CN106243827A - A kind of thermosetting ink of the anti-chemical nickel and gold of selectivity - Google Patents

A kind of thermosetting ink of the anti-chemical nickel and gold of selectivity Download PDF

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Publication number
CN106243827A
CN106243827A CN201610868262.9A CN201610868262A CN106243827A CN 106243827 A CN106243827 A CN 106243827A CN 201610868262 A CN201610868262 A CN 201610868262A CN 106243827 A CN106243827 A CN 106243827A
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gold
modified
selectivity
acid
chemical nickel
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CN106243827B (en
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聂雪峰
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Guangdong Keding New Materials Co ltd
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Nanxiong Ding Ding Chemical Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/102Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/103Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides the thermosetting ink of the anti-chemical nickel and gold of a kind of selectivity, calculates by weight, including: 30~40 parts of phenol-formaldehyde resin modifieds, 3~4 parts of pigment, 30~50 parts of solvents, 20~30 parts of modified talc powders, 1~10 part of firming agent, 0.5~10 part of auxiliary agent;Wherein, described phenol-formaldehyde resin modified is 2 (4 (2-hydroxybenzoyl)) benzoic acid modified phenolic resin, and described modified talc powder is containing stearic octaphenyl eight silsesquioxane modified acroleic acid Pulvis Talci;Described firming agent is a kind of in polyamide, imidazole curing agent, 590 firming agent.

Description

A kind of thermosetting ink of the anti-chemical nickel and gold of selectivity
Technical field
The present invention relates to the manufacture field of printed circuit board (PCB), more specifically, the present invention provides a kind of anti-chemical nickel of selectivity The thermosetting ink of gold.
Background technology
The development of electron trade make rapid progress, the design of PCB the most increasingly to highly difficult development, PCB for meeting BGA, FC (Flip-Chip), assembling and the needs of surface mounting technology such as COB (Chip-On-Board), process of surface treatment is being sought always Look for a kind of preferably coating.OSP technique solves the uniformity of coating, flatness problem and good weldability and low cost work Skill is simple and easy to control is used widely, but relatively thin owing to protecting layer, is highly prone to damage, so Elastic Contact cannot be realized. And chemical nickel/gold plating uniform flat and Elastic Contact can be realized, can also act as conductive radiator simultaneously, but because of nickel corrosion and solder joint The problem of fragility causes weld strength not enough, and the most small pad, such as positions such as BGA, IC, affects the reliability of product.
For the advantage having two kinds of techniques concurrently, it is to avoid the hidden danger of coating, PCB industry now uses one to use two kinds of surfaces simultaneously Process the surface-coated of PCB, to meet different performance requirements, here it is selective chemical ni au technique, i.e. same On sheet pcb board, the part for welding uses OSP process, and uses chemistry ni au to process at Elastic Contact, heat radiation PAD.Mesh Front selective chemical ni au technique has been widely used in the electronics such as mobile phone, notebook computer, armarium, automobile product and has produced On product.And when current PCB makes and produces, need to do OSP surface treatment is to cover (by pressure with dry film before chemical nickel and gold Film, para-position, exposure, development realizes), not only flow process is complicated, pollutes relatively big to the liquid medicine of chemistry ni au, reduces nickel cylinder, gold cylinder longevity Life, affects the quality of ni au coating, and relatively costly.It is simple, in the organic dissolution of ni au cylinder that industry is badly in need of a kind of technological process Little, and the products substitution dry film of relative inexpensiveness.
Selectivity anti-chemical nickel and gold thermosetting ink is the material of a kind of comprehensive replacement dry film, by the way of silk screen printing, The part that surface process need to be before chemical nickel and gold processes OSP covers, and stops the upper chemical nickel and gold coating of its deposition, chemical nickel The selectivity anti-chemical nickel and gold thermosetting ink covered is removed after completing by gold by NaOH solution, exposes and need to be what OSP processed Copper face, treats that postorder carries out the process of OSP surface.
Therefore, for the problems referred to above, the present invention provides a kind of high temperature resistant, and adhesive force is strong, and acid resistance is strong, low cost, consumption Few, and there is good flatness, mobility, coating, formability, suppress the anti-chemistry of selectivity of the vulnerability of its solidfied material Nickel gold thermosetting ink.
Summary of the invention
The present invention provides the thermosetting ink of the anti-chemical nickel and gold of a kind of selectivity, calculates by weight, including:
Wherein, described phenol-formaldehyde resin modified is 2-(4-(2-hydroxybenzoyl)) benzoic acid modified phenolic resin, described modified sliding Stone powder is containing stearic octaphenyl eight silsesquioxane modified acroleic acid Pulvis Talci;Described firming agent is polyamide, miaow One in azole firming agent, 590 firming agent.
In one embodiment, 2-(4-(2-hydroxybenzoyl)) benzoic acid and phenolic resin in described phenol-formaldehyde resin modified Mass ratio (1~3.5): 1.
In one embodiment, 2-(4-(2-hydroxybenzoyl)) benzoic acid and phenolic resin in described phenol-formaldehyde resin modified Mass ratio (1~3): 1.
In one embodiment, the weight average molecular weight of described phenol-formaldehyde resin modified is 5000~200000.
In one embodiment, described solvent is ethylene glycol monobutyl ether, diethylene glycol ether, wherein said ethylene glycol list Butyl ether is 1:(1.2~2 with the mass ratio of described diethylene glycol ether).
In one embodiment, the preparation process of described modified talc powder is as follows:
(1) it is in 60 DEG C of high-speed mixers that Pulvis Talci adds barrel temperature, by weight adding acrylic acid and BPO, stirs After mixing 0.5~2h, discharging, after high-speed mixer barrel temperature is risen to 120 DEG C, above-mentioned material is refunded in high-speed mixer, Discharging after high-speed stirred 0.5~1h, obtains acrylic acid Pulvis Talci;
(2) by weight by octaphenyl eight silsesquioxane and 2,4-resorcylic acid is dissolved in polyphosphoric acids, After reacting 5-10h at 180 DEG C, it is down to 120 DEG C, adds calcium stearate, after reacting 3-6h at 120 DEG C, be down to room temperature, pour acetone into In, fully after washing, filter and be dried 12 hours at 120 DEG C in vacuum drying oven, obtain stearic acid and 2,4-dihydroxy benzenes first Octaphenyl eight silsesquioxane that acid is modified;
(3) by eight modified with step (2) stearic acid and 2,4-resorcylic acid for acrylic acid Pulvis Talci in step (1) benzene It is in 120 DEG C of high-speed mixers that base eight silsesquioxane adds barrel temperature, discharging after high-speed stirred 0.5~2h.
In one embodiment, Pulvis Talci described in the preparation process of described modified talc powder, described acrylic acid and institute The mass ratio stating BPO is 100:(10-18): (0.12-0.2).
In one embodiment, Pulvis Talci described in the preparation process of described modified talc powder, described acrylic acid and institute The mass ratio stating BPO is 100:16:0.18.
In one embodiment, octaphenyl eight silsesquioxane described in the preparation process of described modified talc powder, institute The weight ratio stating 2,4-resorcylic acid, described calcium stearate and described polyphosphoric acids is 1:(1-2): (1-3): (10- 18)。
In one embodiment, octaphenyl eight silsesquioxane described in the preparation process of described modified talc powder, institute The weight ratio stating 2,4-resorcylic acid, described calcium stearate and described polyphosphoric acids is 1:1.2:1.3:15.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Detailed description of the invention
Participate in the election of the detailed description being preferable to carry out method of the invention below and the embodiment that includes can be more easily understood this Bright content.Unless otherwise defined, all technology used herein and scientific terminology have common with art of the present invention The identical implication that technical staff is generally understood that.When there is contradiction, it is as the criterion with the definition in this specification.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " including ", " have ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.Such as, the combination of listed elements is comprised Thing, step, method, goods or device are not necessarily solely those key elements, but can include other not expressly listed key element or The key element that this kind of compositions, step, method, goods or device are intrinsic.
Conjunction " Consists of " gets rid of any key element, step or component do not pointed out.If in claim, this Phrase will make claim be closed so that it is does not comprise the material in addition to the material that those describe, but relative often Except rule impurity.When being rather than immediately following during phrase " Consists of " occurs in the clause of claim main body after theme, It is only limited to the key element described in this clause;Other key element is not excluded outside as overall described claim.
Equivalent, concentration or other value or parameter are excellent with scope, preferred scope or a series of upper limit preferred value and lower limit During the Range Representation that choosing value limits, this is appreciated that and specifically discloses by any range limit or preferred value and any scope All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether this scope separately discloses.Such as, when open During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numerical range is described in this article, unless otherwise indicated, otherwise this scope is intended to include its end Value and all integers within the range and mark.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or " arbitrarily A kind of " refer to that the item described thereafter or event may or may not occur, and this description include situation that event occurs with The situation that event does not occurs.
Approximation term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this concrete Quantity, also includes close to this quantity acceptable without causing the part of the correction of the change of relevant basic function.Phase Answer, modify a numerical value with " about ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximation Term likely corresponds to measure the precision of the instrument of numerical value.In present specification and claims, scope limits permissible Combination and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
Additionally, indefinite article " a kind of " before key element of the present invention or component and " one " are to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one or at least one, and odd number The key element of form or component also include plural form, unless the obvious purport of described quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by being polymerized identical or different type.Generic term " polymer " comprises term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by polymerization at least two different monomers.Generic term " copolymer " includes (it is general with term " terpolymer " for term " copolymer " (it is typically in order to refer to the polymer prepared by two kinds of different monomers) In order to refer to the polymer prepared by three kinds of different monomers).It also comprises the polymer manufactured by being polymerized more kinds of monomers. " blend " mean two or more polymer by physics or the method for chemistry jointly mix and the polymer that formed.
The present invention provides the thermosetting ink of the anti-chemical nickel and gold of a kind of selectivity, calculates by weight, including:
Wherein, described phenol-formaldehyde resin modified is 2-(4-(2-hydroxybenzoyl)) benzoic acid modified phenolic resin, described modified sliding Stone powder is containing stearic octaphenyl eight silsesquioxane modified acroleic acid Pulvis Talci;Described firming agent is imidazole curing agent; Preferably, the thermosetting ink of the anti-chemical nickel and gold of described selectivity, calculate by weight, including:
Phenolic resin
The polycondensation product of phenols and aldehydes is commonly referred to as phenolic resin, and synthesis and the solidification process of phenolic resin fully comply with body The rule of type polycondensation reaction.Thermosetting phenolic resin, it is a kind of tree containing the methylol active group that can react further Fat, if synthesizing uncontrolled, then can make polycondesation carry out to the three-way network that has that formation is molten, insoluble always and tie The solidification resin of structure.
The present invention provides a kind of phenol-formaldehyde resin modified, and the preparation process of described phenol-formaldehyde resin modified is as follows:
(1) by phenols, join in 250mL four-hole boiling flask, add heat fusing, after melting, open stirring, be cooled to 60 DEG C slowly The formaldehyde of dropping 37%, in 65 DEG C of insulation reaction 4~5h after adding, is cooled to 50 DEG C;When being neutralized to pH=6 with the hydrochloric acid of 10% Only, stopping stirring and stand 0.5h layering, organic layer is washed twice, abandons water layer and obtains lurid first stage phenolic slurry;Described phenolic aldehyde Mol ratio 1:2;
(2) under nitrogen protection, heating 2-(4-(2-hydroxybenzoyl)) benzoic acid, to melting, is slowly added to phenol at 150 DEG C Aldehyde is starched, and after (strict control adds slurry speed, in case pot phenomenon that rises) adds phenolic aldehyde slurry, is warming up to 230~240 DEG C, and addition is many Unit's alcohol and catalyst zinc oxide, and insulation reaction 1h at this temperature, then heat to about 275 DEG C, carry out esterification 10 ~14h, when acid number drops to below 22, stopped reaction, evacuation 1h boils off low-boiling point material, discharging, obtains modified phenolic resin Fat;Described 2-(4-(2-hydroxybenzoyl)) benzoic acid is 1:0.52 with the mol ratio of polyhydric alcohol;Described catalyst zinc oxide and 2-(4- (2-hydroxybenzoyl)) benzoic mass ratio is 0.005:1.
In one embodiment, described phenols include carbolic acid, cresol, amylic phenol, bisphenol-A, butylphenol, octyl phenol, In nonyl phenol and dodecylphenol one or more;Preferably, described phenols is p-tert-butylphenol, Octylphenol.
In one embodiment, described p-tert-butylphenol is 1:1 with the mol ratio of described Octylphenol.
In one embodiment, one during described formaldehyde is formalin, paraformaldehyde.
In one embodiment, described base catalyst include sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, The alkylamines such as metallic catalyst class, ammonia, methylamine, dimethylamine, diethylamine, trimethylamine, ethamine, diethylamine, triethylamine such as zinc oxide, In the alkanolamines such as ethanolamine, diethanolamine, triethanolamine one or more;Preferably, described base catalyst is sodium hydroxide.
In one embodiment, described sodium hydroxide is 0.03:1 with the mass ratio of described phenols, described sodium hydroxide Concentration be 6%.
In one embodiment, 2-(4-(2-hydroxybenzoyl)) benzoic acid and phenolic resin in described phenol-formaldehyde resin modified Mass ratio (1~3.5): 1.
In one embodiment, 2-(4-(2-hydroxybenzoyl)) benzoic acid and phenolic resin in described phenol-formaldehyde resin modified Mass ratio (1~3): 1.
In one embodiment, described polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, Polyethylene Glycol, the third two The dihydroxylic alcohols such as alcohol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, hexanediol, ethohexadiol, nonanediol, neopentyl glycol, three Unit alcohol, diglycerol, trimethylolethane, trimethylolpropane, double trimethylolpropane, tetramethylolmethane, dipentaerythritol, Pyrusussuriensis One in alcohol;Preferably, described polyhydric alcohol is tetramethylolmethane.
In one embodiment, the weight average molecular weight of described phenol-formaldehyde resin modified is 5000~200000;Preferably, institute The weight average molecular weight stating phenol-formaldehyde resin modified is 10000~150000.
Weight average molecular weight is (hreinafter referred to as " GPC " based on gel permeation chromatography.) measure and carry out polystyrene and change Value after calculation.The condition determination of GPC uses the condition test that this area is conventional, such as, following mode can be used to test and obtain.
Post: following post is connected in series and uses.
" TSKgelG5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector: RI (differential refractometer);Column temperature: 40 DEG C;Eluent: oxolane;Flow velocity: 1.0mL/ minute;Note Enter amount: 100 μ L (tetrahydrofuran solution of sample solution concentration 4mg/mL);Standard specimen: use following monodisperse polystyrene, makes Standard curve.
Acid value measuring is carried out with reference to LY/T 1179-95 rosin modified phenolic resin assay method.The acid number impact oil of resin The printability of ink, the flocculability of the too big then granules of pigments of acid number is too strong, and the wettability of the too small then pigment of acid number is poor.In addition acid number Or control a major parameter of resin reaction degree.The test concrete operations of resinous acid value are as follows.
Method of testing: measure 50mL ethanol-toluene mixed solvent (volume ratio 1:2) in 250mL conical flask, adds 3~5 Drip phenolphthalein indicator, be neutralized to blush with standard potassium hydroxide solution.Accurately weigh finely ground resin about 0.4g (to be accurate to 0.01g) join in conical flask, fully shake with mixed solution after making it dissolve, be about 0.1mol/L's with demarcating concentration Standard potassium hydroxide solution drops to micro-red, and in 30 seconds, redness does not disappear for terminal.
Acid number (AV) calculating formula is as follows:
AV=(56.1VN)/W
In formula: the standard potassium hydroxide liquor capacity that V-consumes, mL;
N-standard potassium hydroxide solution molar concentration, mol/L;
W-resin quality, g;
The molal weight of 56.1-potassium hydroxide.
2-(4-(2-hydroxybenzoyl)) benzoic acid has rigid structure, and has carboxylic acid and oh group, passes through in the present invention Phenolic resin is modified by 2-(4-(2-hydroxybenzoyl)) benzoic acid, the three-dimensional network size knot with height of phenolic resin Structure, the molecular weight of phenolic resin increases, and improves the softening point of phenolic resin and dissolves viscosity, it addition, 2-(4-hydroxy benzenes first Acyl) in benzoic acid the introducing of hydroxyl promote phenolic resin dissolubility in each kind solvent, modified phenolic resin has very Good solubility property, in 2-(4-(2-hydroxybenzoyl)) benzoic acid, carboxyl carries out condensation reaction with the hydroxyl in phenolic resin and is produced Thing has acidproof corrosion resistance.
In one embodiment, described solvent is ethylene glycol monobutyl ether, diethylene glycol ether, wherein said ethylene glycol list Butyl ether is 1:(1.2~2 with the mass ratio of described diethylene glycol ether).
In one embodiment, described pigment is alizarol saphirol.
Pulvis Talci
Talcous main component is Talcum.Talcum main component is the magnesium silicate that Talcum is aqueous, and molecular formula is Mg3 [Si4O10](OH)2.Talcum belongs to monoclinic system, and crystal is false six sides or the lamellar of rhombus, generally become fine and close bulk, foliaceous, Radial, fibrous agrregate.Water white transparency or white, but the most shallow because presenting palm fibre light green, pale yellow, shallow containing a small amount of impurity Red;In pearly luster in cleavage surface.Talcum has that lubricity, fire resistance, acid-resisting, insulating properties, fusing point be high, chemical is not lived Sprinkle, covering power is good, softness, good luster, the absorption affinity excellent Wuli-Shili-Renli system approach such as by force, owing to the crystal structure of Talcum is In stratiform, easily split into tending to and special slip of scale so having.
In one embodiment, the preparation process of described modified talc powder is as follows:
(1) it is in 60 DEG C of high-speed mixers that Pulvis Talci adds barrel temperature, by weight adding acrylic acid and BPO, stirs After mixing 0.5~2h, discharging, after high-speed mixer barrel temperature is risen to 120 DEG C, above-mentioned material is refunded in high-speed mixer, Discharging after high-speed stirred 0.5~1h, obtains acrylic acid Pulvis Talci;
(2) by weight by octaphenyl eight silsesquioxane and 2,4-resorcylic acid is dissolved in polyphosphoric acids, After reacting 5-10h at 180 DEG C, it is down to 120 DEG C, adds calcium stearate, after reacting 3~6h at 120 DEG C, be down to room temperature, pour third into In ketone, fully after washing, filter and be dried 12 hours at 120 DEG C in vacuum drying oven, obtain stearic acid and 2,4-dihydroxy benzenes Octaphenyl eight silsesquioxane that formic acid is modified;
(3) by eight modified with step (2) stearic acid and 2,4-resorcylic acid for acrylic acid Pulvis Talci in step (1) benzene It is in 120 DEG C of high-speed mixers that base eight silsesquioxane adds barrel temperature, discharging after high-speed stirred 0.5~2h.
In one embodiment, Pulvis Talci described in the preparation process of described modified talc powder, described acrylic acid and institute The mass ratio stating BPO is 100:(10-18): (0.12-0.2).
In one embodiment, Pulvis Talci described in the preparation process of described modified talc powder, described acrylic acid and institute The mass ratio stating BPO is 100:16:0.18.
In one embodiment, octaphenyl eight silsesquioxane described in the preparation process of described modified talc powder, institute The weight ratio stating 2,4-resorcylic acid, described calcium stearate and described polyphosphoric acids is 1:(1-2): (1-3): (10- 18)。
In one embodiment, octaphenyl eight silsesquioxane described in the preparation process of described modified talc powder, institute The weight ratio stating 2,4-resorcylic acid, described calcium stearate and described polyphosphoric acids is 1:1.2:1.3:15.
The reactivity passing through acrylic acid AA in the present invention is the highest, and its one end is highly acid carboxyl, can be with Pulvis Talci table There is chemical bonding in face, under the reaction condition of solid phase grafting, product is combined in Pulvis Talci surface, octaphenyl eight silsesquioxane The 2 of upper grafting, 4-resorcylic acid carries out graft reaction with acrylic acid modified Pulvis Talci and stearic acid, the modified talc obtained Powder surface covers the polar group that Organic substance contains carboxyl, hydroxyl etc., makes modified talc powder particle have surface lipophilic group, with The affinity of phenolic resin strengthens, improve its dispersibility in phenolic resin, additionally rigidity octaphenyl eight silsesquioxane Introduce, further increase modified talc powder particle dispersibility in phenolic resin, additionally also enhance anti-chemical nickel and gold The acid resistance of thermosetting ink and corrosion resistance.
Auxiliary agent
On the basis of not affecting the invention, the addition of auxiliary agent can be carried out as required.Auxiliary agent is not it may be that but It is limited to, one or more in firming agent, dispersant, adhesion promoter, thickening agent, lubricant, Liu Ping agent etc..
Firming agent
Phenolic resin self cannot drying and forming-film, it is necessary to add firming agent, when temperature reaches 120~150 DEG C so that it is hand over Being unified into and do not melt insoluble network structure macromole, film solidifies rapidly, and formation has certain degree of hardness, adheres to good dry skin Film.
In one embodiment, one during described firming agent is polyamide, imidazole curing agent, 590 firming agent; Preferably, described firming agent is imidazole curing agent.
In one embodiment, described imidazole curing agent includes imidazoles, 2-methylimidazole, 2-ethyl imidazol(e), 2-benzene Base imidazoles, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 704 firming agent, 705 firming agent, 708 One in firming agent;Preferably, described imidazole curing agent is 2-methylimidazole.
Dispersant
Dispersant can reduce the material that in dispersion, solid or liquid particle are assembled.Preparing cream and wettable powder Time add dispersant and suspending agent and be easily formed dispersion liquid and suspension, and keep the metastable function of dispersion.
In one embodiment, described dispersant is maleic acid-acrylic acid copolymer, the one of sodium polyacrylate or many Kind.
Adhesion promoter
Adhesion promoter i.e. coupling agent, coupling agent is the material that a class has two heterogeneity functional groups, and its molecule is tied The maximum feature of structure is containing different two groups of chemical property in molecule, and one is the group of parent's inorganic matter, easily with inorganic Thing surface chemically reactive;Another is organophilic group, can be with synthetic resin or other polymer generation chemical reaction Or generation hydrogen bond is dissolved in wherein.Therefore coupling agent is referred to as " molecular bridge ", in order to improve the interface between inorganic matter and Organic substance Effect, thus it is greatly improved the performance of composite.
In one embodiment, during described coupling agent includes titanate coupling agent, silane coupler one or more;Excellent Selection of land, described coupling agent is titanate coupling agent.
Thickening agent
Thickening agent is a kind of auxiliary rheological agents, and ink is not only played thickening power by it, the most also gives the machinery that ink is excellent And physical and chemical stability, it is possible to control ink rheology, improve the thixotropic property of ink.We select silicon dioxide to make ink Thickening agent, it can meet simultaneously thickening and improve thixotropic requirement.
Thickening agent have aqueous and oiliness point.Especially water phase thickener application is the most universal, can adjust after adding thickening agent Throttling degeneration, makes adhesive and sealant thickening, prevents filler from precipitating, and gives good physical mechanical stability, controls construction The rheological characteristic of process (during applying glue not sagging, non-drip, do not fly liquid), moreover it is possible to play a part to reduce cost.Especially for gluing Agent and the manufacture of sealant, store, use the most critically important, it is possible to improve and regulate viscosity, it is thus achieved that stable, anti-settling, subtract ooze, anti- Drop down, the performance such as thixotroping.
In one embodiment, described thickening agent is sodium polyacrylate, hydroxyethyl cellulose, polyacrylamide, gas phase In silicon dioxide one or more;Preferably, described thickening agent is aerosil.
Lubricant
Lubricant is in order to reduce the frictional resistance of friction pair, to slow down the lubricant medium of its abrasion.
In one embodiment, described lubricant is Tissuemat E.
Levelling agent
Levelability when levelling agent is used to improve ink printing.The quality of ink levelability directly determines ink and exists An ink film steady, smooth, uniform can be formed after printing, and smooth, the slickness of ink film outward appearance are reflection ink qualities An important parameter.
In one embodiment, described Liu Ping agent is acrylate copolymer.
In one embodiment, described acrylate copolymer levelling agent includes that EL-2820 levelling agent, EL-2819 flow One in flat agent, EL-2818 levelling agent, EL-2537 fluorine carbon levelling agent.
In one embodiment, the preparation process of the thermosetting ink of the anti-chemical nickel and gold of described selectivity is as follows:
(1) it is blended: in reactor, add phenol-formaldehyde resin modified, pigment, solvent, modified talc powder according to weight portion, consolidate Agent, auxiliary agent, and be sufficiently stirred for;
(2) grind: blend solution in step (1) is delivered to dispersion on three-roll grinder and grinds 2~3 times to fineness less than 10 Micron, detect qualified after, obtain the thermosetting ink of the anti-chemical nickel and gold of selectivity.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example are only used In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some nonessential improvement and adjustment that content according to the invention described above is made, still fall within protection scope of the present invention.
Described levelling agent is purchased from Dongguan City Yi Lian Chemical Industry Science Co., Ltd.
It addition, illustrate without other, raw materials used is all commercially available, is purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
The thermosetting ink of the anti-chemical nickel and gold of described selectivity, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.5 with the mass ratio of described diethylene glycol ether;Described Firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is Maleic acid-acrylic acid copolymer;Described levelling agent is EL-2818 levelling agent.
The preparation process of the thermosetting ink of the anti-chemical nickel and gold of described selectivity is as follows:
(1) it is blended: in reactor, add phenol-formaldehyde resin modified, pigment, solvent, modified talc powder according to weight portion, consolidate Agent, auxiliary agent, and be sufficiently stirred for;
(2) grind: blend solution in step (1) is delivered to dispersion on three-roll grinder and grinds 2~3 times to fineness less than 10 Micron, detect qualified after, obtain the thermosetting ink of the anti-chemical nickel and gold of selectivity.
The preparation process of described phenol-formaldehyde resin modified is as follows:
(1) by phenols (p-tert-butylphenol, Octylphenol mixture), 3% sodium hydrate aqueous solution (concentration is 6%) adds Enter in 250mL four-hole boiling flask, add heat fusing, molten after open stirring, be cooled to 60 DEG C be slowly added dropwise 37% formaldehyde, after adding 65 DEG C of insulation reaction 5h, it is cooled to 50 DEG C;Stop when being neutralized to pH=6 with the hydrochloric acid of 10%, stop stirring and stand 0.5h layering, have Machine layer is washed twice, abandons water layer and obtains lurid first stage phenolic slurry;Described phenolic aldehyde mol ratio 1:2;Described p-tert-butylphenol It is 1:1 with the mol ratio of described Octylphenol;
(2) under nitrogen protection, heating 2-(4-(2-hydroxybenzoyl)) benzoic acid, to melting, is slowly added to phenol at 150 DEG C Aldehyde is starched, and after (strict control adds slurry speed, in case pot phenomenon that rises) adds phenolic aldehyde slurry, is warming up to 230 DEG C, addition tetramethylolmethane With catalyst zinc oxide, and insulation reaction 1h at this temperature, then heat to 275 DEG C, carry out esterification 12h, work as acid number When dropping to less than 22, stopped reaction, evacuation 1h boils off low-boiling point material, discharging, obtains phenol-formaldehyde resin modified;Described modified phenol 2-(4-(2-hydroxybenzoyl)) benzoic acid and the mass ratio 2.15:1 of phenolic resin in urea formaldehyde;Described 2-(4-(2-hydroxybenzoyl)) benzene Formic acid is 1:0.52 with the mol ratio of tetramethylolmethane;Described catalyst zinc oxide and 2-(4-(2-hydroxybenzoyl)) benzoic quality Ratio is 0.005:1;The weight average molecular weight of described phenol-formaldehyde resin modified is 120000.
The preparation process of described modified talc powder is as follows:
(1) it is in 60 DEG C of high-speed mixers that Pulvis Talci adds barrel temperature, by weight adding acrylic acid and BPO, stirs After mixing 1h, discharging, after high-speed mixer barrel temperature is risen to 120 DEG C, above-mentioned material is refunded in high-speed mixer, high-speed stirring Mix discharging after 1h, obtain acrylic acid Pulvis Talci;Pulvis Talci described in the preparation process of described modified talc powder, described acrylic acid and The mass ratio of described BPO is 100:16:0.18;
(2) by weight by octaphenyl eight silsesquioxane and 2,4-resorcylic acid is dissolved in polyphosphoric acids, After reacting 8h at 180 DEG C, it is down to 120 DEG C, adds calcium stearate, after reacting 5h at 120 DEG C, be down to room temperature, pour in acetone, fill After dividing washing, filter in vacuum drying oven, also at 120 DEG C, be dried 12h, obtain stearic acid and 2, the modification of 4-resorcylic acid Octaphenyl eight silsesquioxane;Octaphenyl eight silsesquioxane described in the preparation process of described modified talc powder, described 2,4- The weight ratio of resorcylic acid, described calcium stearate and described polyphosphoric acids is 1:1.2:1.3:15;
(3) by eight modified with step (2) stearic acid and 2,4-resorcylic acid for acrylic acid Pulvis Talci in step (1) benzene It is in 120 DEG C of high-speed mixers that base eight silsesquioxane adds barrel temperature, discharging after high-speed stirred 1h.
Embodiment 2
The thermosetting ink of the anti-chemical nickel and gold of described selectivity, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:2 with the mass ratio of described diethylene glycol ether;Described solid Agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is horse Carry out sour-acrylic copolymer;Described levelling agent is EL-2819 levelling agent;
The thermosetting ink preparation process of the anti-chemical nickel and gold of described selectivity, described phenol-formaldehyde resin modified preparation process, institute State modified talc powder preparation process with embodiment 1.
Embodiment 3
The thermosetting ink of the anti-chemical nickel and gold of described selectivity, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.2 with the mass ratio of described diethylene glycol ether;
Described firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;
Described dispersant is maleic acid-acrylic acid copolymer;Described levelling agent is EL-2820 levelling agent;
The thermosetting ink preparation process of the anti-chemical nickel and gold of described selectivity, described phenol-formaldehyde resin modified preparation process, institute State modified talc powder preparation process with embodiment 1.
Embodiment 4
The thermosetting ink of the anti-chemical nickel and gold of described selectivity, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.5 with the mass ratio of described diethylene glycol ether;Described Firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is Maleic acid-acrylic acid copolymer;Described levelling agent is EL-2537 fluorine carbon levelling agent;
The thermosetting ink preparation process of the anti-chemical nickel and gold of described selectivity, described phenol-formaldehyde resin modified preparation process, institute State modified talc powder preparation process with embodiment 1;
Difference is described in described phenol-formaldehyde resin modified preparation process 2-(4-(2-hydroxybenzoyl)) in phenol-formaldehyde resin modified Benzoic acid and the mass ratio 3.5:1 of phenolic resin;The weight average molecular weight of described phenol-formaldehyde resin modified is 200000.
Embodiment 5
The thermosetting ink of the anti-chemical nickel and gold of described selectivity, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.5 with the mass ratio of described diethylene glycol ether;Described Firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is Maleic acid-acrylic acid copolymer;Described levelling agent is EL-2818 levelling agent;
The thermosetting ink preparation process of the anti-chemical nickel and gold of described selectivity, described phenol-formaldehyde resin modified preparation process, institute State modified talc powder preparation process with embodiment 1;
Difference is described in described phenol-formaldehyde resin modified preparation process 2-(4-(2-hydroxybenzoyl)) in phenol-formaldehyde resin modified Benzoic acid and the mass ratio 1:1 of phenolic resin;The weight average molecular weight of described phenol-formaldehyde resin modified is 10000.
Embodiment 6
The thermosetting ink of the anti-chemical nickel and gold of described selectivity, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.5 with the mass ratio of described diethylene glycol ether;Described Firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is Maleic acid-acrylic acid copolymer;Described levelling agent is EL-2818 levelling agent;
The thermosetting ink preparation process of the anti-chemical nickel and gold of described selectivity, described phenol-formaldehyde resin modified preparation process, institute State modified talc powder preparation process with embodiment 1;
Difference is Pulvis Talci, described acrylic acid and the matter of described BPO described in the preparation process of described modified talc powder Amount ratio is 100:18:0.2;Described octaphenyl eight silsesquioxane, described 2,4-resorcylic acid, described calcium stearate and The weight ratio of described polyphosphoric acids is 1:2:3:18.
Embodiment 7
The thermosetting ink of the anti-chemical nickel and gold of described selectivity, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.5 with the mass ratio of described diethylene glycol ether;Described Firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is Maleic acid-acrylic acid copolymer;Described levelling agent is EL-2818 levelling agent;
The thermosetting ink preparation process of the anti-chemical nickel and gold of described selectivity, described phenol-formaldehyde resin modified preparation process, institute State modified talc powder preparation process with embodiment 1;
Difference is Pulvis Talci, described acrylic acid and the matter of described BPO described in the preparation process of described modified talc powder Amount ratio is 100:10:0.12;Described octaphenyl eight silsesquioxane, described 2,4-resorcylic acid, described calcium stearate with And the weight ratio of described polyphosphoric acids is 1:1:1:15.
Embodiment 8
The thermosetting ink of the anti-chemical nickel and gold of described selectivity, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.5 with the mass ratio of described diethylene glycol ether;Described Firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is Maleic acid-acrylic acid copolymer;Described levelling agent is EL-2818 levelling agent;
The thermosetting ink preparation process of the anti-chemical nickel and gold of described selectivity, described phenol-formaldehyde resin modified preparation process, institute State modified talc powder preparation process with embodiment 1;
Difference is that 2-(4-toluyl) benzoic acid replaces described 2-(4-(2-hydroxybenzoyl)) benzoic acid.
Comparative example 1
The thermosetting ink of described anti-chemical nickel and gold, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.5 with the mass ratio of described diethylene glycol ether;Described Firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is Maleic acid-acrylic acid copolymer;Described levelling agent is EL-2818 levelling agent;
The thermosetting ink preparation process of described anti-chemical nickel and gold, described phenol-formaldehyde resin modified preparation process, same to embodiment 1;
Comparative example 2
The thermosetting ink of described anti-chemical nickel and gold, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.5 with the mass ratio of described diethylene glycol ether;Described Firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is Maleic acid-acrylic acid copolymer;Described levelling agent is EL-2818 levelling agent;
The thermosetting ink preparation process of described anti-chemical nickel and gold, described modified talc powder preparation process are with embodiment 1;
The preparation process of described phenolic resin is as follows:
By phenols (p-tert-butylphenol, Octylphenol mixture), 3% sodium hydrate aqueous solution (concentration is 6%) adds In 250mL four-hole boiling flask, add heat fusing, molten after open stirring, be cooled to 60 DEG C be slowly added dropwise 37% formaldehyde, after adding 65 DEG C of insulation reaction 5h, are cooled to 50 DEG C;Stop when being neutralized to pH=6 with the hydrochloric acid of 10%, stop stirring and stand 0.5h layering, organic Layer washing twice, abandons water layer and obtains lurid resol;Described phenolic aldehyde mol ratio 1:2;Described p-tert-butylphenol It is 1:1 with the mol ratio of described Octylphenol;The weight average molecular weight of described phenolic resin is 10000.
Comparative example 3
The thermosetting ink of described anti-chemical nickel and gold, calculates by weight, including:
Wherein, ethylene glycol monobutyl ether described in described solvent is 1:1.5 with the mass ratio of described diethylene glycol ether;Described Firming agent is 2-methylimidazole;Described thickening agent is aerosil;Described lubricant is Tissuemat E;Described dispersant is Maleic acid-acrylic acid copolymer;Described levelling agent is EL-2818 levelling agent;
The thermosetting ink preparation process of described anti-chemical nickel and gold is with embodiment 1;The preparation process of described phenolic resin is same Comparative example 2.
Performance test methods
Use the silk screen of PET120 mesh by embodiment 1~8 and the thermosetting of comparative example 1~3 select carburetion ink to be applied to each base On plate, (10cm × 10cm) is the thickness of thickness 20 μm, by heated air circulation type drying oven, heats 40min at 110 DEG C, Heating makes its heat cure, makes test film.
1, chemically-resistant plating nickel gold
The each test film being formed with the copper clad laminate FR-4 substrate of circuit and manufacture, is being pre-configured with the chemistry heated Nickel plating bath (85 DEG C), each immersion 30 minutes in chemistry gold plating solution (90 DEG C), washing in 10 minutes air-dries, by visual valuation film layer Expansion, stripping, variable color.
Metewand is as follows,
Zero: can't see change completely
△: only slight variations
×: film has expansion, stripping.
2, the stripping quantity in chemical nickel (chemistry gold) plating solution
Brassboard (10cm × 10cm) is soaked in after heating in advance in good 1 liter of chemical nickel plating solution 30 minutes, after take plating Liquid ultraviolet spectrophotometer (wavelength 267.1) surveys absorbance.
3, the removal of oil film
The each test film being formed with the copper clad laminate FR-4 substrate of circuit and manufacture, soaks and is previously heated to 50 degree In 4%NaOH solution 30 seconds, 1 minute, 2 minutes.
4, electrical insulating property
The comb-type electrode of each test film being formed with the copper clad laminate of IPCB-25 comb-type electrode B sample and manufacture, applies The bias voltage of DC5.5V, after placing 150h, measures insulating resistance value at humidity 85%, temperature 130 DEG C.
5, bending strength
Use rent GER-20 type electronic universal tester to test under room temperature, perform according to GB/T2570-1995 standard.
6, impact strength
The unnotched impact strength of test sample on XCJ-L simple beam impact strength testing machine is used, according to GB/ under room temperature T2571-1995 standard performs.
7, acid resistance
Under the conditions of 20~50 DEG C, by test film mass fraction be 5~10% sulfuric acid solution in soak 10h, pass through mesh Depending on the expansion of evaluation test sheet Sprouting resistance oxidant layer, stripping, variable color.
Metewand is as follows,
Zero: can't see change completely
△: only slight variations
×: film has expansion, stripping.
Table 1 the performance test results
From above-mentioned test result it can be seen that compared with phenolic resin, Pulvis Talci, the modified phenolic resin that the present invention provides Fat and modified talc powder to a great extent enhance the performances such as the thermostability of solder mask, acid resistance, mechanical strength.
Aforesaid example is merely illustrative, for explaining some features of the method for the invention.Appended right is wanted Ask and be intended to the widest scope that requirement it is contemplated that, and embodiments as presented herein is only according to all possible enforcement The explanation of the embodiment of the selection of the combination of example.Therefore, the purpose of applicant is that appended claim is not illustrated this The selectional restriction of the example of bright feature.Some numerical rangies used in the claims also include sub-model within Enclosing, the change in these scopes also should be construed to be covered by appended claim in the conceived case.

Claims (10)

1. the thermosetting ink of the anti-chemical nickel and gold of selectivity, it is characterised in that calculate by weight, including:
Wherein, described phenol-formaldehyde resin modified is 2-(4-(2-hydroxybenzoyl)) benzoic acid modified phenolic resin, described modified talc powder For containing stearic octaphenyl eight silsesquioxane modified acroleic acid Pulvis Talci;Described firming agent is polyamide, imidazoles One in firming agent, 590 firming agent.
The thermosetting ink of the anti-chemical nickel and gold of selectivity the most according to claim 1, it is characterised in that described modified phenolic resin 2-(4-(2-hydroxybenzoyl)) benzoic acid and the mass ratio (1~3.5) of phenolic resin in fat: 1.
The thermosetting ink of the anti-chemical nickel and gold of selectivity the most according to claim 1, it is characterised in that described modified phenolic resin 2-(4-(2-hydroxybenzoyl)) benzoic acid and the mass ratio (1~3) of phenolic resin in fat: 1.
The thermosetting ink of the anti-chemical nickel and gold of selectivity the most according to claim 1, it is characterised in that described modified phenolic resin The weight average molecular weight of fat is 5000~200000.
The thermosetting ink of the anti-chemical nickel and gold of selectivity the most according to claim 1, it is characterised in that described solvent is second two Alcohol monobutyl ether, diethylene glycol ether, wherein said ethylene glycol monobutyl ether is 1:(1.2 with the mass ratio of described diethylene glycol ether ~2).
The thermosetting ink of the anti-chemical nickel and gold of selectivity the most according to claim 1, it is characterised in that described modified talc powder Preparation process as follows:
(1) it is in 60 DEG C of high-speed mixers that Pulvis Talci adds barrel temperature, by weight adding acrylic acid and BPO, stirs 0.5 ~after 2h, discharging, after high-speed mixer barrel temperature is risen to 120 DEG C, above-mentioned material is refunded in high-speed mixer, high-speed stirring Discharging after mixing 0.5~1h, obtains acrylic acid Pulvis Talci;
(2) by weight by octaphenyl eight silsesquioxane and 2,4-resorcylic acid is dissolved in polyphosphoric acids, 180 DEG C After lower reaction 5-10h, it is down to 120 DEG C, adds calcium stearate, after reacting 3-6h at 120 DEG C, be down to room temperature, pour in acetone, fill After dividing washing, filtering and be also dried 12 hours at 120 DEG C in vacuum drying oven, obtain stearic acid and 2,4-resorcylic acid is modified Octaphenyl eight silsesquioxane;
(3) by octaphenyl eight modified with step (2) stearic acid and 2,4-resorcylic acid for acrylic acid Pulvis Talci in step (1) It is in 120 DEG C of high-speed mixers that silsesquioxane adds barrel temperature, discharging after high-speed stirred 0.5~2h.
The thermosetting ink of the anti-chemical nickel and gold of selectivity the most according to claim 6, it is characterised in that described modified talc powder Preparation process described in Pulvis Talci, the mass ratio of described acrylic acid and described BPO be 100:(10-18): (0.12-0.2).
The thermosetting ink of the anti-chemical nickel and gold of selectivity the most according to claim 6, it is characterised in that described modified talc powder Preparation process described in Pulvis Talci, the mass ratio of described acrylic acid and described BPO be 100:16:0.18.
The thermosetting ink of the anti-chemical nickel and gold of selectivity the most according to claim 6, it is characterised in that described modified talc powder Preparation process described in octaphenyl eight silsesquioxane, described 2,4-resorcylic acid, described calcium stearate and described The weight ratio of polyphosphoric acids is 1:(1-2): (1-3): (10-18).
The thermosetting ink of the anti-chemical nickel and gold of selectivity the most according to claim 6, it is characterised in that described modified talc Octaphenyl eight silsesquioxane described in the preparation process of powder, described 2,4-resorcylic acid, described calcium stearate and institute The weight ratio stating polyphosphoric acids is 1:1.2:1.3:15.
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CN101045839A (en) * 2007-04-10 2007-10-03 深圳市容大电子材料有限公司 Liquid photosensitive ink and applied in printing circuit board
CN103627248A (en) * 2012-08-27 2014-03-12 卡姆特有限公司 Curable ink and a method for printing and curing the curable ink

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CN1396218A (en) * 2001-07-13 2003-02-12 叶嗣韬 Non-solvent thermohardening photosensitive rabbet ink
US20030089613A1 (en) * 2001-11-15 2003-05-15 Ching Chang Yu Method of selectively electroplating by screen-plating technology
CN101045839A (en) * 2007-04-10 2007-10-03 深圳市容大电子材料有限公司 Liquid photosensitive ink and applied in printing circuit board
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CN109021502A (en) * 2018-07-06 2018-12-18 南雄市科鼎化工有限公司 A kind of outer layer plug socket resin and preparation method thereof
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