CN103869615A - Photocurable composition, solder resist layer and printed circuit board - Google Patents
Photocurable composition, solder resist layer and printed circuit board Download PDFInfo
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- CN103869615A CN103869615A CN201310632657.5A CN201310632657A CN103869615A CN 103869615 A CN103869615 A CN 103869615A CN 201310632657 A CN201310632657 A CN 201310632657A CN 103869615 A CN103869615 A CN 103869615A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C09D11/30—Inkjet printing inks
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
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- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The invention provides a photocurable composition with low viscosity and excellent adaptation and reflectivity, a solder resist layer and a printed circuit board. The photocurable composition is characterized by comprising (A) photocurable resins, (B) photopolymerization initiators, (C) (methyl) acrylate monomers with phosphate structures, (D) (methyl) acrylate monomers without phosphate structures and (E) rutile-type titanium oxide.
Description
Technical field
The present invention relates to Photocurable composition, solder mask and printed circuit board (PCB), specifically, relate to low viscosity and can obtain adaptation and the Photocurable composition of the white solidfied material of reflectivity excellence and use its solder mask, printed circuit board (PCB).
Background technology
Photocurable composition is applied on the base materials such as printed circuit board (PCB) and photocuring and make the insulation courses such as solder mask and use and be subject to widespread use (patent documentation 1).When Photocurable composition utilizes as the insulation course of the printed circuit board (PCB) of the light-emitting components such as diode installed (LED), electroluminescence (EL), in order effectively to utilize light, the white Photocurable composition of often making high reflectance forms.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-311233 communique
Summary of the invention
the problem that invention will solve
In order to make white solidfied material, need to be in Photocurable resin composition a large amount of compoundings are as the titanium dioxide of Chinese white.But, when compounding titanium dioxide, exist the ratio of the organic principle in Photocurable composition to tail off, the film obtaining becomes fragile, the problem of the adaptation variation to base material.And then, due to the compounding of titanium dioxide, the viscosity rise of composition, treatability, the poor problem of operability while also having.
In order to tackle viscosity rise as above, can consider that compounding solvent reduces viscosity in composition.But, while reducing viscosity by the high compounding of solvent, in order to remove solvent, need long drying process, the problem that exists operability to reduce.
Therefore, the object of the invention is to, low viscosity is provided and can obtains adaptation and the Photocurable composition of the white solidfied material of reflectivity excellence and use its solder mask, printed circuit board (PCB).
for the scheme of dealing with problems
The inventor etc. In view of the foregoing conduct in-depth research, found that, there is (methyl) acrylate monomer of phosphate ester structure and do not there is (methyl) acrylate monomer of phosphate ester structure by compounding in the Photocurable composition that comprises light-cured resin, Photoepolymerizationinitiater initiater and Titanium Dioxide Rutile Top grade, can address the above problem, thereby complete the present invention.
; Photocurable composition of the present invention is characterised in that, comprises: (A) light-cured resin, (B) Photoepolymerizationinitiater initiater, (C) have (methyl) acrylate monomer of phosphate ester structure, (methyl) acrylate monomer that (D) do not have phosphate ester structure and (E) Titanium Dioxide Rutile Top grade.
Photocurable composition of the present invention is preferably ink jet printing and uses.
Solder mask of the present invention is characterised in that, it solidifies above-mentioned Photocurable composition to form.
Printed circuit board (PCB) of the present invention is characterised in that to possess above-mentioned solder mask.
the effect of invention
According to the present invention, low viscosity can be provided and can obtain adaptation and the Photocurable composition of the white solidfied material of reflectivity excellence and use its solder mask, printed circuit board (PCB).
Embodiment
Below, each composition of Photocurable composition of the present invention is described in detail.It should be noted that, (methyl) acrylate refers to, uses as the term of being referred to as acrylate and methacrylate, comprises any one or both in acrylate or methacrylate.Other is similarly expressed too.
[(A) light-cured resin]
The resin of the contained light-cured resin of Photocurable composition of the present invention as long as being cured by irradiation, preferably has the prepolymer (or oligomer) of more than one ethylenic unsaturated bond in molecule.In addition, (A) light-cured resin also can be called (D) composition (methyl) acrylate monomer except (C).
Light-cured resin can have carboxyl, also can not have carboxyl.When use has the light-cured resin of carboxyl, can make Photocurable composition is alkali developable, but Photocurable composition of the present invention is not limited to alkali developable.
As the example of above-mentioned oligomer, for example can list unsaturated polyester (UP) is oligomer, (methyl) acrylic ester oligomer etc.As (methyl) acrylic ester oligomer, can list epoxy (methyl) acrylate such as phenol novolaks epoxy (methyl) acrylate, cresols novolaks epoxy (methyl) acrylate, bisphenol type epoxy (methyl) acrylate, carbamate (methyl) acrylate, epoxy amino formic ether (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) acrylate, polybutadiene-modified (methyl) acrylate etc.
In addition, in addition also can list the such prepolymer in following (1)～(9).
(1) make the epoxy radicals of the multi-functional epoxy compound in 1 molecule with at least two epoxy radicals and the carboxyl of unsaturated monocarboxylic carry out esterification (full esterification or partial esterification, preferably full esterification), the hydroxyl that makes to generate further react with saturated or undersaturated multi-anhydride and obtain contain carboxyl photoresist;
(2) multipolymer that makes to be formed by (methyl) alkyl acrylate and (methyl) glycidyl acrylate reacts with (methyl) acrylic acid, then further make saturated or undersaturated multi-anhydride react and obtain contain carboxyl photoresist;
(3) make the multipolymer of (methyl) acrylic acid hydroxyalkyl acrylate and (methyl) alkyl acrylate and (methyl) glycidyl acrylate react with (methyl) acrylic acid, then further make saturated or undersaturated multi-anhydride react and obtain contain carboxyl photoresist;
(4) make (methyl) alkyl acrylate and (methyl) acrylic acid multipolymer partly react with (methyl) glycidyl acrylate and obtain contain carboxyl photoresist;
(5) make to have in 1 molecule in the multi-functional epoxy compound of at least two epoxy radicals and unsaturated monocarboxylic and 1 molecule, have at least two hydroxyls and with the reaction product of the compound of other reactive group beyond the hydroxyl-removal of epoxy reaction, react with saturated or undersaturated multi-anhydride and obtain contain carboxyl photoresist;
(6) multipolymer that makes unsaturated multi-anhydride and the styrene etc. such as maleic anhydride there is the aromatic hydrocarbon of vinyl react with (methyl) acrylic acid hydroxyl alkane ester and obtain containing carboxyl photoresist;
(7) the multifunctional oxetane compound that makes to have at least two oxetanes rings in 1 molecule reacts with unsaturated monocarboxylic, the primary hydroxyl in the modification oxetane resin that makes to obtain react with saturated or unsaturated multi-anhydride and obtain containing carboxyl photoresist;
(8) reaction product of phenolic varnish type phenolics and alkylene oxide is reacted with unsaturated monocarboxylic, the reaction product that makes to obtain react with saturated or unsaturated multi-anhydride and obtain containing carboxyl photoresist;
(9) make to have in 1 molecule and in the multi-functional epoxy compound of at least two epoxy radicals and unsaturated monocarboxylic and 1 molecule, there are at least two hydroxyls and contain the polybasic carboxylic acid urethane resin of unsaturated group with reaction product, the product obtaining with saturated or undersaturated multi-anhydride with containing unsaturated group monoisocyanates reacts etc. of the compound of other reactive group beyond the hydroxyl-removal of epoxy reaction.
In the middle of above-mentioned prepolymer, preferably carbamate (methyl) acrylate, polyester acrylate.Carbamate (methyl) acrylate comprises above (methyl) acryloxy and comprises multiple amino-formate bonds.Carbamate (methyl) acrylate for example can be manufactured as follows: utilize polyvalent alcohol and polyisocyanates synthesis of carbamates prepolymer, its addition is had to (methyl) acrylate of hydroxyl, thereby manufacture.
As polyvalent alcohol, can use without particular limitation the known polyvalent alcohols such as hydrocarbon polyvalent alcohol, polyether glycol, polyester polyol, polycarbonate polyol.In addition, as polyisocyanates, can use without particular limitation the known polyisocyanates such as aromatic polyisocyanate, aliphatic polyisocyante, aromatic series aliphatic polyisocyante, ester ring type polyisocyanates.
When functional group's number is excessive, have that cross-linking density uprises, the warpage of solidfied material becomes large, the also tendency of variation of obdurability, be therefore preferably 2 officials can, 3 official's energy.In addition, as (A) light-cured resin, preferably comprise at least two kinds of carbamates (methyl) acrylate that structure is different.As the commercially available product of carbamate (methyl) acrylate, for example, can list Daicel-Cytec Co., the EBECRYL8402 that Ltd. manufactures etc.
Polyester acrylate is the terminal acrylate of polyester, and for example can enumerating sends as an envoy to reacts polyvalent alcohol (polyol) and obtain polyester polyol with polybasic carboxylic acid reacts with (methyl) acrylic acid derivatives such as (methyl) acrylic acid, 2-hydroxyl (methyl) acrylate the material forming.As polyvalent alcohol, can list above-mentioned material.As polybasic carboxylic acid, can use without particular limitation the known polybasic carboxylic acids such as aromatic polycarboxylic acid such as alicyclic polybasic carboxylic acid, phthalic acid, trimellitic acid such as the aliphatics such as hexane diacid, maleic acid polybasic carboxylic acid, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic.When functional group's number is excessive, have that cross-linking density uprises, the warpage of solidfied material becomes large, the also tendency of variation of obdurability, be preferably 2 officials can, 3 official's energy.As the commercially available product of polyester acrylate, for example, can list the ARONIX M-6200 that East Asia synthetic chemical industry Co., Ltd. manufactures.
(A) weight-average molecular weight of light-cured resin is preferably 1000～20000.When weight-average molecular weight less than 1000, the cross-linking density that existence is brought by the light-cured resin with multiple ethylenically unsaturated groups uprises, the cure shrinkage of resin also becomes greatly, the warpage of solidfied material becomes large worry.On the other hand, weight-average molecular weight exceedes at 20000 o'clock, and the viscosity of composition uprises, the worry that exists treatability to worsen.
[(B) Photoepolymerizationinitiater initiater]
As Photoepolymerizationinitiater initiater contained in Photocurable composition of the present invention, be not particularly limited, can use known Photoepolymerizationinitiater initiater.For example can list the benzoin classes such as benzoin, benzil, benzoin methylether, benzoin ethyl ether, benzoin positive propyl ether, benzoin iso-propylether, benzoin n-butylether, benzoin alkylether class, benzophenone, to methyldiphenyl ketone, Michler's keton, methyldiphenyl ketone, 4,4 '-dichloro benzophenone, 4, the 4 '-benzophenones such as bis-diethylamino benzophenone, acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, N, the acetophenones such as N-dimethylamino benzoylformaldoxime, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, CTX, 2, the thioxanthones Class such as 4-diisopropyl thioxanthones, the Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-amino anthraquinones, the ketal classes such as acetophenone dimethyl ketal, benzil dimethyl ketal, ethyl-4-dimethylaminobenzoic acid ester, 2-(dimethylamino) ethylamino benzonitrile acid esters, to benzoates such as mesitylenic acid ethyl esters, 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] 1, 2-acetyl caproyl, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] the oxime ester class such as-1-(O-acetyl oxime) ethyl ketone, two (η 5-2, 4-cyclopentadiene-1-yl)-bis-(2, the fluoro-3-of 6-bis-(1H-pyrroles-1-yl) phenyl) titanium, two (cyclopentadienyl groups)-bis-[2, the fluoro-3-of 6-bis-(2-(1-pyrroles-1-yl) ethyl) phenyl] the luxuriant titanium class such as titanium, 2, 4, 6-trimethylbenzene formyl diphenyl phosphine oxide, two (2, 4, 6-trimethylbenzoyl)-acylphosphine oxide the classes such as phenyl phosphine oxide, curing phenyl 2-nitrofluorene, butyroin, anisoin ether, azoisobutyronitrile, tetramethylthiuram disulfide etc.These Photoepolymerizationinitiater initiaters can use separately one, also can combine two or more use.(B) Photoepolymerizationinitiater initiater is with respect to 100 mass parts (A) light-cured resin, preferably with 0.1～15 mass parts, more preferably with 0.1～10 mass parts, further more preferably contain with the ratio of 0.3～8 mass parts.
[(C) thering is (methyl) acrylate monomer of phosphate ester structure]
Photocurable composition of the present invention contains (methyl) acrylate monomer with phosphate ester structure as (C) composition.As long as (methyl) acrylate monomer with phosphate ester structure is just not particularly limited, can use known material.As object lesson, can list list (2-acryloxy ethyl) phosphate ester acid, single (2-methacryloxyethyl) phosphate ester acid, two (2-acryloxy ethyl) phosphate ester acid, two (2-methacryloxyethyl) phosphate ester acid, diphenyl (2-acryloxy ethyl) phosphate, diphenyl (2-methacryloxyethyl) phosphate, phenyl (2-acryloxy ethyl) phosphate, methacrylic acid acid phosphorus 2-ethoxyethyl acetate, methacryloxyethyl phosphate ester acid monoethanolamine salt, the chloro-2-acid of methacrylic acid 3-phosphorus oxygen propyl ester, acid phosphorus oxygen polyoxyethylene glycol monomethacrylates, acid phosphorus oxygen polyoxy trimethylene glycol methacrylate, (methyl) acryloxy ethyl phosphate ester acid, (methyl) acryloxy propyl group phosphate ester acid, (methyl) acryloxy-2-hydroxypropyl phosphate ester acid, (methyl) acryloxy-3-hydroxypropyl phosphate ester acid, (methyl) acryloxy-3-chlorine-2-hydroxyl propyl group phosphate ester acid, allyl alcohol phosphate ester acid, the phosphate of pentaerythritol triacrylate, the phosphate of dipentaerythritol five acrylate etc.Wherein, at room temperature easily processing for aqueous material, is preferred.
[(D) not thering is (methyl) acrylate monomer of phosphate ester structure]
Photocurable composition of the present invention comprises (methyl) acrylate monomer beyond (C) composition., for not thering is (methyl) acrylate monomer of phosphate ester structure.(methyl) acrylate monomer is the photoreactivity monomer with more than one ethylenically unsaturated group, as reactive diluent.As (methyl) acrylate monomer and known material all can use.For example can list (methyl) acrylic acid hydroxyalkyl acrylate classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, acrylic acid 4-hydroxy butyl ester, methacrylic acid 2-hydroxyl methyl esters; Isobornyl acrylate, acrylic acid tetrahydro furfuryl ester, N-acryloyl morpholine, NVP etc. have the simple function photoreactivity monomer class of cyclic skeleton; Mono acrylic ester or the diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol, diethylene glycol; N,N-DMAA, N hydroxymethyl acrylamide, N, the acrylic amides such as N-dimethylaminopropyl acrylamide; Acrylic acid N, N-dimethylamino ethyl ester, acrylic acid N, the acrylic-amino alkane ester classes such as N-dimethylamino propyl ester; Polyvalent alcohol or their multicomponent methacrylate such as ethylene oxide adduct or the propylene oxide adduct classes such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, three-hydroxyethyl isocyanuric acid ester; The esters of acrylic acid such as ethylene oxide adduct or propylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenols; The esters of acrylic acid of the glycidyl ethers such as glycerine diglycidyl ether, glycerine triglycidyl group ether, trimethylolpropane tris glycidyl ether, triglycidyl group isocyanuric acid ester; And melamine acrylate, phthalic acid 2-acryloxy ethyl ester and/or each methyl acrylic ester corresponding with aforesaid propylene acid esters etc.
(D) aforementioned (C) (methyl) acrylate monomer in addition preferably comprises different (methyl) acrylate monomer of functional group's number, and more preferably at least one in (D) composition is (methyl) acrylate monomer that 3 officials can be above.In addition, if 6 officials can more than, occur that solidfied material produces the worry of warpage, therefore functional group's number of (D) composition is preferably below 5.
(D) the compounding amount of composition is preferably 2～50 mass parts, 2～30 mass parts more preferably with respect to 1 mass parts (C) composition.In this ratio, with the compounding amount of (C) composition with respect to 100 mass parts (A) light-cured resin be preferably 1～20 mass parts, more preferably 1～15 mass parts, further more preferably the ratio of 3～7 mass parts contains.In addition, with the compounding amount of (D) composition with respect to above-mentioned 100 mass parts (A) composition be preferably 2～500 mass parts, more preferably the ratio of 5～300 mass parts contains.
[(E) Titanium Dioxide Rutile Top grade]
Photocurable composition of the present invention contains (E) Titanium Dioxide Rutile Top grade as Chinese white.There is rutile-type, Detitanium-ore-type in titanium dioxide, but from obtain the solidfied material of high reflectance, on the few aspect of the deteriorated impact of resin, can composite inhibiting the aspect of viscosity rise, use Titanium Dioxide Rutile Top grade.Titanium dioxide is not limited to the method for makings such as chlorine method, sulfuric acid process.In addition, also can use aptly surface-treated titanium dioxide such as implementing the processing of peroxidating aluminium, silica-treated.
In addition to rutile-type titanium oxide as a white pigment may also be mixed with zinc oxide, basic lead carbonate, basic lead sulfate, lead sulfate, zinc sulfide, antimony oxide, barium sulfate and the like.
(E) the compounding amount of Titanium Dioxide Rutile Top grade is with respect to 100 mass parts (A) light-cured resin, is preferably 100～350 mass parts, 150～300 mass parts more preferably.(E) when the compounding amount of titanium dioxide exceedes 350 mass parts, it is too high that viscosity becomes, and printing becomes difficulty.On the other hand, when compounding quantity not sufficient 100 mass parts, be sometimes difficult to obtain the solidfied material of high reflectance.
(colorant)
In the present invention, as required, can in the scope of not damaging effect of the present invention, use (E) Titanium Dioxide Rutile Top grade colorant in addition.For example, can manufacture grizzly Photocurable composition by compounding black colorant.
As other colorant, can use the conventional known colorants such as red, blue, green, yellow, white, black, purple, orange, dark brown, pigment, dyestuff, pigment all can.As object lesson, can list with Colour Index (C.I.; The Society of Dyers and Colourists distribution) material of numbering.But, from reducing the viewpoint of carrying capacity of environment and the impact on human body, preferably not halogen-containing.
As red stain, can list monoazo system, bisdiazo system, azo lake system, benzimidazolone system, perylene system, diketopyrrolo-pyrrole system, condensation azo system, anthraquinone system, quinacridone based compound etc.
As blue colorant, can list metal and replace or unsubstituted phthalocyanine system, anthraquinone based compound etc.
As green colourant, can list metal and replace or unsubstituted phthalocyanine system, anthraquinone Xi, perylene based compound etc.
As yellow colorants, can list monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone based compound etc.
As black colorant, can list carbon black etc.
Compounding amount to other colorant is not particularly limited, aforementioned containing carboxy resin (A) with respect to 100 mass parts, is preferably 0～10 mass parts, is particularly preferably 0.1～5 mass parts.
[other composition]
In Photocurable composition of the present invention, not damaging in the scope of effect of the present invention, the known adjuvant beyond can also compounding mentioned component.As adjuvant, can list thermal polymerization inhibitor, ultraviolet light absorber, silane coupling agent, plastifier, fire retardant, antistatic agent, aging resister, antibacterial mildew inhibitor, defoamer, levelling agent, filler, thickening agent, adaptation imparting agent, thixotropy imparting agent etc.As solder resist, be applied to substrate surface, dry, then when photocuring, also can use solvent.In addition, during as solder resist, the heat-curing resins such as preferred compounding epoxy compound.Above-mentioned preferably do not contain, preferably not compounding refers to, does not get rid of this composition that contains trace in composition.
Photocurable composition of the present invention for example utilizes following painting method to be coated to after base material etc., and the ultraviolet ray of irradiation ultraviolet radiation, optimal wavelength 10～400nm, is cured.
As ultraviolet irradiation light source, can list low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp, laser, UV-LED etc.
Coating process can be applied any means such as dip coating, flow coat method, rolling method, excellent painting method, silk screen print method, curtain painting method, gravure processes, hectographic printing method, ink jet printing method.
Solder mask of the present invention is characterised in that, it is applied to the invention described above Photocurable composition on substrate and solidifies and forms.
Coating, curing method can be according to known method as described below.
Be adjusted into as required the viscosity that is suitable for coating process with solvent dilution, it is for example coated with to the methods such as method, spraying process, rolling method, ink jet printing method and is applied on the printed circuit board (PCB) that is formed with circuit by silk screen print method, curtain, for example at the temperature of approximately 60～100 DEG C by organic solvent volatile dry contained in composition, thereby can form not sticky film.Then, optionally utilize ultraviolet ray to expose according to pattern direct irradiation laser isoreactivity energy-ray or by forming figuratum photomask, thereby solidify.When Photocurable composition is alkali developable, unexposed portion is developed with dilute alkaline aqueous solution, can form corrosion-resisting pattern.And then, according to expectation, irradiating after ultraviolet Line, be heating and curing or finally solidify (completely curing), thereby forming cured film (solidfied material).
Wherein, use the ink jet printing method of Photocurable composition need to, in printing afterwards by the dry operation of removing the operation of organic solvent and developing with aqueous alkali, can simplified pattern not form operation, so preferably.
In addition, Photocurable composition of the present invention, except being applied to solder mask, can also be applied to the insulating material such as interlayer dielectic, overlayer.In addition, Photocurable composition of the present invention also can be used as Xi Di (solder dam).
Embodiment
Below, further describe the present invention by embodiment, comparative example, but the present invention is not subject to any restriction of these embodiment, comparative example.
By mixing with triple-roller mill the each composition described in following table 1～4, prepare Photocurable composition.
Then,, after each Photocurable composition is applied on substrate with serigraphy, the mode irradiation ultraviolet radiation taking the accumulated light on composition as 1500mJ/cm2 in high-pressure sodium lamp UV furnace conveyor solidifies it, obtains test film.The test film obtaining is evaluated by following evaluation method.
For the Photocurable composition of embodiment 12, use ink-jet printer (FUJIFILM Global Graphic Systems Co., Ltd. manufacture Materials Printer DMP-2831) be applied on substrate after, in high-pressure sodium lamp UV furnace conveyor taking the accumulated light on composition as 1500mJ/cm
2mode irradiation ultraviolet radiation make its solidify, obtain test film.The test film obtaining is evaluated by following evaluation method.
(printing)
Utilize the cone-plate type viscosity meter TVE-33H (cone rotor 3 ° of R9.7,5rpm) that Toki Sangyo Co., Ltd. manufactures to measure the viscosity at 25 DEG C to the each composition obtaining.
(reflectivity)
The test film obtaining is used to Konica Minolta, and the spectrocolorimeter CM-2600d that Inc. manufactures measures reflectivity (Y value).
(adaptation)
On the test film obtaining, form 100 grid with cutter according to JIS K5400-8.5, peel off the adaptation of evaluating film by adhesive tape.
Zero: residual grid number is more than 80
△: residual grid number is 80 of 70 above and less thaies
×: residual grid is counted 70 of less thaies
[table 1]
[table 2]
[table 3]
※ 1:Daicel-Cytec Co., the EBECRYL8402 that Ltd. manufactures, 2 officials' energy urethane acrylates, photo-curable oligomer
※ 2: the ARONIX M-6200 that Toagosei Co., Ltd manufactures, 2 functional polyester acrylate, photo-curable oligomer
※ 3:2-EAQ, Photoepolymerizationinitiater initiater
The Irgacure819 that ※ 4:BASF company manufactures, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, Photoepolymerizationinitiater initiater
※ 5: the KAYAME RPM-2 that Nippon Kayaku K. K manufactures, two (2-methacryloxyethyl) phosphate ester acid, has the methacrylate monomers of phosphate ester structure
※ 6: the LIGHT ESTER P-1M that Kyoeisha Chemical Co., Ltd. manufactures, single (2-methacryloxyethyl) phosphate ester acid, has the methacrylate monomers of phosphate ester structure
※ 7: the HOA-MPL (N) that Kyoeisha Chemical Co., Ltd. manufactures, phthalic acid 2-acryloxy ethyl ester, does not have the acrylate monomer of phosphate ester structure
※ 8: the 4HBA that Nippon Kasei Chemical Company manufactures, acrylic acid 4-hydroxy butyl ester, does not have the acrylate monomer of phosphate ester structure
※ 9: the LIGHT ESTER HO-250 (N) that Kyoeisha Chemical Co., Ltd. manufactures, methacrylic acid 2-hydroxyl methyl esters, does not have the methacrylate monomers of phosphate ester structure
※ 10: the LIGHT ESTER2EG that Kyoeisha Chemical Co., Ltd. manufactures, diethylene glycol dimethylacrylate, does not have the methacrylate monomers of phosphate ester structure
※ 11: the TIPAQUE CR-97-Super70 that Ishihara Sangyo Kaisha, Ltd. manufactures, Titanium Dioxide Rutile Top grade
※ 12:Titan Kogyo, the KRONOS titanium dioxide KA-15 that Ltd. manufactures, anatase-type titanium oxide
[table 4]
※ 13:Daicel-Cytec Co., 1 of Ltd. manufacture, 6-hexanediyl ester
[table 5]
[table 6]
[table 7]
[table 8]
As shown in table 5,6 and 8, embodiment 1～12 contains light-cured resin, Photoepolymerizationinitiater initiater, have (methyl) acrylate monomer of phosphate ester structure, do not have (methyl) acrylate monomer and the Titanium Dioxide Rutile Top grade of phosphate ester structure, therefore has low viscosity, high reflectance, high adhesion.On the other hand, as shown in table 7, comparative example 1～3 is not containing (methyl) acrylate monomer with phosphate ester structure, and therefore, although be low viscosity, high reflectance, adaptation is low.And then the titanium dioxide of comparative example 4 is Detitanium-ore-type but not rutile-type, therefore, although adaptation is good, viscosity is high, and reflectivity is low.In addition, comparative example 5 is not containing (methyl) acrylate monomer without phosphate ester structure, and therefore viscosity is high.
Claims (4)
1. a Photocurable composition, is characterized in that, comprises:
(A) light-cured resin,
(B) Photoepolymerizationinitiater initiater,
(C) have phosphate ester structure (methyl) acrylate monomer,
(D) do not have phosphate ester structure (methyl) acrylate monomer and
(E) Titanium Dioxide Rutile Top grade.
2. Photocurable composition according to claim 1, is characterized in that, it is ink jet printing use.
3. a solder mask, is characterized in that, it is that the Photocurable composition described in claim 1 or 2 is solidified and formed.
4. a printed circuit board (PCB), is characterized in that, possesses solder mask claimed in claim 3.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012-270654 | 2012-12-11 | ||
| JP2012270654 | 2012-12-11 | ||
| JP2013-117812 | 2013-06-04 | ||
| JP2013117812A JP6209365B2 (en) | 2012-12-11 | 2013-06-04 | Photocurable resin composition, solder resist and printed wiring board |
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| CN103869615A true CN103869615A (en) | 2014-06-18 |
| CN103869615B CN103869615B (en) | 2019-12-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104536264A (en) * | 2014-12-26 | 2015-04-22 | 上海孚赛特新材料科技有限公司 | Black photosensitive resin composition and application of black photosensitive resin composition |
| CN116262397A (en) * | 2021-12-15 | 2023-06-16 | 株式会社理光 | Imaging method, imaging device and active energy ray-curable composition combination |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7124948B1 (en) * | 2021-12-15 | 2022-08-24 | 株式会社リコー | Active energy ray-curable composition, active energy ray-curable ink composition, inkjet ink composition, composition container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, cured product , decorative body, laminated body, flexible device member, and flexible device |
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| CN1806186A (en) * | 2003-04-17 | 2006-07-19 | 埃西勒国际通用光学公司 | Photocurable adhesive composition and its use in the optical field |
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| JP2011145640A (en) * | 2009-12-16 | 2011-07-28 | Ricoh Co Ltd | Developing device, process unit, and image forming apparatus |
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| JP5489887B2 (en) * | 2010-06-30 | 2014-05-14 | 富士フイルム株式会社 | Liquid coating apparatus, liquid coating method, and nanoimprint system |
| JP4866969B2 (en) * | 2011-03-18 | 2012-02-01 | 太陽ホールディングス株式会社 | White solder resist composition and printed wiring board having solder resist layer made of cured product thereof |
| JP2012216799A (en) * | 2011-03-25 | 2012-11-08 | Fujifilm Corp | Functional liquid discharge device, functional liquid discharge method, and imprint system |
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| CN1806186A (en) * | 2003-04-17 | 2006-07-19 | 埃西勒国际通用光学公司 | Photocurable adhesive composition and its use in the optical field |
| CN101445644A (en) * | 2007-11-30 | 2009-06-03 | 太阳油墨制造株式会社 | White hardening resin composition |
| CN102459376A (en) * | 2009-06-02 | 2012-05-16 | 住友金属工业株式会社 | Photocurable composition suitable for rust prevention of threaded joint for steel pipe |
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| CN104536264A (en) * | 2014-12-26 | 2015-04-22 | 上海孚赛特新材料科技有限公司 | Black photosensitive resin composition and application of black photosensitive resin composition |
| CN116262397A (en) * | 2021-12-15 | 2023-06-16 | 株式会社理光 | Imaging method, imaging device and active energy ray-curable composition combination |
Also Published As
| Publication number | Publication date |
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| CN103869615B (en) | 2019-12-17 |
| KR102152817B1 (en) | 2020-09-08 |
| KR20140076483A (en) | 2014-06-20 |
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