CN108841235B - Composition for resisting oxygen resistance and improving surface curing degree of photo-curing ink and application - Google Patents
Composition for resisting oxygen resistance and improving surface curing degree of photo-curing ink and application Download PDFInfo
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- CN108841235B CN108841235B CN201810576150.5A CN201810576150A CN108841235B CN 108841235 B CN108841235 B CN 108841235B CN 201810576150 A CN201810576150 A CN 201810576150A CN 108841235 B CN108841235 B CN 108841235B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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Abstract
The invention provides a composition for resisting oxygen resistance and improving the surface curing degree of a photo-curing ink and application thereof. Wherein the composition comprises a silicone leveling agent and a thiol containing mercapto group. The invention improves the crosslinking degree of the ink by adopting the composition for resisting oxygen and/or improving the surface curing degree of the photo-curing ink, further improves the film retention rate of the ink, improves the adhesive force of the ink attached to the coated surface, improves the photosensitivity of the ink, improves the corrosion resistance and other chemical resistances.
Description
Technical Field
The invention belongs to the field of circuit board ink, and particularly relates to a composition for resisting oxygen resistance and improving the surface curing degree of photo-curing ink, a preparation method thereof and application thereof in a printed circuit board, belonging to a curing coating in an electronic material.
Background
The ultraviolet light cured paint (such as ink composition) is one kind of green paint with high efficiency and environment friendship, and is cured through the chain polymerization reaction between the active reactive matters initiated under the irradiation of ultraviolet light. Specifically, ultraviolet curing refers to a technology of instant polymerization crosslinking curing of an organic formulation material system under ultraviolet irradiation, mainly comprises a photocuring resin, a photocuring active diluent monomer and a photoinitiator, and is mainly applied to the fields of coatings, printing ink and adhesives. Compared with the traditional solvent-based thermosetting coating, the ultraviolet curing coating (such as the ink composition) has the advantages of low volatile organic compound emission, high curing speed, low energy consumption, wide applicability, high coating efficiency and the like, and can be widely applied to the fields of electronic assembly, printed circuit boards or mechanical coating and the like.
Recently, photo-curable thermosetting composition inks have been used in large quantities in the manufacture of printed circuit boards due to the requirements for light weight, thinness, and durability of electronic products. The photo-curing and thermosetting composition ink can be coated on a circuit board substrate by screen printing, roller coating, electrostatic spraying, air spraying and the like, then dried under the condition of good ventilation at 70-80 ℃, and irradiated by contact or non-contact selective light. The non-irradiated portions are then cleaned with a dilute aqueous alkali solution, which may be used is usually an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, or the like, and the irradiated portions remain on the substrate. The composition remaining on the base board is heat-cured at a temperature of 120 to 180 ℃ for 30 to 120 minutes to finally form an insulating heat-resistant protective solder resist coating on the wiring board.
However, in the known ultraviolet curing technology, although the curing speed is high, the surface of the ultraviolet curing coating always has non-negligible oxygen inhibition, so that the polymerization and crosslinking of the surface of the coating are insufficient, the wear resistance of the surface layer is insufficient, and even the surface may be sticky, sticky and the like.
"oxygen inhibition," as the name implies, refers to the inhibition of the polymerization reaction of the photocurable material by oxygen. When photocured in air, oxygen inhibition often leads to instances where the coating is primed, uncured and tacky. Oxygen inhibition can ultimately lead to the appearance of a large number of oxidative structures such as hydroxyl, carbonyl, peroxy and the like on the surface of the coating, thereby affecting the long-term stability of the coating and possibly even the properties such as hardness, glossiness, scratch resistance and the like of the cured paint film. Therefore, it is a trend of developing ultraviolet light curing coatings to overcome the defects that the polymerization inhibition of oxygen causes the limitation of deep curing and surface drying speed of ultraviolet light curing coatings, and the polymerization inhibition of oxygen causes the curing of the bottom layer of the coating and the adhesion of the uncured surface.
However, with the rapid development of LED light sources and direct imaging LDI technology in the light curing industry, the defect of "oxygen inhibition" is also obviously prominent. The reason is that the LED light source is a narrow-spectrum light source, the heat generated during photocuring is very little, the direct imaging LDI technology is a single-wavelength cold light source which is sensitive under a non-vacuum condition, and the LED light source and the LDI technology are all characterized by low power, extremely-fast curing requirement and the like, so that the oxygen inhibition defect of the photocuring ink is very obvious under the condition. Therefore, how to overcome the limitation of the "oxygen inhibition" effect on the surface curing of the uv-curable coating, the "oxygen inhibition" effect causes the coating surface to be uncured and sticky, and becomes the important solution for the uv-curable coating which can be used for LED light sources and direct imaging LDI technology.
Disclosure of Invention
The invention mainly solves the technical problems that: aiming at the problem that the ultraviolet curing ink is limited in deep curing, surface drying speed and surface performance due to the polymerization inhibition of oxygen at present, so that the bottom layer of a coating is cured and the surface is uncured and sticky, an ink composition of the composition for resisting oxygen resistance and improving the surface curing degree of the light curing ink, a preparation method of the ink composition and application of the ink composition are provided.
In order to solve the above technical problems and achieve the above technical effects, the present invention provides an ink composition for preparing an ink, the ink composition comprising a photosensitive resin, a photoinitiator, a thiol containing a mercapto group, and an organosilicon leveling agent.
The ink composition of the present invention may further optionally contain auxiliaries such as a diluent, a filler, a colorant, an epoxy resin curing accelerator, a thermal polymerization inhibitor, a thixotropic tackifier, a dispersant, a leveling agent, and a defoaming agent.
In another aspect, the present invention also provides the use of the ink composition, wherein the ink composition is used for preparing an ink and coating a substrate.
In another aspect, the invention also provides a circuit board with a film formed by coating the ink composition on a substrate.
The ink composition of the present invention contains the leveling agent having an unsaturated bond and the thiol having a mercapto group, and therefore, a film layer formed on various substrates has oxygen resistance, excellent photosensitivity and/or high hardness. Therefore, the invention also provides a composition for improving the oxygen resistance defect on the surface of the photo-cured ink and/or improving the curing degree of the surface of the photo-cured ink, wherein the composition comprises the organic silicon leveling agent and thiol containing sulfhydryl.
The invention also provides a method for resisting oxygen and/or improving the surface curing degree of the photo-curing ink, which comprises the step of adding the organic silicon leveling agent and the mercaptan containing the mercapto into the photo-curing ink composition.
According to the invention, the composition for resisting oxygen resistance and improving the surface curing degree of the photo-curing ink is adopted to improve the crosslinking degree of the ink, so that the corrosion resistance to acidity is improved, the surface film retention rate of the ink is improved, the adhesive force of the ink attached to the coated surface is improved, and the photosensitivity of the ink is improved.
Under the condition of photo-curing by applying a cold light source, the product yield of the circuit board of the ink layer of the composition for resisting oxygen resistance and improving the surface curing degree of the photo-curing ink is improved by 3-5%, especially the surface photosensitivity is improved by one or two grades, or the yield is improved by more than 10%.
Specifically, the invention provides a composition for improving the oxygen resistance defect on the surface of the photo-curing ink and/or improving the surface curing degree of the photo-curing ink, wherein the composition consists of an organic silicon leveling agent and thiol containing sulfhydryl.
Preferably, in the composition for improving the oxygen resistance defect on the surface of the photo-curing ink and/or increasing the curing degree of the surface of the photo-curing ink, the weight ratio of the organosilicon leveling agent to the thiol containing mercapto group is 1: 50-13: 1, preferably 1: 10-10: 1, and most preferably 5:1 or 5: 2.
Preferably, in the composition for improving the oxygen resistance defect on the surface of the photo-curable ink and/or increasing the degree of curing on the surface of the photo-curable ink, the thiol containing thiol is a thiol containing three or four or more thiol groups per molecule, and preferably, the thiol containing thiol is 1, 2, 4-tris (mercaptoethyl) benzene or 1, 2, 3-propanetrithiol; and/or the organic silicon leveling agent is a leveling agent containing two or more than three unsaturated bonds.
The invention also provides a composition for improving the oxygen resistance defect on the surface of the photo-curing ink and/or improving the curing degree of the surface of the photo-curing ink, wherein the composition consists of the organic silicon leveling agent, thiol containing sulfhydryl groups, dimethyldichlorosilane and tetrafluoroethylene, the weight ratio of the organic silicon leveling agent to the thiol containing sulfhydryl groups is 1: 50-13: 1, preferably 1: 10-10: 1, most preferably 5:1 or 5:2, and the mass ratio of the dimethyldichlorosilane to the tetrafluoroethylene is 1: 1.
Preferably, in the composition for improving the oxygen resistance defect on the surface of the photo-curing ink and/or improving the curing degree of the surface of the photo-curing ink, the sum of the mass of the dimethyldichlorosilane and the mass of the tetrafluoroethylene accounts for 10% of the total mass of the composition.
Preferably, in the composition for improving the oxygen resistance defect on the surface of the photo-curing ink and/or improving the curing degree of the surface of the photo-curing ink, the organic silicon leveling agent is BYK-3500, BYK3570 or BYK 371.
The invention also provides the application of the composition of the organic silicon leveling agent and the mercaptan containing the mercapto group in preparing the ink for improving the oxygen resistance defect on the surface of the photo-cured ink and/or improving the surface curing degree of the photo-cured ink.
The invention also provides ink for improving the surface oxygen resistance and the surface curing degree of the photo-curing ink, which is characterized in that the ink is prepared from raw materials containing the composition, and the weight of the composition accounts for 0.9-19% of the weight of the ink.
Preferably, in the above ink for improving oxygen resistance on the surface of a photo-curable ink and the degree of surface curing of the photo-curable ink, the raw materials further include:
A. 60-90% of photosensitive resin;
B. a photoinitiator, 0.5-15%, and
a plurality of raw materials selected from the group consisting of diluents, fillers, colorants, epoxy resin curing accelerators, thermal polymerization inhibitors, thixotropic tackifiers, dispersants, and defoamers.
The invention also provides a circuit board with a film layer formed by the ink for improving the oxygen resistance on the surface of the light-cured ink and the curing degree on the surface of the light-cured ink.
Detailed Description
In the present invention, unless otherwise specified, all operations are carried out at room temperature and normal pressure.
In the present invention, unless otherwise stated, the percentages or proportions of the components in the raw materials for preparing the ink are based on the total weight of the composition, and the sum of the percentages of the components is 100%.
The invention provides a raw material for preparing ink, which comprises
A. 60-90% of photosensitive resin;
B. 0.5-15% of photoinitiator;
C. 0.4-5 per mill of thiol containing sulfhydryl;
D. 0.1-10 per mill of organic silicon flatting agent;
the ink composition also optionally contains auxiliary agents such as a diluent, a filler, a colorant, an epoxy resin curing accelerator, a thermal polymerization inhibitor, a thixotropic tackifier, a dispersing agent, a defoaming agent and the like, wherein the total percentage of the components is 100 percent. .
In the present invention, the thiol group-containing thiol preferably contains 2 to 5 thiol groups per molecule, more preferably 3 to 4 thiol groups per molecule. Further preferably, the thiol containing thiol group is present in an amount of 0.5 to 2%, more preferably 0.8 to 1.5%, most preferably 1.0%.
In the present invention, the silicone-based leveling agent preferably contains an unsaturated bond, and more preferably the silicone-based leveling agent has an average of 2 or more unsaturated bonds per molecule, for example, 2, 3, 4, 5, 6, 7, 8, 9, or 10 unsaturated bonds. Further preferably, the content of the leveling agent containing unsaturated bonds is 0.1 to 10%, more preferably 1 to 9%, 2 to 8%, 3 to 7%, or 4 to 6%, most preferably 5%. The leveling agent containing at least 2 unsaturated bonds is BYK-3500, BYK3570 or BYK371, or the combination of at least two of BYK-3500, BYK3570 and BYK 371.
The invention also provides the use of the ink composition, wherein the ink composition is used for coating a substrate after being prepared into an ink.
In the use of the ink composition of the present invention, the ink composition of the present invention may be coated on a substrate surface. Optionally, the coating can be screen printing, roll coating, electrostatic spraying, air spraying. Further, the substrate may be a substrate of glass, plastic or the like, and is preferably a circuit board. For screen printing, for example, the methods disclosed in CN101355854A, TW200906627A, CN106793534A and CN106793535A may be employed; for roll coating printing, the method disclosed in CN1186127C, for example, can be employed.
In another aspect, the present invention also provides a substrate comprising a film layer formed from the ink composition, wherein the substrate is preferably a circuit board.
Therefore, the present invention also provides a composition for improving the oxygen resistance defect on the surface of the photo-cured ink and/or increasing the degree of curing on the surface of the photo-cured ink, wherein the composition comprises a silicone leveling agent and a thiol containing a mercapto group, wherein the weight ratio of the silicone leveling agent to the thiol containing a mercapto group is 1: 50 to 13: 1, preferably 1: 10 to 10: 1, and most preferably 5: 1.
In the present invention, the photosensitive resin may be a photosensitive resin containing both a carboxyl group and at least two ethylenically unsaturated bonds in the molecule, and the photosensitive resin may be synthesized by any one of the following methods disclosed in the applicant's patent 200810004765.7:
(1) carrying out esterification reaction on an epoxy compound (a) with a polyfunctional group containing more than two epoxy groups in a molecule and an unsaturated monocarboxylic acid (b), and reacting the obtained esterified compound with a saturated or unsaturated polybasic acid anhydride (c), wherein the weight ratio of a to b to c is 3: 1 to 5: 2;
(2) (meth) acrylic acid and other comonomers (d) having ethylenically unsaturated bonds are reacted to form a copolymer and partially reacted with glycidyl (meth) acrylate, wherein the copolymer has a molar ratio of carboxyl groups to glycidyl (meth) acrylate of from 7: 2 to 6: 1;
(3) reacting a copolymer of glycidyl (meth) acrylate and other comonomer (d) having an ethylenically unsaturated bond with an unsaturated monocarboxylic acid (b) and reacting the resultant product with a saturated or unsaturated polybasic acid anhydride (c);
(4) reacting (a) a polyfunctional epoxy compound having two or more epoxy groups in a molecule, (b) an unsaturated monocarboxylic acid with (e) a compound having at least two hydroxyl groups in a molecule and having one other group reactive with an epoxy group to produce an intermediate (I), and reacting the intermediate with (c) a saturated or unsaturated polybasic acid anhydride;
(5) reacting an unsaturated polybasic acid anhydride and an aromatic hydrocarbon having a vinyl group to form a copolymer, and then reacting with a hydroxyalkyl (meth) acrylate; or
(6) The intermediate (I) described in the method (4) is further reacted with a saturated or unsaturated polybasic acid anhydride (c) and a monoisocyanate (f) containing an unsaturated group.
The proportions of the reactants may be arbitrarily adjusted as required, except for the compounds having the specifically defined ranges. Examples of the epoxy compound (a) usable in the above methods (1) and (4) include: bisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol s type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol a novolak type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, triphenol methane type epoxy resin, and N-glycidyl type epoxy resin. The epoxy compounds may be used alone or in combination of two or more. Among these epoxy compounds, novolak epoxy resins, cresol novolak epoxy resins, and bisphenol A novolak epoxy resins are preferably used because they can provide solder resist films having excellent solder heat resistance, chemical resistance, and the like.
Examples of the unsaturated monocarboxylic acid (b) usable in the above-mentioned methods (1), (3) and (4) include: acrylic acid, acrylic acid dimer, methacrylic acid, β -styrylacrylic acid, β -furfurylacrylic acid, crotonic acid, α -cyanocinnamic acid, cinnamic acid, and half esters of reactants of saturated or unsaturated dibasic anhydrides and (meth) acrylates containing one hydroxyl group in the molecule or reactants of saturated or unsaturated dibasic acids and unsaturated monoglycidyl compounds. Among these unsaturated monocarboxylic acids, acrylic acid or methacrylic acid is preferably used in view of photocurability.
Examples of the saturated or unsaturated polybasic acid anhydride (c) usable in the above-mentioned processes (1), (3), (4) and (6) include: dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methano-endo-tetrahydrophthalic anhydride, methylmethano-endo-tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride; aromatic polycarboxylic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic dianhydride; and 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, and similar polycarboxylic anhydride derivatives. These saturated or unsaturated polybasic acid anhydrides may be used singly or in admixture of two or more. In view of the characteristics of the cured coating film, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and succinic anhydride are preferably used. The polybasic acid anhydride (c) is preferably used in such an amount that the acid value of the reaction product is 50 to 150 mgKOH/g.
Examples of other comonomers (d) having an ethylenically unsaturated bond that can be used in the above-mentioned methods (2) and (3) include: styrene, chlorostyrene, alpha-methylstyrene; acrylic or methacrylic esters substituted with methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amino, 2-ethylhexyl, octyl, decanoyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isobornyl, methoxyethyl, butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-chloro-2-hydroxypropyl; monoacrylates or monomethacrylates of polyethylene glycol, or monoacrylates or monomethacrylates of polypropylene glycol; vinyl acetate, vinyl butyrate or vinyl benzoate; acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl acrylamide, acrylonitrile, maleic anhydride, or the like. These comonomers (d) may be used alone or in combination of two or more.
Examples of the compound (e) usable in the above-mentioned methods (4) and (6) include: polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, dimethylolcaproic acid and the like; and dialkanolamines such as diethanolamine and diisopropanolamine. These compounds (e) may be used alone or in combination of two or more.
In the method (4), the total amount of the unsaturated monocarboxylic acid (b) and the compound (e) is preferably about 0.8 to 1.3 molar equivalents, particularly preferably about 0.9 to 1.1 molar equivalents, relative to 1 molar equivalent of the epoxy group of the epoxy compound (a). Wherein the molar equivalent of compound (e) is from 5 to 50%, particularly preferably from 10 to 30%, of the total amount of (b) and (e). For the reaction of the intermediate (I) and the polybasic acid anhydride (c), it is preferable that 1 molar equivalent of hydroxyl group and 0.1 to 0.9 molar equivalent of the polybasic acid anhydride (c) are reacted with respect to the hydroxyl group in the intermediate (I).
Examples of the unsaturated monoisocyanate (f) usable in the above-mentioned method (4) include: methacryloyloxyethyl isocyanate or organic diisocyanate and (meth) acrylic acid having one hydroxyl group in the molecule in an approximately equimolar ratio. These unsaturated monoisocyanates (f) may be used alone or in combination of two or more.
The photosensitive resin is not limited to the above, and different photosensitive resins may be mixed and used.
The photoinitiator in the present invention is not particularly limited, and examples thereof include: benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone and 1, 1-dichloroacetophenone; ketoxime esters such as 1- (6-O-methylbenzoyl-9-ethyl-9. H. -carbazol-3-yl) -ethanone oxime-O-acetate and 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime); aminoacetophenones such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and N, N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2, 4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; organic peroxides such as benzoyl peroxide and cumyl peroxide; thiol compounds such as 2, 4, 5-triarylimidazole dimer, riboflavin tetrabutyl ester, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; organic halides such as 2, 4, 6-tris-s-triazine, 2, 2, 2-tribromoethanol, tribromomethylphenyl ketone, and the like; benzophenones such as benzophenone and 4, 4' -bisdiethylaminobenzophenone, or thioxanthones; 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide, and the like, and the above-mentioned ultraviolet light photoinitiator may be used alone or in a mixture of two or more. The photoinitiator may further include a tertiary amine photoinitiator aid selected from ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, amyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, and the like. Wherein the photoinitiator is used in an amount of 0.5 to 15%, preferably 1 to 10%, based on the total weight of the composition of the present invention.
The diluent in the present invention may be an organic solvent, for example: 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, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, etc.; esters such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and dipropylene glycol monobutyl ether acetate; and commonly used ketone solvents such as butanone, cyclohexanone, isophorone; aromatic solvents such as toluene, xylene, tetramethylbenzene; and petroleum solvents such as naphtha, oxidized naphtha, solvent naphtha, etc., and these solvents may be used alone or in combination of two or more.
In addition, the diluent in the present invention may also be a photopolymerizable monomer, for example: hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate; monofunctional (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and lauryl (meth) acrylate; bifunctional (meth) acrylates such as 1, 6-hexanediol bis (meth) acrylate, dipropylene glycol bis (meth) acrylate, diethylene glycol bis (meth) acrylate, ethoxylated bisphenol a bis (meth) acrylate, and neopentyl glycol diethoxy/propoxy bis (meth) acrylate; polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; and ethoxylated polyfunctional acrylates and propoxylated polyfunctional acrylates, and the like, and the above-mentioned compounds may be used alone or in a mixture of two or more.
In the composition of the present invention, the photopolymerizable monomer or the organic solvent may be used alone or may be used together with the diluent. Alternatively, the diluent is used in an amount of 5 to 70% by weight based on the total weight of the composition of the present invention, and can be appropriately adjusted by those skilled in the art according to the needs of the coating method.
The ink compositions of the invention may also comprise customary fillers, in particular inorganic fillers, such as: barium sulfate, barium titanate, calcium dioxide, talcum powder, fumed silica, silicon dioxide, clay, magnesium carbonate, calcium carbonate, alumina, mica powder, kaolin and the like. The fillers are used in an amount of 0 to 40% by weight, based on the total weight of the composition according to the invention, and have a particle size of < 15 μm, preferably < 5 μm.
The ink composition of the present invention may further contain a commonly used colorant, examples of which include: phthalocyanine green, phthalocyanine blue, crystal violet, titanium dioxide, carbon black, and the like, and these may be used alone or in a mixture of two or more. Wherein the coloring agent is used in an amount of 0 to 20%, preferably 0 to 10%, based on the total weight of the composition of the present invention.
The ink composition of the present invention may further optionally contain one or more additives of an epoxy resin curing accelerator, a thermal polymerization inhibitor, a thixotropic tackifier, a dispersant, an antifoaming agent, and the like. The total weight of the various additives is 0 to 40%, preferably 0 to 10%, of the total weight of the composition of the invention.
The ink composition of the present invention is obtained by mixing the components. If not used immediately after formulation, it is preferably stored protected from light to avoid curing. Of course, the photoinitiator can also be placed separately and mixed with the other components at the time of use.
In addition, the invention also provides the application of the ink composition in forming a film layer on a substrate by a conventional coating method. The ink composition has excellent moldability, developability, and photosensitivity on a substrate. The substrate of the substrate may be metal, plastic or other materials, such as Indium Tin Oxide (ITO) film, chrome material, copper material, aluminum material, glass, polyethylene terephthalate (PET), polypropylene (PP), and the like. In use, the ink composition is directly applied (e.g., spray coating, flow coating, roll coating, wire bar coating, screen printing, etc.) to the surface of a substrate and cured by 365nm ultraviolet radiation.
The invention also provides the use of a combination of a silicone levelling agent and a thiol containing a mercapto group in the preparation of a composition for the inhibition of oxygen and/or increasing the degree of surface cure of a photo-curable ink.
The invention also provides a method for resisting oxygen and/or improving the surface curing degree of the photo-curing ink, which comprises the step of adding the organic silicon flatting agent and the mercaptan containing the mercapto into the photo-curing ink.
The invention improves the crosslinking degree of the ink by adopting the composition for resisting oxygen and improving the surface degree of the photo-curing ink, further improves the film retention rate of the ink, improves the adhesive force of the ink attached to the coated surface, improves the photosensitivity of the ink, improves the corrosion resistance and other chemical resistances.
Examples
Resin Synthesis example
Synthesis example 1 (photosensitive resin 1)
200g of phenolic epoxy resin CNE-202 (epoxy equivalent 210, Techongchun shogaku works, Taiwan), 250g of propylene glycol methyl ether acetate (PMA) and 69g of acrylic acid are added into a reactor, heated and melted, then 0.5g of hydroquinone and 1.5g of triphenylphosphine are added, and the mixture reacts for 12 hours at 110 ℃ to obtain a product with the acid value of less than 5. Then, 85g of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 100 ℃ to react for 6 hours, thereby obtaining pale yellow resin solution A1 (photosensitive resin 1) having an acid value of 52mgKOH/g, a solid content of 59% and an Mw of about 2000.
Synthesis example 2 (photosensitive resin 2)
Methyl methacrylate, butyl methacrylate and acrylic acid were added to a reactor at a molar ratio of 1: 2, carbitol acetate was used as a solvent, Azobisisobutyronitrile (AIBN) was used as a catalyst, and the mixture was stirred at 80 ℃ for 4 hours to obtain a resin solution. Cooling the resin solution, using methyl hydroquinone as a polymerization inhibitor and tetrabutyl phosphonium bromide as a catalyst, carrying out addition reaction with the glycidyl (meth) acrylate at the temperature of 90-105 ℃, wherein the molar ratio of resin carboxyl to the glycidyl (meth) acrylate is 5:1, carrying out the reaction for 16 hours, and taking out the resultant resin solution after cooling. In the obtained resin solution A2 (photosensitive resin 2), the acid value of the solid content was 120mgKOH/g, the solid content was 65%, and the Mw was about 15000.
Combined preparation examples
Combined preparation example 1:
1, 2, 3-propanetrithiol and BYK-3500 (from Bike chemical company) were mixed and mixed in a weight ratio of 1: 5 to obtain composition 1 (referred to as "composition 1" for short) having improved oxidation resistance and surface curing degree of photocurable ink.
Combined preparation example 2:
1, 2, 4-tris (mercaptoethyl) benzene and BYK-3500 (from Bike chemical company) were mixed and mixed in a weight ratio of 1: 5 to obtain composition 2 (referred to as "composition 2" for short) having improved oxidation resistance and surface curing degree of photocurable ink.
Combined preparation example 3:
1, 2, 4-tris (mercaptoethyl) benzene and BYK3570 (available from Bikk chemical Co.) were mixed and mixed in a weight ratio of 2: 5 to obtain composition 3 (referred to as "composition 3" for short) having an improved surface curing degree of a photocurable ink against oxygen.
Combined preparation example 4:
1, 2, 3-propanetrithiol and BYK3570 (available from Bick chemical Co.) were mixed and blended at a weight ratio of 2: 5 to obtain composition 4 (referred to as "composition 4" for short) which resists oxygen and improves the degree of surface cure of the photocurable ink.
Preparation examples 5 to 6 were combined:
on the basis of the combinations 1 and 2 prepared in the combination preparation examples 1-2, a mixture of dimethyldichlorosilane and tetrafluoroethylene in a mass ratio of 1:1 was further added and mixed uniformly, and the mixture accounted for 10% of the total mass, to obtain a composition 5 (referred to as "combination 5" for short) and a composition 6 (referred to as "combination 6" for short) which were resistant to oxygen and improved in the degree of surface curing of the photo-curable ink.
Ink preparation example:
inks 1 to 6 and comparative inks 1 to 2 were prepared respectively by accurately weighing the respective materials in the ink raw materials in the weight ratios listed in table 1 in a container, dispersing the materials for 15 minutes by a high-speed dispersing machine with stirring at a speed of 500 rpm, and then grinding the composition three times with a three-roll grinder so that the fineness of the composition was less than 15 μm, the compounding weights of each ink and the raw materials for preparing the inks being as shown in table 1 below.
Table 1: ingredient batching table in ink preparation raw materials
Note:
photosensitizer ITX: isopropyl thioxanthone, available from Tianjin Jiu chemical Co., Ltd;
photosensitizer 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, available from the Lichi trade of Guangzhou;
DPHA: multifunctional monomer EM267 of taiwan changxing chemical industry;
silicon dioxide: degussa fumed silica R974;
defoaming agent: foamcx N defoamer from dega corp, germany.
The application example is as follows: preparation of ink comprising composition and Performance testing thereof
The above-mentioned inks 1 to 6 and comparative inks 1 to 2 were subjected to performance tests, and were numbered as application examples 1 to 6 and comparative examples 1 to 2, respectively. The ink was evaluated for developability, film retention, photosensitivity, adhesion, and corrosion resistance. The evaluation methods were as follows, and the evaluation results are shown in table 2.
1. Developing property:
coating the ink of the composition of the embodiment on a prepared clean substrate by using a 15-micrometer wire rod, controlling the coating thickness to be 15 micrometers, placing the substrate into a 90-DEG C constant-temperature ventilation drying oven after coating, pre-drying for 10 minutes, irradiating and curing the substrate containing the ink for 15 seconds under an LED light source with the wavelength of 405nm, wherein the power is 10 percent, and the lamp distance is about 12cm, so that the ultraviolet curing ink is cured on the surface of the substrate. Then, a conventional circuit board development method (developer solution of 1% Na) was used2CO3Aqueous solution, the temperature of the developing solution is 30 ℃, the spraying pressure of the developing solution is 1.5kg/cm 2) for 1 minute, the sample plate is cleaned by deionized water, and the sample plate is dried by hot air. The developing effect of the ink after pre-drying is visually detected, and the evaluation method comprises the following steps:
the copper surface is completely developed to be clean; the copper surface has a slight white mist which is good; the development of the copper surface was poor due to severe white fog. The results are shown in Table 2.
2. Film retention rate:
coating the ink on a 5X5cm substrate by using a 15-micrometer wire rod, controlling the coating thickness to be 15 micrometers, placing the coated substrate into a 90-DEG C constant-temperature ventilation drying oven, pre-drying for 10 minutes, placing the dried substrate containing the ink on an LED light source with the wavelength of 405nm, wherein the power is 10%, the lamp distance is about 12cm, and multiplying the 50% exposure time after development by the UV illumination intensity to obtain the sensitivity. After weighing with a one-ten-thousandth balance (to an accuracy of 0.1mg), the conventional circuit board development method is used (the developer is 1% Na)2CO3Aqueous solution at a developer temperature of30 ℃, the spraying pressure of the developing solution is 1.5kg/cm 2), cleaning the sample plate with deionized water, drying with hot air, cooling, and weighing to constant weight. The film remaining rate was calculated by referring to the following formula, and the average value of 3 experiments was taken as the film remaining rate of the ink.
Film retention rate (M)t-M0)/(M1-M0)×100％
Wherein: mtDeveloping the dried substrate quality after the exposure time t;
M0is the quality of the blank substrate;
M1the quality of the inked unexposed substrate.
Evaluation criteria: the higher the residual film rate, the better the curing effect of the ink.
3. Photosensitivity:
coating the ink of the composition of the embodiment on a prepared clean substrate by using a 15-micrometer wire rod, controlling the coating thickness to be 15 micrometers, placing the substrate into a 90-DEG C constant-temperature ventilation drying oven after coating, pre-drying for 10 minutes, placing a 21-grade optical gradient ruler on the dried substrate containing the ink, placing the substrate under an LED light source with the wavelength of 405nm, setting the power to be 10 percent and the lamp distance to be about 12cm, and irradiating and curing for 15 seconds to enable the ultraviolet curing ink to be cured on the surface of the substrate. Then, a conventional circuit board development method (developer solution of 1% Na) was used2CO3Aqueous solution, the temperature of the developing solution is 30 ℃, the spraying pressure of the developing solution is 1.5kg/cm 2) for 1 minute, the sample plate is cleaned by deionized water, and the sample plate is dried by hot air. And visually detecting the number of the position where the ink coating is left on the optical gradient ruler, namely the sensitivity of the combined ink.
Evaluation criteria: the larger the number of the residual film, the better the sensitivity and the higher the degree of crosslinking.
A sample for evaluation of properties such as adhesion and corrosion resistance was prepared in the same manner as the photosensitive sample.
4. Adhesion:
according to the standard of the scratch test for GBT9286-1998 color and clear paint films, 1cm is put on the coating by a hundred grid knife2The coating is divided into 100 lattices on average and 1mm2Small case, scratch should be scribedAnd (3) penetrating the coating, adhering an 1/2-inch wide No. 3M brand 600 pressure-sensitive adhesive tape to the surface of the coating, forcibly pulling the adhesive tape off by the force of forming an angle of 90 degrees between the adhesive tape and the coating, observing whether the coating is adhered on the adhesive tape to fall off or not, and judging that the adhesion of the coating is excellent within 5 percent and poor above 5 percent. Recorded in table 2.
5. Corrosion resistance:
and (3) placing the prepared sample plate in an aqueous solution with the sulfuric acid content of 155g/l, the hydrogen peroxide content of 30g/l and the benzene sulfonic acid phenol content of 12g/l, soaking for 15 minutes at the temperature of 45 +/-2 ℃, then taking out and washing cleanly, drying by hot air, observing whether the cured ink coating falls off or whether the coating is layered or cracked, and judging whether the cured coating has excellent corrosion resistance or not, wherein the cured coating has no fall off, no layered or cracked completely.
Table 2: evaluation results of developability, film-remaining rate, photosensitivity, adhesion, and etching resistance of the ink
Although the present invention has been described in the above-mentioned embodiments, it is to be understood that the present invention may be further modified and changed without departing from the spirit of the present invention, and that such modifications and changes are within the scope of the present invention.
Claims (4)
1. The composition comprises an organic silicon leveling agent, mercaptan containing sulfydryl, dimethyldichlorosilane and tetrafluoroethylene, wherein the weight ratio of the organic silicon leveling agent to the mercaptan containing sulfydryl is 5:1 or 5:2, the mass ratio of the dimethyldichlorosilane to the tetrafluoroethylene is 1:1, the sum of the mass of the dimethyldichlorosilane and the mass of the tetrafluoroethylene accounts for 10% of the total mass of the composition, the mercaptan containing sulfydryl is 1, 2, 4-tris (mercaptoethyl) benzene or 1, 2, 3-propanetrithiol, and the organic silicon leveling agent is BYK-3500, BYK3570 or BYK 371.
2. Use of the composition of claim 1 for preparing an ink that improves oxygen resistance defects on the surface of a photo-curable ink and increases the degree of surface cure of the photo-curable ink.
3. An ink for improving the surface oxygen resistance and the surface curing degree of a photo-curing ink, which is characterized in that the ink is prepared from a raw material containing the composition of claim 1, the weight percentage of the composition in the ink is 0.9-19%, and the raw material further contains:
A. 60-90% of photosensitive resin;
B. a photoinitiator, 0.5-15%, and
a plurality of raw materials selected from the group consisting of diluents, fillers, colorants, epoxy resin curing accelerators, thermal polymerization inhibitors, thixotropic tackifiers, dispersants, and defoamers.
4. A circuit board having a film layer formed from the ink of claim 3.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004211025A (en) * | 2003-01-08 | 2004-07-29 | Jsr Corp | Coating composition |
| CN105175622A (en) * | 2015-07-31 | 2015-12-23 | 安徽嘉智信诺化工股份有限公司 | Reaction-type paint, auxiliary agent for printing ink and synthetic method |
| CN106700894A (en) * | 2016-12-30 | 2017-05-24 | 中科院广州化学有限公司南雄材料生产基地 | Ultraviolet-curable coating with oxygen inhibition resistance, and preparation method thereof |
| CN106750318A (en) * | 2016-12-08 | 2017-05-31 | 天津久日新材料股份有限公司 | A kind of amino-contained silicone acrylates and its preparation method and application |
| CN107418505A (en) * | 2017-07-18 | 2017-12-01 | 江西绿洲环保新材料股份有限公司 | Ultraviolet light solidification sulfydryl/alkene organosilicon adhesive and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348634B (en) * | 2007-07-20 | 2010-08-04 | 北京化工大学 | Photo-curing ink-jet nano conductive printing ink, and preparation and use method thereof |
| CN101465408B (en) * | 2008-12-31 | 2010-12-29 | 电子科技大学 | Substrate for flexible organic optoelectronic device and preparation method thereof |
| CN101916813A (en) * | 2010-07-09 | 2010-12-15 | 电子科技大学 | Light-emitting diode (LED) and preparation method thereof |
| CN107109096A (en) * | 2014-10-31 | 2017-08-29 | 旭硝子株式会社 | Powder coating composition, powder coating and coated article |
| CN105919831A (en) * | 2016-06-22 | 2016-09-07 | 上海零玖科技有限公司 | Scrubbing-free photocuring nail polish gel |
-
2018
- 2018-06-05 CN CN201810576150.5A patent/CN108841235B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004211025A (en) * | 2003-01-08 | 2004-07-29 | Jsr Corp | Coating composition |
| CN105175622A (en) * | 2015-07-31 | 2015-12-23 | 安徽嘉智信诺化工股份有限公司 | Reaction-type paint, auxiliary agent for printing ink and synthetic method |
| CN106750318A (en) * | 2016-12-08 | 2017-05-31 | 天津久日新材料股份有限公司 | A kind of amino-contained silicone acrylates and its preparation method and application |
| CN106700894A (en) * | 2016-12-30 | 2017-05-24 | 中科院广州化学有限公司南雄材料生产基地 | Ultraviolet-curable coating with oxygen inhibition resistance, and preparation method thereof |
| CN107418505A (en) * | 2017-07-18 | 2017-12-01 | 江西绿洲环保新材料股份有限公司 | Ultraviolet light solidification sulfydryl/alkene organosilicon adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 巯基/烯紫外光聚合反应体系的研究及其应用;郭银明等;《中国胶粘剂》;20080630;第17卷(第6期);第53-56页 * |
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