitive solder resist composition of the present invention; in alkali solubility photosensitive resin (A) described in 100 weight portions; the consumption of the described light trigger (C) that contains at least one acylphosphine oxide type light trigger is preferably 1-30 weight portion, preferably 3-20 weight portion, more preferably 6-15 weight portion.When the consumption of light trigger (C) is less, composition exposure posterior photocuring is incomplete, while developing by alkaline-based developer, can not obtain needed figure; When consumption is too high, the ultraviolet ray of the light trigger on top layer hyperabsorption in exposure process, causes the photo-curable of bottom to reduce.
The present invention uses titania (D) as Chinese white, because high (rutile titanium dioxide refractive index n=2.80 of titania refractive index, anatase titanium dioxide n=2.55), other Chinese whites of energy force rate of light scattering are all strong, and have fabulous covering power and good surface brightness.Preferred rutile-type and anatase titanium dioxide, more preferably rutile titanium dioxide, has better weatherability, water tolerance and feature inhibited from yellowing because it is compared with anatase titanium dioxide.Use rutile titanium dioxide (D) can obtain the soldering-resistance layer of excellent in stability as Chinese white.
In photosensitive solder resist composition of the present invention, in alkali solubility photosensitive resin (A) described in 100 weight portions, the consumption of described rutile titanium dioxide (D) is 30-200 weight portion, preferably 50-100 weight portion, more preferably 60-90 weight portion.When consumption is less than 30 weight portion, covering power is little, whiteness is low, is difficult to obtain the soldering-resistance layer of high reflectance; When consumption is too high, can cause the photo-curable of bottom to reduce, simultaneously because the ratio of alkali solubility photosensitive resin (A) is low, easily produce the phenomenon of poor visualization.
Described rutile titanium dioxide pigment (D) is available commercially, and its granularity (being particle diameter) is below 25 μ m, preferably below 15 μ m.
Thinning agent in the present invention (E) can be organic solvent, for example ethers, ester class, ketone, aromatic hydrocarbon solvent or petroleum solvent, and these solvents can be used alone or two or more mixing is used.Described ethers such as the ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE, Dipropylene glycol mono-n-butyl Ether; Described ester class is ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol single-butyl ether acetic acid esters, DPGME acetic acid esters, dihydroxypropane single-ethyl ether acetic acid esters, dipropylene glycol single-butyl ether acetic acid esters for example; Described ketones solvent, as butanone, cyclohexanone, isophorone; Described aromatic hydrocarbon solvent, as toluene, dimethylbenzene, durene; Described petroleum solvent, as naphtha, oxidation naphtha, solvent naphtha etc.
Thinning agent in the present invention (E) also can be photopolymerization monomer, such as: (methyl) esters of acrylic acid that contains hydroxyl of (methyl) hydroxy-ethyl acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc.; Simple function (methyl) esters of acrylic acids such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) lauryl acrylate; Difunctionality (methyl) esters of acrylic acids such as two (methyl) acrylate of 1,6-hexanediol, two (methyl) acrylate of two contracting/triethylene Glycols, two (methyl) acrylate of two contracting/tripropylene glycols, two (methyl) acrylate of ethoxyquin bisphenol-A, two (methyl) acrylate of neopentyl glycol diethoxy/propoxyl group; Multifunctional (methyl) esters of acrylic acids such as trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate; N, (methyl) acrylic amides such as N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide; (methyl) acrylic acid N, (methyl) acrylic-amino alkyl esters such as N-dimethylaminoethyl; And ethoxylation polyfunctional acrylic ester and the multifunctional acrylic acid of propoxylation etc.Above-mentioned substance can be used alone or two or more mixing is used.
In photosensitive solder resist composition of the present invention, in alkali solubility photosensitive resin (A) described in 100 weight portions, the consumption of the poly-property monomer of above-mentioned light is up to 50 weight portions, is preferably up to 30 weight portions, is more preferably up to 25 weight portions.
In the present invention, described thinning agent (E) can be used separately photopolymerization monomer or organic solvent, also can use this two classes material simultaneously.
In photosensitive solder resist composition of the present invention, in alkali solubility photosensitive resin (A) described in 100 weight portions, the consumption of described thinning agent (E) is 3-100 weight portion, preferably 5-30 weight portion, more preferably 10-25 weight portion.
Optionally, in photosensitive solder resist composition of the present invention, also can comprise one or more in the auxiliary agents such as epoxy resin cure promoter, inorganic filler, thixotropic agent, defoamer and levelling agent.
Described epoxy resin cure promoter can be: imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-the imdazole derivatives such as 2-ethyl-4-methylimidazole; Dicyano diamides, phenyl dimethyl amine, 4-(dimethylamino)-N, the amines such as N-dimethyl benzyl amine, melamine; The hydrazide kind compounds such as adipoyl hydrazine, decanedioyl hydrazine; The phosphorus compounds such as triphenyl phosphorus etc.Epoxy resin cure promoter, without particular limitation of in the above compound, as long as can promote epoxy resin cure, promotes the material of epoxy radicals and carboxyl reaction all to can be used for the present invention.These materials can be used alone or two or more mixing is used, and by alkali solubility photosensitive resin (A) described in 100 weight portions, its consumption is preferably 0.2-40 weight portion, more preferably 0.5-20 weight portion.
In addition in order to improve the features such as hardness, thermotolerance, as required, in the present composition, can also contain conventional inorganic filler, such as: barium sulphate, barium titanate, calcium dioxide, talcum powder, gas-phase silica, aerosil, clay, magnesium carbonate, calcium carbonate, aluminium oxide, mica powder, porcelain earth etc.The consumption of described inorganic filler, in photoresist (A) described in 100 weight portions, is below 200 weight portions.
Thixotropic agent, defoamer and levelling agent are conventional those that use in this area, thixotropic agent BYK-411 for example, defoamer KS-66, BYK-057, levelling agent BYK-301, BYK-331.Its consumption is all below 5 weight portions.
Photosensitive solder resist composition of the present invention can be by said components is mixed, and dispersed in dispersing apparatus, then grinds and obtain.The dispersing apparatus using in preparation process can be, as U400 80-220 high speed dispersor, milling apparatus can be, for example S-65 three-roll grinder.
Photosensitive solder resist composition of the present invention be take TGIC resin and is formed as hardening agent as matrix resin is equipped with not containing the epoxy resin of phenyl ring.Owing to containing the triazine ring structure of highly stable not xanthochromia in TGIC structure, and in each molecule, contain three (methyl) acrylic acid unsaturated functional groups, after photocuring, there is very high cross-linking density, therefore the cured coating film of being prepared by composition of the present invention has extraordinary thermotolerance and hardness, also has good preliminary drying drying property, developability, solvent resistance and adhesion simultaneously.
In addition,, owing to not containing the easy xanthochromia groups such as phenyl ring in the alkali solubility photosensitive resin molecular structure of the present composition, the soldering-resistance layer therefore consisting of the present composition has outstanding light aging resisting property.
In addition, the present invention also provide described photosensitive solder resist composition with soldering-resistance layer form the purposes for the preparation of printed wiring board.
In addition, the present invention also provides a kind of printed wiring board, and it contains described photosensitive solder resist composition as soldering-resistance layer.
Below in connection with embodiment, illustrate the present invention, but the present invention is not limited to following examples.
In the present invention, " acid number " is all by common determination of acid-basetitration.
" weight-average molecular weight " all by gel permeation chromatograph PL GPC 50 plus(purchased from U.S. Polymer Laboratory company) detect.
The preparation of the alkali solubility photosensitive resin A1 that synthetic example 1(is obtained by TGIC)
In the reactor of a 1L that thermometer, stirrer, reflux condensing tube and tap funnel be housed, add 150 grams of TGIC(epoxide equivalents 102, purchased from Changzhou Niutang Chemical Industry Co., Ltd.), under agitation add 300 grams of diethylene glycol monoethyl ether acetic acid esters as solvent, 0.5 gram of p-dihydroxy-benzene as polymerization inhibitor and 2 grams of triphenylphosphines as catalysts.This potpourri is heated to 95 ℃, after TGIC dissolves completely, slowly drips 104 grams of acrylic acid, then under 95 ℃ of-100 ℃ of conditions, react 15 hours, until the detection acid number of potpourri is less than 5mg KOH/g.In question response device, temperature is down to after 85 ℃-90 ℃, adds 100 grams of tetrabydrophthalic anhydrides, reacts 6 hours, and obtaining acid number is the light yellow transparent liquid Resin A 1 that 58mgKOH/g, solid content are 55%.
The preparation of synthetic example 2(epoxy resin of the present invention)
In the reactor of a 1L that thermometer, stirrer, reflux condensing tube and tap funnel be housed, add 150 grams of diethylene glycol monoethyl ether acetic acid esters as solvent, be heated to 80-82 ℃; Under agitation with nitrogen protection under; add 10 grams of peroxidating azoisobutyronitriles; maintain the temperature at 80-82 ℃; in two hours, splash into 200 grams, the potpourri of glycidyl methacrylate and methyl methacrylate (weight ratio is 140:60); insulated and stirred is two hours afterwards, and temperature is raised to 120 ℃ of insulations one hour.It is 20000 that cooling obtains weight-average molecular weight, and solids epoxy equivalent is 200, the polymer solution that solid content is 58.3% (M-1).
Synthetic comparative example (preparation of Resin A 2 used in prior art welding resistance composition)
In the reactor of a 1L that thermometer, stirrer, reflux condensing tube and tap funnel be housed, add 400 grams of diethylene glycol monoethyl ether acetic acid esters as solvent, be heated to 80-82 ℃; Under agitation with nitrogen protection under; add 10 grams of peroxidating azoisobutyronitriles; maintain the temperature at 80-82 ℃; in two hours, splash into 200 grams, the potpourri of methacrylic acid and methyl methacrylate (weight ratio is 85:115); insulated and stirred is two hours afterwards, and temperature is raised to 120 ℃ of insulations one hour.Cooling to 80 ℃ adds 0.5 p-dihydroxy-benzene as polymerization inhibitor, add 130 grams of glycidyl methacrylate, 1 gram of triphenylphosphine is as catalysts, this potpourri is heated to 90-95 ℃, reacts 20 hours, until detecting reactant acid number result is less than 10mgKOH/g, keep reactor temperature 90-95 ℃, add 120 grams of tetrabydrophthalic anhydrides, react 6 hours, obtain weight-average molecular weight 23000, acid number is the light yellow transparent liquid Resin A 2 that 56mgKOH/g, solid content are 53%.
Embodiment 1-8 and comparative example 1-4
By the Resin A 1 obtaining in synthesis example above and Resin A 2 respectively by table 1, table 1 ' and table 2 in formula mix, first use dispersion machine (U400 80-220 high speed dispersor) high speed dispersion 15 minutes, then use three-roll grinder (S-65 three-roll grinder) to grind 3 times, obtain respectively photosensitive solder resist composition.Numeral weight portion in table.
Table 1
| Material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Resin A 1 | 45 | 45 | 45 | 45 |
| M-1 | 15 | 15 | 15 | 15 |
| Irgacure?TPO | 3 | 3 | - | 3 |
| Irgacure?819 | - | - | 3 | 3 |
| Irgacure?907 | - | - | - | - |
| ITX | - | 3 | - | - |
| Rutile titanium dioxide | 36 | 36 | 36 | 36 |
| DPHA | 4 | 4 | 4 | 4 |
| Diethylene glycol ether acetic acid esters | 5 | 5 | 5 | 5 |
| Melamine | 1 | 1 | 1 | 1 |
| R972 | 1.2 | 1.2 | 1.2 | 1.2 |
| KS-66 | 1 | 1 | 1 | 1 |
Irgacure TPO: light trigger (TMDPO), purchased from Jiangsu Hua Tai company
Irgacure 819: light trigger (two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide), and purchased from BASF Aktiengesellschaft
ITX: light trigger, purchased from Tianjin Jiuri Chemical Co., Ltd.
Irgacure 907: light trigger, and purchased from Zhejiang Yangfan Fine Chemical Co., Ltd.
Rutile titanium dioxide: Tiona RCL595 type, purchased from Australia Mei Lilian company
DPHA: dipentaerythritol acrylate, purchased from U.S. Sartomer company
Melamine: purchased from Nanjing Mei Kai Science and Technology Ltd.
R972: aerosil, purchased from winning wound industrial group
KS-66: organic silicone oil type defoamer, purchased from Japanese Shin-Etsu Chemial Co., Ltd
Table 2
| Material | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Resin A 2 | 45 | 45 | 45 | 45 |
| CNE202 | 8 | 8 | 8 | 8 |
| Irgacure?TPO | 3 | - | - | - |
| Irgacure?819 | - | - | - | - |
| Irgacure?907 | - | 3 | - | 3 |
| ITX | - | - | 3 | 3 |
| Rutile titanium dioxide | 36 | 36 | 36 | 36 |
| DPHA | 4 | 4 | 4 | 4 |
| Diethylene glycol ether acetic acid esters | 5 | 5 | 5 | 5 |
| Melamine | 0.5 | 0.5 | 0.5 | 0.5 |
| R972 | 1.2 | 1.2 | 1.2 | 1.2 |
| KS-66 | 1 | 1 | 1 | 1 |
CNE202: o-cresol formaldehyde epoxy resin, purchased from Changchun, Taiwan group of enterprises
Table 1 '
Performance embodiment
For the properties of liquid photosensitive composition of the present invention (embodiment 1-8) and liquid photosensitive composition of the prior art (comparative example 1-4) is compared, test as follows, and evaluate.
(1) preliminary drying drying property
By stencil, the composition of aforementioned each embodiment and comparative example being printed on to clean being dried also has made on the wiring board (5x8cm) of conductive pattern, thickness is 5 μ m, in the baking oven of 75 ℃, after predrying 40 minutes, take out cool to room temperature, cover exposure film, in exposure machine, vacuumize, take out the impression of inspection group's compound and the complexity that egative film takes off.Composition film does not have impression completely, and egative film easily takes off as " excellent "; Composition film has slight impression, and egative film more easily takes off and composition film is not stained with egative film for " good "; Composition film has obvious impression, egative film is more difficult take off and composition film be not stained with egative film for " in ", composition film is stained with egative film for " poor ".Result is shown in table 3 and table 4.
(2) developability
With silk screening, composition is coated on to clean dry wiring board substrate (5x8cm) upper, makes in test sample plate, each routine model is 4, puts into 75 ℃ of constant temperature roasters and toasts, and within every 10 minutes, takes out one from baking box, then carries out development operation.Development conditions is: the Na of 1 % by weight
2cO
3aqueous solution, 30 ℃ of liquid temperatures, spray pressure 1kg/cm
2.Within pre-baked 30 minutes, can develop clean, within 40 minutes, can not develop clean is " poor "; Within pre-baked 40 minutes, can develop clean, within 50 minutes, can not develop clean for " in "; Within pre-baked 50 minutes, can develop clean, within 60 minutes, can not develop clean is " good "; Within 60 minutes, can develop is totally " excellent ".Result is shown in table 3 and table 4.
(3) thermotolerance
By stencil, composition is coated on and cleans dry and made on the wiring board (5x8cm) of conductive pattern, make model, the constant temperature oven that model is placed in to 75 ℃ toasts 40 minutes, with the residual 10 lattice institute energy requirements of ink film, expose, then develop (by the development conditions in (2)), at the constant temperature oven that model is placed in to 150 ℃, toast 1 hour, make test sample plate.On each test film, be coated with rosin flux, in the weld groove of 260 ℃, circulated for 10 seconds.Then, after washing and be dried with propylene glycol methyl ether acetate, utilize viscose paper adhesive tape to carry out disbonded test.Film and do not peel off as " excellent ", filmed and peeled off as " poor ".Result is shown in table 3 and table 4.
(4) adhesion
To adopt a stroke lattice adhesive tape method to test model adhesion with (3) same each test sample plate of making.Do not come off completely for " excellent ", draw ruling limit and come off on a small quantity for " good ", have 1 lattice to come off above for " poor ".Result is shown in table 3 and table 4.
(5) solvent resistance
Each test sample plate that process by identical with (3) is made is flooded 30 minutes in propylene glycol methyl ether acetate, dry after, utilize viscose paper adhesive tape to carry out disbonded test, peeling off with variable color of filming evaluated." excellent " represents to film not peel off and variable color, and " poor " represents to have filmed to peel off and variable color.Result is shown in table 3 and table 4.
(6) pencil hardness
In each test sample plate of making in the process by identical with (3), the B that the nib of pen core is polished, to the pencil of 9H, presses with the angle of 45 degree, and record is filmed and do not produced the pencil hardness of peeling off.Result is shown in table 3 and table 4.
Table 3
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Preliminary drying drying property | Excellent | Excellent | Excellent | Excellent |
| Developability | Excellent | Excellent | Excellent | Excellent |
| Thermotolerance | Excellent | Excellent | Excellent | Excellent |
| Adhesion | Excellent | Excellent | Excellent | Excellent |
| Solvent resistance | Excellent | Excellent | Excellent | Excellent |
| Pencil hardness | 7H | 7H | 7H | 7H |
Table 4
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Preliminary drying drying property | Excellent | Excellent | Excellent | Excellent |
| Developability | Excellent | Excellent | Excellent | Excellent |
| Thermotolerance | Poor | Poor | Poor | Poor |
| Adhesion | Excellent | Excellent | Excellent | Excellent |
| Solvent resistance | Excellent | Excellent | Excellent | Excellent |
| Pencil hardness | 6H | 6H | 6H | 6H |
Result from table 3 and table 4, the photosensitive solder resist composition that the alkali solubility photosensitive resin A1 being obtained by TGIC in embodiment of the present invention 1-4 obtains, when for printed-wiring board (PWB), at the aspects such as preliminary drying drying property, developability, thermotolerance, adhesion, solvent resistance, hardness, the conventional photosensitive solder resist composition that is all better than or at least equals to be obtained by alkali solubility photosensitive resin A2 in comparative example.Particularly, thermotolerance and hardness performance are better than the conventional photosensitive solder resist composition being obtained by alkali solubility photosensitive resin A2.
(7) light fastness aging
Each test sample plate that to make by the process identical with (3), measures gained test sample plate with HP-200 colour difference meter (purchased from ShangHai HanPu opto-electrical Science Co., Ltd).Then use 7KV exposure machine with 100J/cm
2come irradiating ultraviolet light to carry out accelerated deterioration in 30 minutes, then test.Result is shown in table 5 and table 6.
Table 5
Table 6
In table 5 and table 6, Y represents the reflectivity of XYZ colorimetric system, L
*represent L
*a
*b
*the lightness of colorimetric system; a
*represent that red is to ,-a
*represent green direction, b
*represent that yellow party is to ,-b
*represent blue party to, its numerical value more approaches null representation does not more have chroma; △ E
*ab represents the chromatic aberration of color, and the chromatic aberration of the less expression color of this value is less.
From the result of table 5 and table 6, photosensitive solder resist composition of the present invention, with 100J/cm
2irradiating ultraviolet light is carried out after accelerated deterioration, and it is little that reflectivity reduces amplitude, and the variation of lightness is smaller.Especially, the aberration △ E of color
*ab changing value is compared little with conventional photosensitive solder resist composition.
(8) each performance of the photosensitive solder resist composition of the present invention of embodiment of the present invention 5-8 is tested, process of the test and evaluation criterion are wherein with reference to (1)-(7), and test result is as shown in the table.
Table 7
| Project | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Preliminary drying drying property | Excellent | Excellent | Excellent | Excellent |
| Developability | Excellent | Excellent | Excellent | Excellent |
| Thermotolerance | Excellent | Excellent | Excellent | Excellent |
| Adhesion | Excellent | Excellent | Excellent | Excellent |
| Solvent resistance | Excellent | Excellent | Excellent | Excellent |
| Pencil hardness | 7H | 7H | 7H | 7H |
Table 8
From upper table 1-8 and table 1 ' result, photosensitive solder resist composition of the present invention, has good preliminary drying drying property, developability, thermotolerance, adhesion, solvent resistance, hardness, light fastness aging.Its soldering-resistance layer, for printed circuit board, meets the requirement of high reflectance, excellent heat resistance and good light fastness aging aspect.
Should be understood that, although describe the present invention with reference to particular, those skilled in the art will appreciate that in the situation that not departing from purport of the present invention and scope, can described embodiment be changed or be improved, the scope of the invention limits by appended claims.
Claims (16)
1. a photosensitive solder resist composition, it comprises
(A) in 100 weight portion molecules, there is the alkali solubility photosensitive resin of triazine ring structure;
And the following component based on alkali solubility photosensitive resin meter described in 100 weight portions:
(B) in 5-70 weight portion molecule, do not contain the epoxy resin of aromatic rings;
(C) light trigger that 1-30 weight portion contains at least one acylphosphine oxide type light trigger;
(D) 30-200 parts by weight of titanium dioxide; And
(E) 3-100 weight portion organic solvent and/or the photopolymerization monomer that is up to 50 weight portions are as thinning agent.
2. the photosensitive solder resist composition of claim 1, it comprises
(A) in 100 weight portion molecules, there is the alkali solubility photosensitive resin of triazine ring structure;
And the following component based on alkali solubility photosensitive resin meter described in 100 weight portions:
(B) in 10-30 weight portion molecule, do not contain the epoxy resin of aromatic rings;
(C) light trigger that 3-20 weight portion contains at least one acylphosphine oxide type light trigger;
(D) 50-100 weight portion rutile titanium dioxide; And
(E) 5-30 weight portion organic solvent and/or the photopolymerization monomer that is up to 30 weight portions are as thinning agent.
Claim 1 photosensitive solder resist composition, it comprises
(A) in 100 weight portion molecules, there is the alkali solubility photosensitive resin of triazine ring structure;
And the following component based on alkali solubility photosensitive resin meter described in 100 weight portions:
(B) in 15-25 weight portion molecule, do not contain the epoxy resin of phenyl ring;
(C) light trigger that 6-15 weight portion contains at least one acylphosphine oxide type light trigger;
(D) 60-90 weight portion rutile titanium dioxide; And
(E) 10-25 weight portion organic solvent and/or the photopolymerization monomer that is up to 25 weight portions are as thinning agent.
4. the photosensitive solder resist composition of one of claim 1-3, the acid number of wherein said (A) alkali solubility photosensitive resin is 50-150mg KOH/g.
5. the photosensitive solder resist composition of one of claim 1-3, wherein said (A) alkali solubility photosensitive resin is the reactant of triglycidyl isocyanurate, unsaturated monocarboxylic and multi-anhydride; Described (B) epoxy resin is not contain the epoxy resin of phenyl ring; In described (C), acylphosphine oxide type light trigger is 2,4,6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide, TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, 2,4,6-trimethylbenzene formyl diethyl phosphonate, two (2,6-dimethylbenzoyl)-(4 ˊ, 4 ˊ-dimethyl octyl group-2) phenyl phosphine oxide; The content of described acylphosphine oxide type light trigger in light trigger (C) is 50-100 % by weight.
6. the photosensitive solder resist composition of claim 5, wherein said (A) alkali solubility photosensitive resin is the reactant of triglycidyl isocyanurate, acrylic acid and tetrabydrophthalic anhydride.
7. the photosensitive solder resist composition of claim 5, wherein said (B) epoxy resin is the multipolymer of glycidyl methacrylate and simple function (methyl) acrylate.
8. the photosensitive solder resist composition of claim 5, in wherein said (C), acylphosphine oxide type light trigger is TMDPO and two (2,4,6-trimethylbenzoyl) phenyl phosphine oxides.
9. the photosensitive solder resist composition of claim 5, the epoxide equivalent of wherein said triglycidyl isocyanurate is less than 115; Described unsaturated monocarboxylic is acrylic acid and/or methacrylic acid, and the epoxy molar equivalent of its consumption based on triglycidyl isocyanurate counted 90%-110%; Described multi-anhydride is not containing the multi-anhydride of aromatic rings, and its consumption is that to make the acid number of (A) alkali solubility photosensitive resin of generating be 50-150mg KOH/g.
10. the photosensitive solder resist composition of claim 9, the epoxide equivalent of wherein said triglycidyl isocyanurate is less than 110.
The photosensitive solder resist composition of 11. claims 9, wherein said unsaturated monocarboxylic is acrylic acid and/or methacrylic acid, the epoxy molar equivalent of its consumption based on triglycidyl isocyanurate counted 98%-102%.
The photosensitive solder resist composition of 12. claims 9, wherein said multi-anhydride is tetrabydrophthalic anhydride, hexahydrophthalic anhydride and succinic anhydride.
The photosensitive solder resist composition of one of 13. claim 1-3, in wherein said (E), organic solvent is ethers, ester class, ketone, aromatic hydrocarbon solvent or petroleum solvent, these solvents can be used alone or two or more mixing is used; Described photopolymerization monomer is (methyl) esters of acrylic acid that contains hydroxyl; Simple function (methyl) esters of acrylic acid; Difunctionality (methyl) esters of acrylic acid; Multifunctional (methyl) esters of acrylic acid; (methyl) acrylic amide; (methyl) acrylic-amino alkyl esters; And ethoxylation polyfunctional acrylic ester and the multifunctional acrylic acid of propoxylation, above-mentioned photopolymerization monomer can be used alone or two or more mixing is used.
The photosensitive solder resist composition of one of 14. claim 1-3, it also can comprise one or more in epoxy resin cure promoter, inorganic filler, thixotropic agent, defoamer and levelling agent; Wherein, in 100 weight portions (A) alkali solubility photosensitive resin, the consumption of described epoxy resin cure promoter is 0.1-20 weight portion; The consumption of described inorganic filler is below 200 weight portions; The consumption of described thixotropic agent, defoamer and levelling agent is all below 5 weight portions.
15. 1 kinds of printed wiring boards, it contains the described photosensitive solder resist composition of one of claim 1-3 as soldering-resistance layer.
Photosensitive solder resist composition described in one of 16. claim 1-3 is the purposes for the preparation of printed wiring board with soldering-resistance layer form.
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| JP6822758B2 (en) * | 2014-09-30 | 2021-01-27 | 日鉄ケミカル＆マテリアル株式会社 | A photosensitive resin composition for a touch panel, a cured film thereof, and a touch panel having the cured film. |
| CN104559456A (en) * | 2014-12-25 | 2015-04-29 | 无锡德贝尔光电材料有限公司 | White solder-resist ink for LED |
| CN104610804B (en) * | 2015-01-30 | 2016-11-23 | 惠州市容大油墨有限公司 | A kind of photosensitive solder resist compositions, its purposes and the printed circuit board (PCB) containing it |
| JP6448447B2 (en) * | 2015-04-07 | 2019-01-09 | 日本化薬株式会社 | White active energy ray-curable resin composition |
| CN107203095B (en) * | 2017-07-19 | 2020-08-18 | 江苏广信感光新材料股份有限公司 | White alkali-soluble photosensitive composition and preparation method and application thereof |
| CN114442425A (en) * | 2020-10-30 | 2022-05-06 | 常州正洁智造科技有限公司 | Curable resin composition, solder resist film formed from the same, interlayer insulating material, and printed wiring board |
| CN114539843B (en) * | 2021-12-21 | 2023-03-28 | 深圳市容大感光科技股份有限公司 | Ink-jet printing solder-resist ink composition and circuit board thereof |
| CN115819361B (en) * | 2022-12-08 | 2024-03-12 | 广东炎墨方案科技有限公司 | Modified TGIC auxiliary agent for UV photosensitive solder resist ink and preparation method thereof |
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| CN1409173A (en) * | 2001-09-21 | 2003-04-09 | 田村化研株式会社 | Photosensitive resin composition and printing circuit board |
| JP2007224169A (en) * | 2006-02-24 | 2007-09-06 | Taiyo Ink Mfg Ltd | Photocurable resin composition, and cured product thereof |
| CN101980081A (en) * | 2010-02-17 | 2011-02-23 | 太阳控股株式会社 | Solder resist composition and printed circuit board |
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| CN1409173A (en) * | 2001-09-21 | 2003-04-09 | 田村化研株式会社 | Photosensitive resin composition and printing circuit board |
| JP2007224169A (en) * | 2006-02-24 | 2007-09-06 | Taiyo Ink Mfg Ltd | Photocurable resin composition, and cured product thereof |
| CN101980081A (en) * | 2010-02-17 | 2011-02-23 | 太阳控股株式会社 | Solder resist composition and printed circuit board |
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Effective date of registration: 20200429 Address after: 516081 block L3, Dayawan Petrochemical District, Huizhou City, Guangdong Province Patentee after: Huizhou City Appearance photosensitive Technology Co., Ltd Address before: Huidong County, Guangdong province 516347 Huizhou City Ren Shan Zhen seaside city development zone Patentee before: HUIZHOU RONGDA PRINTING INK Co.,Ltd. |