CN105733352B - Photosensitive solder resist ink composition and circuit board - Google Patents
Photosensitive solder resist ink composition and circuit board Download PDFInfo
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- CN105733352B CN105733352B CN201610113555.6A CN201610113555A CN105733352B CN 105733352 B CN105733352 B CN 105733352B CN 201610113555 A CN201610113555 A CN 201610113555A CN 105733352 B CN105733352 B CN 105733352B
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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
-
- 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention relates to a photosensitive solder resist ink composition. The composition comprises (A) photosensitive resin, of which a molecule contains both a carboxyl group and at least two olefinic unsaturated bonds, (B) a photoinitiator, (C) an organic surface auxiliary containing a reactive functional group, (D) an organic solvent, (E) a thermosetting component, (F) a photopolymerizable monomer and (G) an inorganic filler, wherein, based on the total amount of 100 parts by weight of solid components of the photosensitive resin (A), the content of the organic surface auxiliary (C) containing the reactive functional group is 0.1 to 30 parts by weight. In addition, the invention further relates to a circuit board comprising a cured film formed by the photosensitive solder resist ink composition. The cured film formed by the photosensitive solder resist ink composition on the circuit board has stable surface tension, so that the solderability of the circuit board is improved.
Description
Technical field
The present invention relates to a kind of new light sensitive anti-solder ink composition and comprising the wiring board by its cured film for being formed.
Background technology
In printed substrate, electronic component is soldered to which by methods such as wave-soldering, Reflow Solderings and is pre-formed with conduction
The weld zone of the printed circuit base material of circuit pattern, and all circuit regions outside weld zone are by as the anti-welding of permanent protecting film
Cured film is covered.So, when electronic component is welded on printed substrate, so that it may which avoiding solder from being bonded at need not be covered by solder
On the region of lid, simultaneously because anti-welding cured film has excellent electric insulating quality, it is also possible to effectively prevent short circuit etc.
The generation of electric fault.
During high-precision circuit board is prepared, light sensitive anti-solder ink is by the side such as silk screen printing, spraying, dip-coating and roller coat
Method is coated with the circuit board.Due to having many irregular figures and dense wire on wiring board, it is therefore desirable to light sensitive anti-solder ink
With good wettability and levelability, so that light sensitive anti-solder ink can be fully filled irregular figure and dense wire
In.The solidification formed by light sensitive anti-solder ink is required also in order to ensure electric property after light sensitive anti-solder ink is dried simultaneously
Film surfacing, can not there are dew copper, shrinkage cavity, the defect such as bubble.In order to realize these requirements, need to combine in light sensitive anti-solder ink
Containing the organic surface modifier with effects such as froth breaking, levelling, dispersions in thing, to avoid producing the problems referred to above.In light sensitive anti-solder
After Ink Application and drying, in this way it is no longer necessary to the effect of these organic surface modifiers.However, these organic surface modifiers exist
Cured film surface can be also constantly gathered in high-temperature baking, wave-soldering and reflow process, is made under the surface tension of cured film
Drop simultaneously produces pollution to pad, so as to the rosin flux generation used during causing wave-soldering, Reflow Soldering paster is certain
Shrink.At part particularly in pad with cured film EDGE CONTACT, the contraction of the Colophonium auxiliary agent at this is projected the most, so as to lead
Send a telegraph subcomponent and occur certain defect after paster, and then produce the problems such as electric property declines, electronic component is easy to fall off.
Accordingly, it is desirable to provide a kind of be suitable to printed substrate and had by its cured film for being formed stable capillary
Light sensitive anti-solder ink.
The content of the invention
To solve the above problems, the present invention provides a kind of light sensitive anti-solder ink composition, and which includes：
(A) photoresist, contains carboxyl and at least two ethylenic unsaturated bonds simultaneously in its molecule,
(B) light trigger,
(C) the organic surface modifier containing reactive functional groups,
(D) organic solvent,
(E) thermosetting component,
(F) photo polymerization monomer, and
(G) inorganic filler；
The solid constituent meter of photoresist (A) wherein, based on 100 weight portions, the having containing reactive functional groups
The content of machine surface modifier (C) is 0.1 to 30 weight portion.
Additionally, the present invention also provides a kind of circuit comprising the cured film formed by above-mentioned light sensitive anti-solder ink composition
Plate.
The cured film for being formed by the light sensitive anti-solder ink composition of the present invention in the circuit board has stable surface tension,
So that the wiring board has improved solderability.
Specific embodiment
The preferred embodiments of the invention are will be described below.Although the disclosed embodiments are for the purpose of illustration,
It should be understood that the invention is not restricted to this, and those skilled in the art are in the case of without departing from the scope of the present invention and essence, can
Various modifications, increase are carried out to the present invention and is replaced.
In the present invention, acid number means the income value measured by the acid-base titrations by means of KOH standard solution, viscosity
It is measured according to GB/T 7193-2008 unsaturated polyester resin test methods, solid content is according to GB/T 7193-2008 insatiable hungers
It is measured with polyester resin test method.
According to the first aspect of the invention, there is provided a kind of light sensitive anti-solder ink composition, which includes：
(A) photoresist, contains carboxyl and at least two ethylenic unsaturated bonds simultaneously in its molecule,
(B) light trigger,
(C) the organic surface modifier containing reactive functional groups,
(D) organic solvent,
(E) thermosetting component,
(F) photo polymerization monomer, and
(G) inorganic filler；
The solid constituent meter of photoresist (A) wherein, based on 100 weight portions, the having containing reactive functional groups
The content of machine surface modifier (C) is 0.1 to 30 weight portion.
In a preferred embodiment in accordance with this invention, the solid constituent acid number of the photoresist (A) be 50 to
150mgKOH/g, its can by the following method in any one method prepare：
(1) there is in making molecule multi-functional epoxy compound (a) and the unsaturated monocarboxylic (b) of two or more epoxy radicals
Esterification is carried out, then the carboxylate for obtaining is reacted with saturation or undersaturated multi-anhydride (c)；
(2) comonomer (d) reaction that (methyl) acrylic acid has ethylenic unsaturated bond with other is formed into copolymer, so
Afterwards the copolymer obtained by a part is reacted with (methyl) glycidyl acrylate；
(3) being total to (methyl) glycidyl acrylate and other comonomer (d) with ethylenic unsaturated bond
Polymers is reacted with unsaturated monocarboxylic (b), then will be the product of gained anti-with saturation or undersaturated multi-anhydride (c)
Should；
(4) there is in making molecule multi-functional epoxy compound (a), the unsaturated monocarboxylic (b) of two or more epoxy radicals
Can obtain with the reaction of the compound (e) of the other groups of epoxy reaction containing at least two hydroxyls and with one with molecule
Intermediate (I) is then reacted by intermediate (I) with saturation or undersaturated multi-anhydride (c)；
(5) unsaturated multi-anhydride and the aromatics hydrocarbon reaction with vinyl is made to form copolymer, then being total to gained
Polymers and hydroxyalkyl (methyl) acrylate reactions；Or
(6) by the intermediate (I) obtained by method (4) and saturation or undersaturated multi-anhydride (c) and contain unsaturated group
Monoisocyanates (f) reaction of group.
In a preferred embodiment of the invention, there are two or more in the molecule in methods described (1) and (4)
The multi-functional epoxy compound (a) of epoxy radicals can be bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol-f type ring
The solvable epoxy resin of oxygen tree fat, bisphenol-s epoxy resin, novolac epoxy resins, cresol, bisphenol-A it is solvable fusible
Epoxy resin, united phenol-type epoxy resin, di- toluene phenol-type epoxy resin, triphenol methylmethane type epoxy resin and N- shrink sweet
Oil type epoxy resin.When the novalac using novolac epoxy resins, the solvable epoxy resin of cresol and bisphenol-A
During resin, the anti-welding cured film with the performance such as excellent scolding tin thermostability and chemical resistance can be obtained, therefore is preferably used
The novalac epoxies of the solvable epoxy resin of novolac epoxy resins, cresol and bisphenol-A.Have in the molecule
The multi-functional epoxy compound of two or more epoxy radicals can be used alone or be used in the form of its mixture.
In a preferred embodiment of the invention, the unsaturated monocarboxylic (b) in methods described (1), (3) and (4)
Can for acrylic acid, acrylic acid dimer, methacrylic acid, β-styrene acrylic, β-furfuryl acrylic acid, butenoic acid, α-
Cyano cinnamic acid, cinnamic acid, and saturation or unsaturated dicarboxylic acid anhydride and (methyl) acrylic acid containing a hydroxyl in molecule
The product of the product or saturation of ester or unsaturated dibasic acid and unsaturated list glycidyl compound.In view of light is solid
The property changed, preferred acrylic or methacrylic acid.
In a preferred embodiment of the invention, the saturation or unsaturation in methods described (1), (3), (4) and (6)
Multi-anhydride (c) can be：Dibasic acid anhydride, such as maleic anhydride, succinic anhydrides, itaconic anhydride, phthalic anhydride, tetrahydrochysene are adjacent
Phthalate anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methano-interior-tetrabydrophthalic anhydride, first
Base methano-interior-tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride etc.；Polybasic aromatic carboxylic acid's acid anhydride, such as trimellitic acid
Acid anhydride, pyromellitic dianhydride, benzophenone tetrabasic carboxylic acid dicarboxylic anhydride etc.；And 5- (2,5- dioxidotetrahydro furyls) -3- methyl -3-
Cyclohexene -1,2- dicarboxylic anhydrides, and its polybasic acid anhydride derivant.In view of the characteristic of cured film, preferred tetrahydrophthalic acid
Acid anhydride, hexahydrophthalic anhydride and succinic anhydrides.The saturation or undersaturated multi-anhydride can be used alone or with its mixing
The form of thing is used.
In a preferred embodiment of the invention, the consumption of the saturation or undersaturated multi-anhydride (c) is to make
The acid number of the solid constituent of product is the amount of 50 to 150mgKOH/g.When the acid number of the solid constituent of product is less than
During 50mgKOH/g, the alkali-solubility of the light sensitive anti-solder ink composition is poor, and the cured film of gained is difficult in subsequent alkene alkali
Develop in aqueous solution.However, when the acid number of the solid constituent of product is more than 150mgKOH/g, the cured film of gained it is anti-
Developing performance is poor, or even can not form sometimes anti-welding cured film.
In a preferred embodiment of the invention, the others in methods described (2) and (3) have olefinic unsaturated
The comonomer (d) of key can be styrene, chlorostyrene, α-methyl styrene；By methyl, ethyl, propyl group, isopropyl, positive fourth
Base, isobutyl group, the tert-butyl group, amino, 2- ethylhexyls, octyl group, caprinoyl, nonyl, decyl, dodecyl, cetyl, octadecane
Base, cyclohexyl, isobornyl, methoxy ethyl, butoxyethyl group, 2- hydroxyethyls, 2- hydroxypropyls and 3- chlorine-2-hydroxyls third
Acrylate or methacrylate that base replaces；The mono acrylic ester or monomethacrylates of Polyethylene Glycol or poly- third
The mono acrylic ester or monomethacrylates of glycol；Vinyl acetate, vinyl butyrate or vinyl benzoate；Acryloyl
Amine, Methacrylamide, N- hydroxymethylacrylamides, N- methoxy acrylamides, N- ethoxymethyl acrylamides,
N- butoxy methyl acrylamides, acrylonitrile or maleic anhydride etc..Described other have the comonomer of ethylenic unsaturated bond can
It is used alone or is used in the form of its mixture.
In a preferred embodiment of the invention, at least two hydroxyls are contained in the molecule in methods described (4) and (6)
Base can be able to be containing polyhydric monocarboxylic acid such as two with the compound (e) of the other groups of epoxy reaction with one
Hydroxymethyl propionic acid, dihydroxymethyl acetic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxymethyl caproic acid etc.；And dialkanol
Amine, such as diethanolamine, diisopropanolamine (DIPA) etc..In the molecule containing at least two hydroxyls and have one can be anti-with epoxy radicals
The compound of the other groups answered can be used alone or be used in the form of its mixture.
In a preferred embodiment of the invention, the monoisocyanates (f) containing unsaturated group can be first
Base acryloyloxyethyl isocyanate or organic diisocyanate are with (methyl) acrylic acid with a hydroxyl in molecule with about
Equimolar ratio carries out reacting the product for obtaining.The unsaturated monoisocyanates can be used alone or with its mixture
Form is used.
The photoresist (A) of the present invention is not limited to the photoresist obtained by said method, and which can be single
Solely use or used in the form of its mixture.
In the light sensitive anti-solder ink composition of one embodiment of the invention, the light trigger (B) can be：Benzene idol
Because of class and benzoin alkyl ether, such as benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether etc.；Benzene second
Ketone, such as 1-Phenylethanone., 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, 1,1- dichloros
1-Phenylethanone. etc.；Aminoacetophenone class, such as 2- methyl isophthalic acids-[4- (methyl thio) phenyl] -2- morpholinopropanones -1,2- benzyls -
2- dimethyl amido -1- (4- morpholino phenyls)-butane -1- ketone, N, N- dimethyl amine benzoylformaldoximes etc.；Anthraquinones, such as 2-
Tectoquinone, 2-ethyl-anthraquinone, 2- tert-butyl group anthraquinones, 1-chloroanthraquinone, isopropyl thioxanthone anthraquinone etc.；Thioxanthene ketone class, such as 2,4-
Dimethyl thioxanthone, 2,4- diethyl thioxanthones, CTX, 2,4- diisopropylthioxanthones etc.；Ketal class, such as benzene second
Ketone dimethyl ketal, benzyl dimethyl ketal etc.；Organic peroxide, such as benzoyl peroxide, dicumyl peroxide base etc.；
Mercaptan compound, such as 2,4,5- tri- aromatic radical imidazoles diploids, hibon, 2- sulfenyl benzimidazoles, 2- sulfenyl benzene
Bing oxazoles, 2- sulfurio benzo thiazoles etc.；Organohalogen compounds, such as 2,4,6- tri--s- triazines, tribromo-ethanol, tribromo first
Base phenyl ketone etc.；Benzophenones, such as benzophenone, 4,4 '-bis- diethyl aminobenzophenones etc.；And 2,4,6- trimethylbenzenes
Formoxyl diphenylphosphine oxide etc..Above-mentioned light trigger can be used alone or be used in the form of its mixture.
The solid constituent of photoresist (A) in a preferred embodiment of the invention, based on 100 weight portions
Meter, the content of the light trigger (B) are preferably 1 to 40 weight portion, more preferably 10 to 25 weight portions.
It is in the light sensitive anti-solder ink composition of one embodiment of the invention, described containing the organic of reactive functional groups
Surface modifier (C) can be to introduce one or more in the molecule selected from hydroxyl, carboxyl, epoxy radicals, vinyl, acrylic etc.
The polyether modified siloxane of reactive functional groups, poly- methyl alkyl siloxane, the poly- methyl alkyl siloxane of polyester modification, polyethers change
The poly- methyl alkyl siloxane of property, aralkyl modified poly- methyl alkyl siloxane, polydimethylsiloxane, polyester modification poly dimethyl
Siloxanes, polyether-modified polydimethylsiloxane, polyacrylic acid, acrylate copolymer etc., for example, containing acrylic-functional
Polyester modification dimethyl silicone polymer, the polyester modification dimethyl silicone polymer of hydroxy functional groups, hydroxy functional groups it is poly-
Ether modified dimethyl polysiloxane etc..Specially suitable commercially available organic surface modifier (C) containing reactive functional groups
Example is BYK-370, BYK-371, BYK-373, BYK-375, BYK-377 purchased from BYK chemistry etc..It is above-mentioned containing reactive functional
Organic surface modifier of group can be used alone or be used in the form of its mixture.
The solid constituent of photoresist (A) in a preferred embodiment of the invention, based on 100 weight portions
Meter, the content of the organic surface modifier (C) containing reactive functional groups are preferably 0.1 to 30 weight portion, more preferably 1 to 15 weight
Amount part.
In the light sensitive anti-solder ink composition of one embodiment of the invention, the example of the organic solvent (D) can
For：Ethers, such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol list
Ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, two
Dihydroxypropane single-ether, Dipropylene glycol mono-n-butyl Ether etc.；Esters, such as ethyl acetate, butyl acetate, ethylene glycol monoethylether acetate,
Ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetass, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether second
Acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetass, dipropylene glycol monomethyl ether
Acetass, DPE acetass, Dipropylene glycol mono-n-butyl Ether acetass etc.；Ketone, such as butanone, Ketohexamethylene, different Buddhist
Your ketone etc.；Arsol, such as toluene, dimethylbenzene, durene etc.；And petroleum solvents, such as Petroleum, Petroleum is aoxidized, it is molten
Agent Petroleum etc..These organic solvents can be used alone or be used in the form of its mixture.
The solid constituent of photoresist (A) in a preferred embodiment of the invention, based on 100 weight portions
Meter, the content of the organic solvent (D) are preferably 40 to 200 weight portions, more preferably 80 to 150 weight portions.
In the light sensitive anti-solder ink composition of one embodiment of the invention, the thermosetting component (E) is molecule
In have two or more epoxy radicals epoxide.The epoxide is usually bisphenol A type epoxy resin, hydrogenation pair
Phenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, novolac epoxy resins, the solvable ring of cresol
Oxygen tree fat, the novalac epoxies of bisphenol-A, united phenol-type epoxy resin, di- toluene phenol-type epoxy resin, three phenolic group first
Alkane type epoxy resin, N- (+)-2,3-Epoxy-1-propanol type epoxy resin, isocyanuric acid three-glycidyl ester, 2,6- xylenols dimer two contract
Water glycerin ether, aliphatic epoxy resin, xylene epoxy resin.Above-mentioned epoxide can be used alone or with its mixture
Form is used.
The solid constituent of photoresist (A) in a preferred embodiment of the invention, based on 100 weight portions
Meter, the content of the thermosetting component (E) are preferably 10 to 80 weight portions, more preferably 20 to 50 weight portions.
In the light sensitive anti-solder ink composition of a particularly preferred embodiment of the present invention, thermosetting component (E)
Weight ratio with the organic surface modifier (C) containing reactive functional groups is 6:1 to 25:1.
It may further be preferable that the solid constituent of photoresist (A) is reacted with containing with thermosetting component weight (E) sum
The ratio of organic surface modifier (C) weight of property functional group is preferably 25:1 to 90:1.
In the light sensitive anti-solder ink composition of one embodiment of the invention, the example of the photo polymerization monomer (F)
Can be：Such as (methyl) 2-(Acryloyloxy)ethanol, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid
(methyl) esters of acrylic acid containing hydroxyl of ester etc.；Such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl)
Simple function (methyl) esters of acrylic acid of butyl acrylate, (methyl) lauryl acrylate etc.；Double (the first of such as 1,6-HD
Base) acrylate, double (methyl) acrylate of two contracting/tripropylene glycols, two contracting/triethylene Glycols pair (methyl) acrylate,
The difunctionality of double (methyl) acrylate of ethoxylated bisphenol A, double (methyl) acrylate of neopentyl glycol diethoxy/propoxyl group etc.
(methyl) esters of acrylic acid；Such as trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two
Multifunctional (methyl) esters of acrylic acid of tetramethylolmethane six (methyl) acrylate etc.；And ethoxylation polyfunctional acrylic ester
With propoxylation polyfunctional acrylic ester etc..These photo polymerization monomers can be used alone or be used in the form of its mixture.
The solid constituent of photoresist (A) in a preferred embodiment of the invention, based on 100 weight portions
Meter, the content of the photo polymerization monomer (F) are preferably 5 to 50 weight portions, more preferably 10 to 30 weight portions.
In the light sensitive anti-solder ink composition of one embodiment of the invention, the example of the inorganic filler (G) can
For：Barium sulfate, Barium metatitanate., calcium dioxide, Pulvis Talci, gas-phase silica, silicon dioxide, clay, magnesium carbonate, Calcium Carbonate, oxidation
Aluminum, mica powder, Kaolin etc..These inorganic fillers can be used alone or be used in the form of its mixture.
The solid constituent of photoresist (A) in a preferred embodiment of the invention, based on 100 weight portions
Meter, the content of the inorganic filler (G) are preferably 50 to 300 weight portions, more preferably 100 to 200 weight portions.
In a particularly preferred embodiment of the present invention, the light sensitive anti-solder ink composition can also be comprising one kind
Or various additives selected from following material：Epoxy resin curing accelerator, light-initiated auxiliary agent, coloring pigment, thixotroping viscosifier
Deng.
As epoxy resin curing accelerator, light-initiated auxiliary agent, coloring pigment, thixotroping viscosifier etc., this area can be used
In all Conventional compounds.The content of the additive can be 0 to 40 weight %, the photoresist based on 100 weight portions
(A) solid constituent meter, but not limited to this.
When preparing the light sensitive anti-solder ink composition of the present invention, each component is uniformly mixed.
According to the second aspect of the invention, the present invention also provides a kind of comprising being formed by above-mentioned light sensitive anti-solder ink composition
Cured film wiring board.
When the light sensitive anti-solder ink composition of the present invention to be used to prepare wiring board, by ink composite by spraying
The methods such as method, flow coat method, rolling method, bar cladding process, silk screen print method are applied to the wiring board for being pre-formed with circuit.Its
Afterwards, it is dried at a temperature of about 50 DEG C to 100 DEG C.Subsequently carry out selectivity exposure and develop in alkaline aqueous solution.Then, will
Which is heated to 140 DEG C to 180 DEG C and is solidified, you can form the wiring board of the present invention.
Hereinafter, the present invention will be more fully described with reference to following examples.However, these examples are only used for illustrating this
It is bright, and the scope of the present invention not limited to this.
Embodiment
The synthesis of photoresist
According to following synthetic examples, photoresist (A) is prepared
By 210g o-cresol formaldehyde epoxy resins (being 210 purchased from the SQPN-704M of Shandong holy well, epoxide equivalent), 0.5g pair
During Benzodiazepiness and 200g diethylene glycol ethers acetass add there-necked flask, 100～110 DEG C are stirred and are heated to and in this temperature
Scope inside holding 1 hour is so that the material to be dissolved.90 DEG C are cooled to until completely dissolved, then Deca 72g acrylic acid and 1g
Temperature is increased to 105 in the range of 90～100 DEG C after completion of dropping during Deca by temperature control by triphenyl phosphorus
～110 DEG C, and react 12 hours in the temperature range, reactant is determined, by reactant if acid number is less than 5mgKOH/g
Greenhouse cooling to 60 DEG C, be subsequently adding 75g tetrahydrochysenes and face phthalate anhydride, and be incubated 3 hours at 90 DEG C.Resulting is solid
Content is 64%, and viscosity is 420dPa.s, and solid acid value is the yellowish-brown chromoresin (A) of 80mgKOH/g.
Embodiment 1-3 and comparative example 1-3
The formula shown in photoresist (A) according to the form below 1 that above-mentioned synthetic example is obtained is mixed with other components.
Then by the mixture of gained dispersion machine (U400 80-220 high speed dispersors) dispersion 20 minutes at a high speed, then ground with three rollers
Machine (S-65 three-roll grinders) grinds, and obtains light sensitive anti-solder ink composition of the particle diameter less than 20 microns.
Table 1：
Note 1：Purchased from the light trigger of Tianjin long day, isopropyl thioxanthone anthraquinone；
Note 2：Purchased from the light trigger of Zhejiang Yang Fan, 2- methyl isophthalic acids-(4- methyl mercapto phenyl) -2- morpholinyl -1- acetone；
Note 3：Purchased from the BYK-371 of German BYK chemistry；
Note 4：Purchased from the BYK-354 of German BYK chemistry；
Note 5:Purchased from the diethylene glycol ether acetass of Dow Chemical
Note 6：Purchased from the phenol aldehyde type epoxy resin SQPN-051 of Shandong holy well；
Note 7：The ultra-fine isocyanuric acid three-glycidyl ester launched company purchased from Nanjing U.S.A；
Note 8：The ultra-fine tripolycyanamide launched company purchased from Nanjing U.S.A；
Note 9：Purchased from the dipentaerythritol acrylate of Taiwan East Asia Synesis Company
Note 10：Purchased from the A1 blanc fixes of Guangzhou Ji Mei companies；
Note 11：Purchased from dark green K9360 of German BASF；
Note 12：Purchased from the fumed silica R972 of German Degussa；
Testing example
By following methods by the light sensitive anti-solder ink composition system prepared by embodiment 1～3 and comparative example 1～3
Into the wiring board containing corresponding light sensitive anti-solder ink composition, and its every characteristic is measured in the following manner, acquired results are shown in
In table 2.
Testing example 1：Coating
It is by 8cm x10cm copper bases that thickness is 35 μm after the polishing of 800 mesh steel brushes of Jing is except oxide layer, clear with clear water
Wash and be dried, then will be the light sensitive anti-solder prepared by embodiment 1～3 and comparative example 1～3 oily by air spray finishing
The whole face of ink composition is coated on to be cleaned on dry copper base, and is dried in putting it into 75 DEG C of heated air circulation type drying oven
50 minutes.After the drying, ink pellet surface is covered in using the film containing the square bat position of 100 0.2mm × 0.2mm, then
It is placed in the exposure device for load 7kW metal halide lamps and uses 500mJ/cm2Energy be exposed, then at 30 DEG C
The lower Na2CO for using 1 weight %3(spray pressure is 1kg/cm to aqueous development2) 60 seconds.According to following criterion evaluation coating.
It is excellent：Surface is uniform, and the surface defectivity such as no bubble, pin hole, white point, shrinkage cavity；
Difference：Surface is uneven, or has the surface defectivities such as bubble, pin hole, white point, shrinkage cavity.
Testing example 2：Surface tension
To prepare model with 1 identical mode of above-mentioned testing example, in being positioned over 150 DEG C of constant temperature oven, baking 1 is little
When, with the aqueous sulfuric acid of 1 weight % in 1kg/cm2Spray pressure under spray 10 seconds afterwards, with clean water and carry out
It is dried, then using the surface tension 1 of a dyne pen (purchased from Japanese Pacific Co., Ltd) test cured film.To survey afterwards
Trying capillary model is carrying out the weldering of 1 secondary wave crest and 1 Reflow Soldering, subsequently reuses the surface that dyne pen tests cured film
Tension force 2.
Testing example 3：Solderability
Model is prepared with 1 identical mode of above-mentioned testing example, prepared model is positioned over into 150 DEG C then
1 hour is toasted in constant temperature oven to prepare test sample plate.Then equably smear rosin flux in test sample plate, and by its
It is placed in 260 DEG C of weld groove and impregnates 10 seconds.The percentage ratio for clapping position is completely covered according to stannum assessing solderability.
Testing example 4：Thermostability
To prepare model with 3 identical mode of above-mentioned testing example.Colophonium is equably smeared in test sample plate subsequently
Scaling powder, and impregnate in being placed on 260 DEG C of weld groove 10 seconds, taking-up afterwards is used propylene glycol methyl ether acetate and washs and do
It is dry.Peel test is carried out using cellophane adhesive tape afterwards.According to following criterion evaluation thermostability.
It is excellent：Cured film is not peeled off；
Difference：Cured film has stripping.
Testing example 5：Adhesive force
By the test sample plate to prepare with 3 identical mode of above-mentioned testing example, then by drawing the test of lattice adhesive tape method
Adhesive force.According to following criterion evaluation adhesive force.
It is excellent：Do not come off completely；
Difference：Drawing ruling side has and comes off.
Testing example 6：Solvent resistance
To be soaked in propylene glycol methyl ether acetate with the test sample plate prepared with 3 identical mode of above-mentioned testing example
Stain 30 minutes, is cleaned and is dried with water after taking-up.Then peel test is carried out using cellophane adhesive tape.According to following
Criterion evaluation solvent resistance.
It is excellent：Cured film is not peeled off and is changed colour；
Difference：Cured film has stripping and changes colour.
Testing example 7：Acid resistance
10 weight % sulfur will be impregnated in the test sample plate prepared with 3 identical mode of above-mentioned testing example at room temperature
30 minutes in aqueous acid, with clean water and it is dried after taking-up.Then stripping survey is carried out using cellophane adhesive tape
Examination.According to following criterion evaluation acid resistance.
It is excellent：Cured film is not peeled off and is changed colour；
Difference：Cured film has stripping and changes colour.
Testing example 8：Pencil hardness
On with the test sample plate for preparing with 3 identical mode of above-mentioned testing example, the 4H that the nib of pen core is polished
Pencil to 7H is pressed with 45 ° of angle, to determine the pencil hardness that film is not peeling.
Above-mentioned test result is shown in table 2 below
Table 2
As can be known from the results of Table 2, compared with comparative example, by the light sensitive anti-solder ink composition assist side of the present invention
The cured film of upper formation has stable surface tension, and makes wiring board have improved solderability.
Claims (10)
1. a kind of light sensitive anti-solder ink composition, which includes：
(A) photoresist, contains carboxyl and at least two ethylenic unsaturated bonds simultaneously in its molecule,
(B) light trigger,
(C) the organic surface modifier containing reactive functional groups,
(D) organic solvent,
(E) thermosetting component,
(F) photo polymerization monomer, and
(G) inorganic filler；
The solid constituent meter of photoresist (A) wherein, based on 100 weight portions, the organic table containing reactive functional groups
The content of face auxiliary agent (C) is 0.1 to 30 weight portion.
2. the light sensitive anti-solder ink composition of claim 1, the wherein acid number of the solid constituent of photoresist (A) be 50 to
The photoresist of 150mgKOH/g.
3. the light sensitive anti-solder ink composition of claim 1, wherein the content of the light trigger (B) is 1 to 40 weight portion, base
In the solid constituent meter of the photoresist (A) of 100 weight portions.
4. the light sensitive anti-solder ink composition of claim 1, wherein the organic surface modifier (C) containing reactive functional groups is
The poly- of one or more reactive functional groups for being selected from hydroxyl, carboxyl, epoxy radicals, vinyl or acrylic is introduced in the molecule
Ether modified siloxane, poly- methyl alkyl siloxane, the poly- methyl alkyl siloxane of polyester modification, polyether-modified poly- methyl alkyl silica
It is alkane, aralkyl modified poly- methyl alkyl siloxane, polydimethylsiloxane, polyester modification dimethyl silicone polymer, polyether-modified
Polydimethylsiloxane, polyacrylic acid or acrylate copolymer.
5. the light sensitive anti-solder ink composition of claim 1, wherein the content of the organic solvent (D) is 40 to 200 weight portions,
The solid constituent meter of the photoresist (A) based on 100 weight portions.
6. the light sensitive anti-solder ink composition of claim 1, wherein thermosetting component (E) are to have two or more rings in molecule
The epoxide of epoxide, its content be 10 to 80 weight portions, the solid constituent of the photoresist (A) based on 100 weight portions
Meter.
7. the light sensitive anti-solder ink composition of claim 1, wherein the content of the photo polymerization monomer (F) is 5 to 50 weight portions,
The solid constituent meter of the photoresist (A) based on 100 weight portions.
8. the light sensitive anti-solder ink composition of claim 1, wherein the content of the inorganic filler (G) is 50 to 300 weight portions,
The solid constituent meter of the photoresist (A) based on 100 weight portions.
9. the light sensitive anti-solder ink composition of claim 1, which is also comprising one or more additive selected from following material：Ring
Oxygen solidified resin promoter, light-initiated auxiliary agent, coloring pigment and thixotroping viscosifier.
10. a kind of wiring board, which is comprising being formed by the light sensitive anti-solder ink composition of any one of claim 1 to 9
The wiring board of cured film.
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| CN110320749A (en) * | 2018-03-28 | 2019-10-11 | 太阳油墨制造株式会社 | The manufacturing method of photosensitive polymer combination, dry film and printed circuit board |
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