CN104974596A - Photosensitive solder-resist printing ink composition and circuit board including cured film of same - Google Patents
Photosensitive solder-resist printing ink composition and circuit board including cured film of same Download PDFInfo
- Publication number
- CN104974596A CN104974596A CN201510381448.7A CN201510381448A CN104974596A CN 104974596 A CN104974596 A CN 104974596A CN 201510381448 A CN201510381448 A CN 201510381448A CN 104974596 A CN104974596 A CN 104974596A
- Authority
- CN
- China
- Prior art keywords
- photosensitive solder
- solder resist
- photoresist
- ink composite
- resist ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a photosensitive solder-resist printing ink composition, comprising (A) photosensitive resin which simultaneously contains a carboxyl group and at least two alkenyl unsaturated bonds in the molecule, (B) a photoinitiator, (C) an anti-oxidant, (D) an organic solvent, (E) a thermosetting component, (F) a photopolymerization monomer and (G) an inorganic filling material, wherein in terms of the solid of 100 parts by weight of the photosensitive resin (A), the content of the anti-oxidant (C) is 0.1 to 20 parts by weight. Moreover, the invention further relates to a circuit board including a cured film formed by the photosensitive solder-resist printing ink composition.
Description
Technical field
The present invention relates to photosensitive solder resist ink composite and comprise the wiring board of the cured film formed by it.
Background technology
In printed-wiring board (PWB), electronic component is soldered to by the method such as wave soldering, Reflow Soldering the welding zone that it is pre-formed with the printed wiring base material of conductive circuit patterns, and all circuit regions outside welding zone are covered by the welding resistance cured film as permanent protective membrane.Therefore, time on welding electronic elements to printed-wiring board (PWB), solder can be avoided to be bonded at do not need on the region that covered by solder, and prevent the solid of forming circuit pattern oxidized owing to being directly exposed in air, or to be corroded due to moisture and mouldy etc.
Recently, along with the development of electronic product, more and more higher to the requirement of printed-wiring board (PWB), in the stability particularly in security and life cycle.Need hot setting, high-temperature high-pressure roasting in the fabrication process owing to there being the wiring board of high-accuracy requirement, layers of copper below its welding resistance cured film there will be redness phenomenon (phenomenon that namely layers of copper is oxidized) to a certain degree, and in use this phenomenon can constantly increase the weight of.Thus cause loss of adhesion, electromigration between welding resistance cured film and layers of copper to increase the weight of, and then easily there is degradation problem under line broken circuit in the stripping of welding resistance cured film and layers of copper, layers of copper, short circuit and electronic product operation parameter, have a strong impact on stability and the security of electronic product.
In order to solve the oxidized problem of layers of copper below above-mentioned welding resistance cured film, describe the concealed method by using tinting material to improve welding resistance cured film in Chinese patent application 200810081857.5,201110288406.0 and 201280018249.4, thus reduce the rubescent appearance of layers of copper.But described method only conceals the rubescent problem of layers of copper, do not reduce that namely layers of copper is rubescent does not reduce the oxidized generation of layers of copper.
Therefore, need to provide a kind of and be suitable for printed-wiring board (PWB), the oxidized photosensitive solder resist ink of layers of copper below welding resistance cured film can be reduced.
Summary of the invention
For solving the problem, the invention provides a kind of photosensitive solder resist ink composite, it comprises:
(A) photoresist, simultaneously containing carboxyl and at least two ethylenic unsaturated bonds in its molecule,
(B) light trigger,
(C) antioxidant,
(D) organic solvent,
(E) thermosetting component,
(F) photo polymerization monomer, and
(G) mineral filler;
Wherein, based on the solid component meter of the photoresist (A) of 100 weight parts, the content of described antioxidant (C) is 0.1 to 20 weight part.
In addition, the present invention also provides a kind of wiring board comprising the cured film formed by above-mentioned photosensitive solder resist ink composite.
The cured film formed in the circuit board by photosensitive solder resist ink composite of the present invention has good thermotolerance, acid resistance, solvent resistance, adaptation and hardness, and can reduce the phenomenon of the layers of copper oxidation below welding resistance cured film.
Embodiment
Below the preferred embodiments of the invention will be described in detail in detail.Although the disclosed embodiments for illustration of object, should understand and the present invention is not limited thereto, and those skilled in the art are not when departing from scope of the present invention and essence, various amendment, increase and replacement can be carried out to the present invention.
In the present invention, acid number means the income value by measuring by means of the acid base titration of KOH standardized solution, viscosity measures according to GB/T 7193-2008 unsaturated polyester resin test method, and solid content measures according to GB/T 7193-2008 unsaturated polyester resin test method.
According to a first aspect of the invention, provide a kind of photosensitive solder resist ink composite, it comprises:
(A) photoresist, simultaneously containing carboxyl and at least two ethylenic unsaturated bonds in its molecule,
(B) light trigger,
(C) antioxidant,
(D) organic solvent,
(E) thermosetting component,
(F) photo polymerization monomer, and
(G) mineral filler;
Wherein, based on the solid component meter of the photoresist (A) of 100 weight parts, the content of described antioxidant (C) is 0.1 to 20 weight part.
In a preferred embodiment in accordance with this invention, the solids component acid number of described photoresist (A) is 50 to 150mgKOH/g, and it is by any one method preparation in following methods:
(1) make the multi-functional epoxy compound (a) in molecule with two or more epoxy group(ing) carry out esterification with unsaturated monocarboxylic (b), then the carboxylate obtained and saturated or undersaturated multi-anhydride (c) are reacted;
(2) (methyl) vinylformic acid and other the comonomer (d) with ethylenic unsaturated bond are reacted and form multipolymer, the multipolymer then a part obtained and (methyl) glycidyl acrylate react;
(3) (methyl) glycidyl acrylate and other the multipolymer with the comonomer (d) of ethylenic unsaturated bond and unsaturated monocarboxylic (b) are reacted, then the reaction product of gained and saturated or undersaturated multi-anhydride (c) are reacted;
(4) to make to have in molecule in the multi-functional epoxy compound (a) of two or more epoxy group(ing), unsaturated monocarboxylic (b) and molecule containing at least two hydroxyls and there is one and can be obtained by reacting intermediate (I) with the compound (e) of other groups of epoxy reaction, then intermediate (I) and saturated or undersaturated multi-anhydride (c) are reacted;
(5) unsaturated multi-anhydride is made to form multipolymer, then by the multipolymer of gained and hydroxyalkyl (methyl) acrylate reactions with the aromatic hydrocarbon reaction with vinyl; Or
(6) intermediate (I) of method (4) gained and saturated or undersaturated multi-anhydride (c) and the monoisocyanates (f) containing unsaturated group are reacted.
In a preferred embodiment of the invention, the multi-functional epoxy compound (a) in the molecule in described method (1) and (4) with two or more epoxy group(ing) can be bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resins, the solvable epoxy resin of cresols, the novalac epoxies of dihydroxyphenyl propane, united phenol-type epoxy resin, di-toluene phenol-type epoxy resin, triphenol methylmethane type epoxy resin and N-Racemic glycidol type epoxy resin.When using the novalac epoxies of novolac epoxy resins, the solvable epoxy resin of cresols and dihydroxyphenyl propane, the welding resistance cured film with performances such as excellent scolding tin thermotolerance and chemical resistant propertiess can be obtained, therefore preferably use the novalac epoxies of the solvable epoxy resin of novolac epoxy resins, cresols and dihydroxyphenyl propane.The multi-functional epoxy compound in described molecule with two or more epoxy group(ing) can be used alone or use with the form of its mixture.
In a preferred embodiment of the invention, unsaturated monocarboxylic (b) in described method (1), (3) and (4) can be vinylformic acid, acrylic acid dipolymer, methacrylic acid, β-styrene acrylic, β-furfuryl acrylic acid, butenoic acid, alpha-cyano styracin, styracin, and the reaction product of (methyl) acrylate containing a hydroxyl in saturated or unsaturated dicarboxylic acid anhydride and molecule or saturated or unsaturated dibasic acid and unsaturated single glycidyl compound reaction product.In view of light solidified, preferred acrylic or methacrylic acid.
In a preferred embodiment of the invention, saturated or undersaturated multi-anhydride (c) in described method (1), (3), (4) and (6) can be: dibasic acid anhydride, such as maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Jia Qiao-Nei-Tetra Hydro Phthalic Anhydride, methyl first bridge-Nei-Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride etc.; Polybasic aromatic carboxylic acid's acid anhydride trimellitic acid 1,2-anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid dicarboxylic anhydride etc.; And 5-(2,5-dioxidotetrahydro furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, and polybasic acid anhydride derivative.In view of the characteristic of cured film, preferred Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride and succinyl oxide.This saturated or undersaturated multi-anhydride can be used alone or use with the form of its mixture.
In a preferred embodiment of the invention, described consumption that is saturated or undersaturated multi-anhydride (c) is the acid number of the solid ingredient making reaction product is the amount of 50 to 150mgKOH/g.When the acid number of the solid ingredient of reaction product is less than 50mgKOH/g, the alkali-solubility of described photosensitive solder resist ink composite is poor, and the cured film of gained is difficult to develop in alkene alkali aqueous solution subsequently.But when the acid number of the solid ingredient of reaction product is greater than 150mgKOH/g, the anti-developing performance of the cured film of gained is poor, even sometimes can not form welding resistance cured film.
In a preferred embodiment of the invention, other the comonomer (d) with ethylenic unsaturated bond in described method (2) and (3) can be vinylbenzene, chloro-styrene, alpha-methyl styrene; The acrylate replaced by methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amino, 2-ethylhexyl, octyl group, caprinoyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isobornyl, methoxy ethyl, butoxyethyl group, 2-hydroxyethyl, 2-hydroxypropyl and 3-chlorine-2-hydroxyl propyl group or methacrylic ester; The mono acrylic ester of the mono acrylic ester of polyoxyethylene glycol or monomethacrylates or polypropylene glycol or monomethacrylates; Vinyl-acetic ester, vinyl butyrate or vinyl benzoate; Acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxy methyl acrylamide, vinyl cyanide or maleic anhydride etc.The described comonomer that other have ethylenic unsaturated bond can be used alone or uses with the form of its mixture.
In a preferred embodiment of the invention, there is one can be containing polyhydric monocarboxylic acid with the compound (e) of other groups of epoxy reaction containing at least two hydroxyls, such as dimethylol propionic acid, dihydroxymethyl acetic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl caproic acid etc. in molecule in described method (4) and (6); And dioxane hydramine, such as diethanolamine, diisopropanolamine (DIPA) etc.Contain at least two hydroxyls and there is one in described molecule and can be used alone with the compound of other groups of epoxy reaction or use with the form of its mixture.
In a preferred embodiment of the invention, the described monoisocyanates (f) containing unsaturated group can be the product that (methyl) vinylformic acid in methylacryoyloxyethyl isocyanic ester or organic diisocyanate and molecule with a hydroxyl carries out with about equimolar ratio being obtained by reacting.Described unsaturated monoisocyanates can be used alone or uses with the form of its mixture.
Photoresist of the present invention (A) is not limited to the photoresist obtained by aforesaid method, and it can be used alone or uses with the form of its mixture.
In the photosensitive solder resist ink composite of one embodiment of the invention, described light trigger (B) can be: benzoin and benzoin alkyl oxide, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether etc.; Acetophenones, such as methyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone etc.; Aminoacetophenone class, such as 2-methyl isophthalic acid-[4-(methyl thio) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethyl amido-1-(4-morpholino phenyl)-butane-1-ketone, N, N-dimethyl amine benzoylformaldoxime etc.; Anthraquinones, such as 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone, isopropyl thioxanthone anthraquinone etc.; Thioxanthene ketone, such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone etc.; Ketal class, such as methyl phenyl ketone dimethyl ketal, benzyl dimethyl ketal etc.; Organo-peroxide, such as benzoyl peroxide, dicumyl peroxide base etc.; Mercaptan compound, such as 2,4,5-tri-aromatic base imidazoles diploids, hibon, 2-sulfenyl benzoglyoxaline, 2-sulfenyl benzoxazole, 2-sulfurio benzo thiazole etc.; Organohalogen compounds, such as 2,4,6-tri--s-triazines, tribromo-ethanol, trisbromomethyl phenyl ketone etc.; Benzophenones, such as benzophenone, 4,4 '-bis-diethyl aminobenzophenones etc.; And 2,4,6-trimethyl benzoyl diphenyl base phosphorous oxides etc.Above-mentioned light trigger can be used alone or uses with the form of its mixture.
In a preferred embodiment of the invention, based on the solid component meter of the photoresist (A) of 100 weight parts, the content of described light trigger (B) is preferably 1 to 40 weight part, more preferably 10 to 25 weight parts.
In the photosensitive solder resist ink composite of one embodiment of the invention, described antioxidant (C) can be, such as, and 2,6-toluene di-tert-butyl phenol, tricarbimide three (3,3-di-tert-butyl-4-hydroxyl benzyl) ester, 2,6-, tri-grades of butyl-4-methylphenols, 2,6-di-t-butyl is to ethyl phenol, two (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether, Triethylene glycol two [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 2,2 '-thiobis (4-methyl-6-tert-butylphenol), 4,4 '-thiobis (6-butyl o-cresol), thiobis-(3,5-di-t-butyl-4-hydroxyl benzyl), 2,5 di tert butyl hydroquinone, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, three monooctyl esters, three the last of the ten Heavenly stems ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate, three (Lauryl Alcohol) ester, distearyl pentaerythritol diphosphite, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites, the hard ester group pentaerythritol ester of diphosphorous acid two, three (16 carbon alcohol) ester, N, N '-hexamethylene-two-[3,5-di-t-butyl-4-hydroxybenzene propionic acid amide] etc.Above-mentioned antioxidant can be used alone or uses with the form of its mixture.
In a preferred embodiment of the invention, based on the solid component meter of the photoresist (A) of 100 weight parts, the content of described antioxidant (C) is preferably 0.1 to 20 weight part, more preferably 2 to 10 weight parts.
In the photosensitive solder resist ink composite of one embodiment of the invention, the example of described organic solvent (D) can be: ethers, such as ethylene glycol monomethyl 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 etc.; Ester class, such as ethyl acetate, butylacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, butyl carbitol acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic ester, dipropylene glycol monomethyl ether acetic ester, DPE acetic ester, Dipropylene glycol mono-n-butyl Ether acetic ester etc.; Ketone, such as butanone, pimelinketone, isophorone; Aromatic solvent, as toluene, dimethylbenzene, durene; And petroleum solvents, as petroleum naphtha, oxidation petroleum naphtha, solvent naphtha etc.These organic solvents can be used alone or use with the form of its mixture.
In a preferred embodiment of the invention, based on the solid component meter of the photoresist (A) of 100 weight parts, the content of described organic solvent (D) is preferably 40 to 200 weight parts, more preferably 80 to 150 weight parts.
In the photosensitive solder resist ink composite of one embodiment of the invention, described thermosetting component (E) is for having the epoxy compounds of two or more epoxy group(ing) in molecule.Described epoxy compounds is generally bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resins, the solvable epoxy resin of cresols, the novalac epoxies of dihydroxyphenyl propane, united phenol-type epoxy resin, di-toluene phenol-type epoxy resin, triphenol methylmethane type epoxy resin, N-Racemic glycidol type epoxy resin, isocyanuric acid three-glycidyl ester, 2，6-xylenol dimer diglycidylether, aliphatic epoxy resin, xylene epoxy resin.Above-mentioned epoxy compounds can be used alone or uses with the form of its mixture.
In a preferred embodiment of the invention, based on the solid component meter of the photoresist (A) of 100 weight parts, the content of described thermosetting component (E) is preferably 10 to 80 weight parts, more preferably 20 to 50 weight parts.
In the photosensitive solder resist ink composite of a particularly preferred embodiment of the present invention, thermosetting component (E) is 7:1 to 16:1 with the weight ratio of antioxidant (C).
Further preferably, the solids component of photoresist (A) and the ratio of thermosetting component weight (E) sum and antioxidant (C) weight are preferably 28:1 to 58:1.
In the photosensitive solder resist ink composite of one embodiment of the invention, the example of described photo polymerization monomer (F) can be: (methyl) Hydroxyethyl acrylate, (methyl) esters of acrylic acid containing hydroxyl of tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate etc.; (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, simple function (methyl) esters of acrylic acids such as (methyl) lauryl acrylate; Difunctionality (methyl) esters of acrylic acids such as two (methyl) acrylate of 1,6-hexylene glycol, two (methyl) acrylate of two contracting/tripropylene glycols, two (methyl) acrylate of two contracting/triethylene Glycols, two (methyl) acrylate of ethoxylated bisphenol A, two (methyl) acrylate of neopentyl glycol diethoxy/propoxy-; Trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, etc. multifunctional (methyl) esters of acrylic acid; And ethoxylation polyfunctional acrylic ester and propoxylation polyfunctional acrylic ester etc.These photo polymerization monomers can be used alone or use with the form of its mixture.
In a preferred embodiment of the invention, based on the solid component meter of the photoresist (A) of 100 weight parts, the content of described photo polymerization monomer (E) is preferably 5 to 50 weight parts, more preferably 10 to 30 weight parts.
In the photosensitive solder resist ink composite of one embodiment of the invention, the example of described mineral filler (G) can be: barium sulfate, barium titanate, calcium dioxide, talcum powder, gas-phase silica, silicon-dioxide, clay, magnesiumcarbonate, calcium carbonate, aluminum oxide, mica powder, kaolin etc.These mineral fillers can be used alone or use with the form of its mixture.
In a preferred embodiment of the invention, based on the solid component meter of the photoresist (A) of 100 weight parts, the content of described mineral filler (G) is preferably 50 to 300 weight parts, more preferably 100 to 200 weight parts.
In a particularly preferred embodiment of the present invention, described photosensitive solder resist ink composite also can comprise the additive that one or more are selected from following material: epoxy resin curing accelerator, light-initiated auxiliary agent, tinting pigment, thixotroping tackifier, dispersion agent, flow agent and defoamer etc.
As epoxy resin curing accelerator, light-initiated auxiliary agent, tinting pigment, thixotroping tackifier, dispersion agent, flow agent and defoamer, all Conventional compounds in this area can be used.The content of described additive can be 0 to 40 % by weight, based on the solid component meter of the photoresist (A) of 100 weight parts, but is not limited thereto.
When preparing photosensitive solder resist ink composite of the present invention, by each component Homogeneous phase mixing.
According to a second aspect of the invention, the present invention also provides a kind of wiring board comprising the cured film formed by above-mentioned photosensitive solder resist ink composite.
By photosensitive solder resist ink composite of the present invention for the preparation of wiring board time, ink composite is applied to by spraying method, flow coat method, rolling method, the line rod method such as cladding process, silk screen print method the wiring board being pre-formed with circuit.Thereafter, dry under about 50 DEG C to the temperature of 100 DEG C.Carry out selectivity exposure subsequently and develop in alkaline aqueous solution.Then, be heated 140 DEG C and be cured to 180 DEG C, wiring board of the present invention can be formed.
Hereinafter, in more detail the present invention is described with reference to following examples.But these examples are only for illustrating the present invention, and scope of the present invention is not limited thereto.
Embodiment
The synthesis > of < photoresist
According to following synthetic example, prepare photoresist (A)
210g o-cresol formaldehyde epoxy resin (be 210 purchased from the SQPN-704M of Shandong holy well, epoxy equivalent (weight)), 0.5g Resorcinol and 200g diethylene glycol ether acetic ester are added in there-necked flask, stirs and be heated to 100 ~ 110 DEG C and this temperature range inside holding 1 hour with by described substance dissolves.Cool to 90 DEG C until completely dissolved, then 72g vinylformic acid and 1g triphenyl phosphorus is dripped, temperature is controlled within the scope of 90 ~ 100 DEG C in dropping process, after dropwising, temperature is elevated to 105 ~ 110 DEG C, and react 12 hours in described temperature range, assaying reaction thing, if acid number is less than 5mgKOH/g, by the greenhouse cooling of reactant to 60 DEG C, then add 75g tetrahydrochysene and face phthalate anhydride, and be incubated 3 hours at 90 DEG C.What obtained be solid content is 64%, and viscosity is 420dPa.s, and solid acid value is the tawny resin (A) of 80mgKOH/g.
< embodiment 1-6 and comparative example 1-2 >
The photoresist (A) above-mentioned synthetic example obtained mixes with other components by the formula shown in table 1.Then by the mixture of gained dispersion machine (U400 80-220 high speed dispersor) high speed dispersion 10 minutes, then use three-roll grinder (S-65 three-roll grinder) to grind, obtain the photosensitive solder resist ink composite that particle diameter is less than 20 microns.
Table 1:
Note 1: purchased from the uv photopolymerization initiator of Tianjin day of a specified duration, isopropyl thioxanthone anthraquinone;
Note 2: purchased from the uv photopolymerization initiator of Zhejiang Yang Fan, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone;
Note 3: purchased from the antioxidant Irganox1010 of German BASF, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Note 4: purchased from the antioxidant Irganox1098 of German BASF, N, N '-hexamethylene-two-[3,5-di-t-butyl-4-hydroxybenzene propionic acid amide];
Note 5: Shandong holy well phenol aldehyde type epoxy resin SQPN-051;
Note 6: the ultra-fine isocyanuric acid three-glycidyl ester of launching company purchased from Nanjing U.S.A;
Note 7: the ultra-fine trimeric cyanamide of launching company purchased from Nanjing U.S.A;
Note 8: purchased from the dipentaerythritol acrylate of East Asia, Taiwan Synesis Company
Note 9: purchased from the A1 process white of Guangzhou Ji Mei company;
Note 10: purchased from the phthalocyanine blue D-7079 of German BASF;
Note 11: purchased from the Yellow204 of TKC chemical industry;
Note 12: purchased from the fumed silica of German Di Gaosha;
Note 13: purchased from the silicone antifoam agent of Japanese SHIN-ETSU HANTOTAI chemistry;
< testing example >
Photosensitive solder resist ink composite prepared by embodiment 1 ~ 6 and comparative example 1 ~ 2 made the wiring board containing corresponding photosensitive solder resist ink composite by following method, and measure its every characteristic in the following manner, acquired results is shown in Table 2.
Testing example 1: photosensitivity
Be that the 8cm x10cm copper wire substrate of 35 μm is in washing after 800 order steel brush polishings are except oxide layer, drying by thickness, then the whole face of photosensitive solder resist ink composite prepared by embodiment 1 ~ 6 and comparative example 1 ~ 2 is printed on clean dry copper wire substrate by silk screen print method, and puts it in the heated air circulation type drying oven of 75 DEG C dry 50 minutes.After the drying, use the exposure apparatus loading 7kW metal halide lamp to be exposed by 21 rank exposure guide rules, then at 30 DEG C with 1 % by weight Na
2cO
3aqueous development (spray pressure is 1kg/cm
2) 60 seconds.According to following criterion evaluation photosensitivity.
Excellent: after exposure, residual 9 lattice of development ink film need luminous energy to be less than 500mJ/cm
2;
Good: after exposure, residual 9 lattice of development ink film need luminous energy to be more than or equal to 500mJ/cm
2and be less than 700mJ/cm
2;
Difference: after exposure, residual 9 lattice of development ink film need luminous energy to be more than or equal to 700mJ/cm
2.
Testing example 2: cured film color
Prepare model in the mode identical with above-mentioned testing example 1, and prepared model is positioned in the constant temperature oven of 150 DEG C toast 1 hour to prepare test sample plate.By Color Evaluation above-described embodiment and the comparative example of cured film in visual test sample plate.
Testing example 3: copper wire discolouration
The test sample plate prepared in the mode identical with above-mentioned testing example 2 is heated 2 hours at 160 DEG C.According to following criterion evaluation copper wire discolouration.
Excellent: there is no difference or some variable color a little with prima facies ratio, but the thin part of cured film and thick part do not have difference;
Good: to confirm variable color, but the thin part of cured film and thick part do not have difference completely;
Difference: the variable color confirming the thin part of cured film, with the marked difference of thick part.
Testing example 4: thermotolerance
The test sample plate prepared in the mode identical with above-mentioned testing example 2 is coated with rosin flux, then the weld groove being placed in 260 DEG C floods 10 seconds, taking-up is also dry with propylene glycol methyl ether acetate washing, then utilizes glassine paper adhesive tape to carry out stripping test.According to following criterion evaluation thermotolerance.
Excellent: film is not peeled off;
Difference: film has stripping.
Testing example 5: sticking power
The test sample plate prepared in the mode identical with above-mentioned testing example 2 is heated 2 hours at 160 DEG C, then by drawing lattice adhesive tape method test sticking power.According to following criterion evaluation sticking power.
Excellent: not come off completely;
Difference: drawing a ruling limit has and come off.
Testing example 6: solvent resistance
The test sample plate prepared in the mode identical with above-mentioned testing example 2 is flooded 30 minutes in propylene glycol methyl ether acetate, washes with water after taking-up and drying.Then glassine paper adhesive tape is utilized to carry out stripping test.According to following criterion evaluation solvent resistance.
Excellent: film is not peeled off and variable color;
Difference: film has stripping and variable color.
Testing example 7: acid resistance
At room temperature the test sample plate prepared in the mode identical with above-mentioned testing example 2 be impregnated in 10 volume %H
2sO
4in the aqueous solution 30 minutes, to wash with water after taking-up and dry.Then glassine paper adhesive tape is utilized to carry out stripping test.According to following criterion evaluation acid resistance.
Excellent: film is not peeled off and variable color;
Difference: film has stripping and variable color.
Testing example 8: pencil hardness
In the test sample plate prepared in the mode identical with above-mentioned testing example 2, the pencil of the 4H to 7H polished by the nib of pen core presses with the angle of 45 °, to measure the pencil hardness that film is not peeling.
Table 2
As can be known from the results of Table 2, the embodiment of the present invention is owing to employing photosensitive solder resist ink composite of the present invention, and the copper wire discolouration that tool has clear improvement compared with comparative example.
Claims (12)
1. a photosensitive solder resist ink composite, it comprises:
(A) photoresist, simultaneously containing carboxyl and at least two ethylenic unsaturated bonds in its molecule,
(B) light trigger,
(C) antioxidant,
(D) organic solvent,
(E) thermosetting component,
(F) photo polymerization monomer, and
(G) mineral filler;
Wherein, based on the solid component meter of the photoresist (A) of 100 weight parts, the content of described antioxidant (C) is 0.1 to 20 weight part.
2. the photosensitive solder resist ink composite of claim 1, wherein the acid number of the solids component of photoresist (A) is the photoresist of 50 to 150mgKOH/g.
3. the photosensitive solder resist ink composite of claim 1, the content of wherein said light trigger (B) is 1 to 40 weight part, based on the solid component meter of the photoresist (A) of 100 weight parts.
4. the photosensitive solder resist ink composite of claim 1, the content of wherein said antioxidant (C) is 2 to 10 weight parts, based on the solid component meter of the photoresist (A) of 100 weight parts.
5. the photosensitive solder resist ink composite of claim 1, the content of wherein said organic solvent (D) is 40 to 200 weight parts, based on the solid component meter of the photoresist (A) of 100 weight parts.
6. the photosensitive solder resist ink composite of claim 1, wherein thermosetting component (E) is for having the epoxy compounds of two or more epoxy group(ing) in molecule, its content is 10 to 80 weight parts, based on the solid component meter of the photoresist (A) of 100 weight parts.
7. the photosensitive solder resist ink composite of claim 1, wherein thermosetting component (E) is 7:1 to 16:1 with the weight ratio of antioxidant (C).
8. the photosensitive solder resist ink composite of claim 1, wherein the solids component of photoresist (A) and the ratio of thermosetting component weight (E) sum and antioxidant (C) weight are preferably 28:1 to 58:1.
9. the photosensitive solder resist ink composite of claim 1, the content of wherein said photo polymerization monomer (F) is 5 to 50 weight parts, based on the solid component meter of the photoresist (A) of 100 weight parts.
10. the photosensitive solder resist ink composite of claim 1, the content of wherein said mineral filler (G) is 50 to 300 weight parts, based on the solid component meter of the photoresist (A) of 100 weight parts.
The photosensitive solder resist ink composite of 11. claims 1, it also comprises the additive that one or more are selected from following material: epoxy resin curing accelerator, light-initiated auxiliary agent, tinting pigment, thixotroping tackifier, dispersion agent, flow agent and defoamer.
12. 1 kinds of wiring boards, it comprises the wiring board of the cured film formed by the photosensitive solder resist ink composite of any one in claim 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510381448.7A CN104974596A (en) | 2015-07-02 | 2015-07-02 | Photosensitive solder-resist printing ink composition and circuit board including cured film of same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510381448.7A CN104974596A (en) | 2015-07-02 | 2015-07-02 | Photosensitive solder-resist printing ink composition and circuit board including cured film of same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104974596A true CN104974596A (en) | 2015-10-14 |
Family
ID=54271578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510381448.7A Pending CN104974596A (en) | 2015-07-02 | 2015-07-02 | Photosensitive solder-resist printing ink composition and circuit board including cured film of same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104974596A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733352A (en) * | 2016-02-29 | 2016-07-06 | 深圳市容大感光科技股份有限公司 | Photosensitive solder resist ink composition and circuit board |
| CN108395765A (en) * | 2018-01-29 | 2018-08-14 | 东莞市大兴化工有限公司 | Photosensitive solder resist white ink, LED circuit board and preparation method |
| CN110527350A (en) * | 2019-08-26 | 2019-12-03 | 广东炎墨科技有限公司 | A kind of high heat resistance high-crosslinking-degree photocuring solder mask and preparation method thereof |
| CN110563925A (en) * | 2019-09-16 | 2019-12-13 | 上海昭和高分子有限公司 | Anhydride modified epoxy acrylic resin, alkali development high-heat-resistance polyurethane resin and solder resist ink thereof |
| CN110845909A (en) * | 2019-11-21 | 2020-02-28 | 珠海宏博电子科技有限公司 | Photosensitive solder resist white oil and preparation method thereof |
| CN111704825A (en) * | 2020-07-11 | 2020-09-25 | 张家港科思创感光新材料有限公司 | Photosensitive solder resist ink composition containing novel curing agent and application thereof |
| CN115819361A (en) * | 2022-12-08 | 2023-03-21 | 广东炎墨方案科技有限公司 | Modified TGIC (triglycidyl isocyanurate) auxiliary agent for UV (ultraviolet) photosensitive solder resist ink and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220225A (en) * | 2008-01-30 | 2008-07-16 | 深圳市容大电子材料有限公司 | Light sensitive anti-solder ink composition, application and circuit board containing the same |
| CN101344724A (en) * | 2008-09-01 | 2009-01-14 | 深圳市容大电子材料有限公司 | Sensitive imaging composition, its preparation method and uses |
-
2015
- 2015-07-02 CN CN201510381448.7A patent/CN104974596A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220225A (en) * | 2008-01-30 | 2008-07-16 | 深圳市容大电子材料有限公司 | Light sensitive anti-solder ink composition, application and circuit board containing the same |
| CN101344724A (en) * | 2008-09-01 | 2009-01-14 | 深圳市容大电子材料有限公司 | Sensitive imaging composition, its preparation method and uses |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733352A (en) * | 2016-02-29 | 2016-07-06 | 深圳市容大感光科技股份有限公司 | Photosensitive solder resist ink composition and circuit board |
| CN108395765A (en) * | 2018-01-29 | 2018-08-14 | 东莞市大兴化工有限公司 | Photosensitive solder resist white ink, LED circuit board and preparation method |
| CN110527350A (en) * | 2019-08-26 | 2019-12-03 | 广东炎墨科技有限公司 | A kind of high heat resistance high-crosslinking-degree photocuring solder mask and preparation method thereof |
| CN110563925A (en) * | 2019-09-16 | 2019-12-13 | 上海昭和高分子有限公司 | Anhydride modified epoxy acrylic resin, alkali development high-heat-resistance polyurethane resin and solder resist ink thereof |
| CN110563925B (en) * | 2019-09-16 | 2022-02-01 | 上海昭和高分子有限公司 | Anhydride modified epoxy acrylic resin, alkali development high-heat-resistance polyurethane resin and solder resist ink thereof |
| CN110845909A (en) * | 2019-11-21 | 2020-02-28 | 珠海宏博电子科技有限公司 | Photosensitive solder resist white oil and preparation method thereof |
| CN111704825A (en) * | 2020-07-11 | 2020-09-25 | 张家港科思创感光新材料有限公司 | Photosensitive solder resist ink composition containing novel curing agent and application thereof |
| CN115819361A (en) * | 2022-12-08 | 2023-03-21 | 广东炎墨方案科技有限公司 | Modified TGIC (triglycidyl isocyanurate) auxiliary agent for UV (ultraviolet) photosensitive solder resist ink and preparation method 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104974596A (en) | Photosensitive solder-resist printing ink composition and circuit board including cured film of same | |
| CN100482752C (en) | Light sensitive anti-solder ink composition, application and circuit board containing the same | |
| CN102385244B (en) | Black curable resin composition | |
| CN104974594B (en) | The ink composite of a kind of water-soluble solvent, its application and printed circuit board (PCB) | |
| CN100469843C (en) | Liquid photosensitive ink and applied in printing circuit board | |
| CN102944977B (en) | Photosensitive solder resist composite, application thereof and printed circuit board (PCB) containing same | |
| CN104610804A (en) | Photoreception solder resistance compound, application thereof and PCB (Printed Circuit Board) comprising compound | |
| US9880467B2 (en) | Photo-curable and thermo-curable resin composition and dry film solder resist | |
| CN108287451A (en) | A kind of photosensitive cover film resin combination of low dielectric | |
| CN105086604A (en) | Printing ink composition, application thereof and printed circuit board | |
| CN104536266B (en) | A kind of dry film photoresist layered product | |
| CN101675113B (en) | Resin composition, dry film, and fabrications of the same | |
| CN105629665A (en) | Method for low-pressure spraying of infrared-solidified liquid photosensitive solder mask material on PCB | |
| CN104470962B (en) | Alkali developable resin, the photosensitive polymer combination using the resin | |
| CN108350107A (en) | Photocurable and heat-curable resin composition and dry film solder mask | |
| CN105511227A (en) | Dry film resist with good hole shielding function and laminated body thereof | |
| CN107801316A (en) | The manufacture method of printed circuit board (PCB) and printed circuit board (PCB) | |
| CN103080168B (en) | Method for producing photosensitive resin and photosensitive resin composition | |
| CN105733352A (en) | Photosensitive solder resist ink composition and circuit board | |
| JPH0532746A (en) | Resin composition, solder resist resin composition and their hardened material | |
| EP3243854B1 (en) | Low dk/df solder resistant composition used for printed circuit board | |
| CN110895381A (en) | Photosensitive solder resist ink composition, application thereof and circuit board containing same | |
| CN105086605B (en) | A kind of photocuring heat-curing composition ink, purposes and the wiring board containing it | |
| JP4844002B2 (en) | Acid pendant type epoxy acrylate resin composition | |
| US20020120031A1 (en) | Photothermosetting component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151014 |