CN103869615B - Photocurable composition, solder resist layer, and printed wiring board - Google Patents
Photocurable composition, solder resist layer, and printed wiring board Download PDFInfo
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- CN103869615B CN103869615B CN201310632657.5A CN201310632657A CN103869615B CN 103869615 B CN103869615 B CN 103869615B CN 201310632657 A CN201310632657 A CN 201310632657A CN 103869615 B CN103869615 B CN 103869615B
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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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Abstract
the invention provides a photocurable composition, a solder resist layer and a printed circuit board, wherein the photocurable composition has low viscosity and can obtain a white cured product with excellent adhesiveness and reflectivity. A photocurable composition comprising (A) a photocurable resin, (B) a photopolymerization initiator, (C) a (meth) acrylate monomer having a phosphate ester structure, (D) a (meth) acrylate monomer having no phosphate ester structure, and (E) rutile titanium oxide.
Description
Technical Field
The present invention relates to a photocurable composition, a solder resist layer, and a printed wiring board, and more particularly, to a photocurable composition that has low viscosity and can give a white cured product having excellent adhesion and reflectivity, and a solder resist layer and a printed wiring board using the same.
Background
A photocurable composition is widely used for coating a substrate such as a printed wiring board and photocuring the coating to form an insulating layer such as a solder resist layer (patent document 1). When the photocurable composition is used as an insulating layer of a printed wiring board on which a light emitting element such as a Light Emitting Diode (LED) or Electroluminescence (EL) is mounted, the photocurable composition is often formed into a white color having a high reflectance in order to effectively utilize light.
Documents of the prior art
Patent document
patent document 1: japanese patent laid-open publication No. 2005-311233
Disclosure of Invention
Problems to be solved by the invention
In order to obtain a white cured product, it is necessary to blend a large amount of titanium oxide as a white pigment in the photocurable resin composition. However, when titanium oxide is blended, the ratio of organic components in the photocurable composition decreases, and the resulting coating film becomes brittle, resulting in a problem of poor adhesion to a substrate. Further, the compounding of titanium oxide increases the viscosity of the composition, and there is a problem that the handling property and the workability are sometimes poor.
In order to cope with the viscosity increase as described above, it is conceivable to blend a solvent in the composition to reduce the viscosity. However, when the viscosity is reduced by high blending of the solvent, a long drying step is required to remove the solvent, and there is a problem that the workability is lowered.
Accordingly, an object of the present invention is to provide a photocurable composition which has a low viscosity and can give a white cured product having excellent adhesion and reflectivity, and a solder resist layer and a printed wiring board using the same.
Means for solving the problems
The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that the above problems can be solved by blending a (meth) acrylate monomer having a phosphate ester structure and a (meth) acrylate monomer having no phosphate ester structure in a photocurable composition comprising a photocurable resin, a photopolymerization initiator, and rutile titanium oxide, and have completed the present invention.
That is, the photocurable composition of the present invention is characterized by comprising: (A) a photocurable resin, (B) a photopolymerization initiator, (C) a (meth) acrylate monomer having a phosphate ester structure, (D) a (meth) acrylate monomer having no phosphate ester structure, and (E) rutile-type titanium oxide.
The photocurable composition of the present invention is preferably for inkjet printing.
The solder resist layer of the present invention is obtained by curing the photocurable composition.
The printed wiring board of the present invention is characterized by comprising the solder resist layer.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a photocurable composition which has low viscosity and can give a white cured product having excellent adhesion and reflectivity, and a solder resist layer and a printed wiring board using the same.
Detailed Description
Hereinafter, each component of the photocurable composition of the present invention will be described in detail. The term (meth) acrylate is used as a generic term for acrylate and methacrylate, and includes either or both of acrylate and methacrylate. The same applies to other similar expressions.
[ (A) Photocurable resin ]
The photocurable resin contained in the photocurable composition of the present invention may be any resin that can be cured by light irradiation, and is preferably a prepolymer (or oligomer) having one or more ethylenically unsaturated bonds in the molecule. The (a) photocurable resin may be referred to as a component other than the (C) (D) (meth) acrylate monomer.
The photocurable resin may or may not have a carboxyl group. When a photocurable resin having a carboxyl group is used, the photocurable composition can be made to be an alkali-developable type, but the photocurable composition of the present invention is not limited to the alkali-developable type.
Examples of the oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of the (meth) acrylate oligomer include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, bisphenol epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and polybutadiene-modified (meth) acrylate.
in addition, prepolymers described in the following (1) to (9) can be cited.
(1) A carboxyl group-containing photosensitive resin obtained by subjecting an epoxy group of a polyfunctional epoxy compound having at least two epoxy groups in 1 molecule to an esterification reaction (full esterification or partial esterification, preferably full esterification) with a carboxyl group of an unsaturated monocarboxylic acid, and further reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride;
(2) A carboxyl group-containing photosensitive resin obtained by reacting a copolymer formed from an alkyl (meth) acrylate and a glycidyl (meth) acrylate with (meth) acrylic acid and then further reacting a saturated or unsaturated polybasic acid anhydride;
(3) A carboxyl group-containing photosensitive resin obtained by reacting a copolymer of a hydroxyalkyl (meth) acrylate, an alkyl (meth) acrylate and glycidyl (meth) acrylate with (meth) acrylic acid and further reacting a saturated or unsaturated polybasic acid anhydride;
(4) A carboxyl group-containing photosensitive resin obtained by partially reacting a copolymer of an alkyl (meth) acrylate and (meth) acrylic acid with glycidyl (meth) acrylate;
(5) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product of 1 molecule of a polyfunctional epoxy compound having at least two epoxy groups, an unsaturated monocarboxylic acid, and 1 molecule of a compound having at least two hydroxyl groups and one reactive group other than a hydroxyl group which reacts with an epoxy group, with a saturated or unsaturated polybasic acid anhydride;
(6) A carboxyl group-containing photosensitive resin obtained by reacting a copolymer of an unsaturated polybasic acid anhydride such as maleic anhydride and an aromatic hydrocarbon having a vinyl group such as styrene with a hydroxyalkyl (meth) acrylate;
(7) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional oxetane compound having at least two oxetane rings in 1 molecule with an unsaturated monocarboxylic acid to react a primary hydroxyl group in the obtained modified oxetane resin with a saturated or unsaturated polybasic acid anhydride;
(8) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a novolak-type phenol resin and an alkylene oxide with an unsaturated monocarboxylic acid and reacting the obtained reaction product with a saturated or unsaturated polybasic acid anhydride;
(9) Unsaturated group-containing polycarboxylic acid urethane resins such as a reaction product of 1 molecule of a polyfunctional epoxy compound having at least two epoxy groups, and an unsaturated monocarboxylic acid, and 1 molecule of a compound having at least two hydroxyl groups and one reactive group other than a hydroxyl group which reacts with an epoxy group, and a reaction product of a saturated or unsaturated polybasic acid anhydride and an unsaturated group-containing monoisocyanate.
Among the above prepolymers, urethane (meth) acrylates and polyester acrylates are preferable. The urethane (meth) acrylate contains one or more (meth) acryloyloxy groups and contains a plurality of urethane bonds. The urethane (meth) acrylate can be produced, for example, as follows: a urethane prepolymer is synthesized from a polyol and a polyisocyanate, and a (meth) acrylate having a hydroxyl group is added thereto.
As the polyol, known polyols such as hydrocarbon polyol, polyether polyol, polyester polyol, polycarbonate polyol and the like can be used without particular limitation. As the polyisocyanate, known polyisocyanates such as aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, and alicyclic polyisocyanate can be used without particular limitation.
When the number of functional groups is too large, the crosslinking density tends to be high, the warpage of the cured product tends to be large, and the toughness tends to be poor, and therefore, 2-functional groups and 3-functional groups are preferable. The photocurable resin (a) preferably contains at least two types of urethane (meth) acrylates having different structures. Examples of commercially available urethane (meth) acrylates include EBECRYL8402 manufactured by Daicel-Cytec Co., Ltd.
The polyester acrylate is a terminal acrylate of a polyester, and examples thereof include a polyester polyol obtained by reacting a polyol (polyol) with a polycarboxylic acid, and a polyester obtained by reacting a (meth) acrylic acid derivative such as a (meth) acrylic acid or a 2-hydroxy (meth) acrylate. The polyhydric alcohol includes the above-mentioned ones. As the polycarboxylic acid, known polycarboxylic acids such as aliphatic polycarboxylic acids such as adipic acid and maleic acid, alicyclic polycarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid, and aromatic polycarboxylic acids such as phthalic acid and trimellitic acid can be used without particular limitation. When the number of functional groups is too large, the crosslinking density tends to be high, the warpage of the cured product tends to be large, and the toughness tends to be poor, and 2-functional groups and 3-functional groups are preferable. As a commercially available product of the polyester acrylate, ARONIX M-6200, manufactured by Toyo Synthesis chemical industries, Ltd.
(A) The weight average molecular weight of the photocurable resin is preferably 1000 to 20000. When the weight average molecular weight is less than 1000, the crosslinking density of the photocurable resin having a plurality of ethylenically unsaturated groups may be increased, the curing shrinkage of the resin may be increased, and the warpage of the cured product may be increased. On the other hand, when the weight average molecular weight exceeds 20000, the viscosity of the composition increases, and the handling property may deteriorate.
[ (B) photopolymerization initiator ]
The photopolymerization initiator contained in the photocurable composition of the present invention is not particularly limited, and a known photopolymerization initiator can be used. Examples thereof include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4 ' -dichlorobenzophenone, and 4,4 ' -bisdiethylaminobenzophenone; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and N, N-dimethylaminoacetophenone; thioxanthone such as 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2, 4-diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, and ethyl p-dimethylbenzoate; 1- [4- (phenylthio) -2- (O-benzoyloxime) ]1, 2-octanedione, oxime esters such as 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) ethanone, titanocenes such as bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2, 6-difluoro-3- (2- (1-pyrrol-1-yl) ethyl) phenyl ] titanium, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, phosphine oxide, Acylphosphine oxides such as bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, phenyl 2-nitrofluorene disulfide, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. These photopolymerization initiators may be used alone or in combination of two or more. (B) The photopolymerization initiator is preferably contained in an amount of 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.3 to 8 parts by mass, based on 100 parts by mass of the photocurable resin (a).
[ (C) a (meth) acrylate monomer having a phosphate ester Structure ]
The photocurable composition of the present invention contains a (meth) acrylate monomer having a phosphate ester structure as the component (C). The (meth) acrylate monomer having a phosphate structure is not particularly limited, and known ones can be used. Specific examples thereof include mono (2-acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) acid phosphate, bis (2-acryloyloxyethyl) acid phosphate, bis (2-methacryloyloxyethyl) acid phosphate, diphenyl (2-acryloyloxyethyl) phosphate, diphenyl (2-methacryloyloxyethyl) phosphate, phenyl (2-acryloyloxyethyl) phosphate, acid phosphoethyl methacrylate, methacryloyloxyethyl acid phosphate monoethanolamine salt, 3-chloro-2-acid phosphopropyl methacrylate, acid phosphooxyethylene mono methacrylate, acid phosphooxypropylene glycol methacrylate, (meth) acryloyloxyethyl acid phosphate, acid phosphooxypropylene glycol methacrylate, acid phosphooxyethylene mono methacrylate, acid phosphooxypropylene glycol methacrylate, acid phosphooxyethyl acid phosphate, acid phosphoethyl phosphate, acid phosphate, (meth) acryloyloxypropyl acid phosphate, (meth) acryloyloxy-2-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, allyl alcohol acid phosphate, phosphate of pentaerythritol triacrylate, phosphate of dipentaerythritol pentaacrylate, and the like. Among them, a substance which is liquid at room temperature is preferable because handling is easy.
[ (D) a (meth) acrylate monomer having no phosphate ester Structure ]
The photocurable composition of the present invention contains a (meth) acrylate monomer other than the component (C). That is, the (meth) acrylate monomer has no phosphate structure. The (meth) acrylate monomer is a photoreactive monomer having one or more ethylenically unsaturated groups and serves as a reactive diluent. Any known (meth) acrylate monomer can be used. Examples thereof include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and 2-hydroxymethyl methacrylate; monofunctional photoreactive monomers having a cyclic skeleton such as isobornyl acrylate, tetrahydrofurfuryl acrylate, N-acryloylmorpholine, and N-vinylpyrrolidone; monoacrylates or diacrylates of glycols such as ethylene glycol, methoxyethylene glycol, polyethylene glycol, propylene glycol, and diethylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, and N, N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, and polyvalent acrylates such as ethylene oxide adducts and propylene oxide adducts thereof; acrylic esters such as phenoxy acrylate, bisphenol a diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; acrylic acid esters of glycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine acrylate, 2-acryloxyethyl phthalate, and/or various methacrylates corresponding to the above acrylates.
(D) The (meth) acrylate monomer other than the (C) preferably contains (meth) acrylate monomers having different numbers of functional groups, and more preferably at least one of the (D) components is a 3-or more-functional (meth) acrylate monomer. Further, since the cured product may be warped when the functional group is 6 or more, the number of functional groups of the component (D) is preferably 5 or less.
(D) The amount of component (C) is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, per 1 part by mass of component (C). The amount of component (C) is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 3 to 7 parts by mass, based on 100 parts by mass of the photocurable resin (A). The amount of component (D) is preferably 2 to 500 parts by mass, more preferably 5 to 300 parts by mass, per 100 parts by mass of component (A).
[ (E) rutile type titanium oxide ]
The photocurable composition of the present invention contains (E) rutile titanium oxide as a white pigment. Although titanium oxide is rutile type or anatase type, rutile type titanium oxide is used because a cured product having a high reflectance is obtained, the influence on the deterioration of a resin is small, and the increase in viscosity of a composition can be suppressed. The titanium oxide is not limited to the production method such as the chlorine method and the sulfuric acid method. Further, titanium oxide subjected to surface treatment such as aluminum peroxide treatment or silica treatment can be suitably used.
In addition to the rutile type titanium oxide, zinc oxide, basic lead carbonate, basic lead sulfate, zinc yellow sulfate, zinc sulfide, antimony oxide, barium sulfate, and the like may be blended as the white pigment.
(E) The amount of rutile titanium oxide is preferably 100 to 350 parts by mass, more preferably 150 to 300 parts by mass, per 100 parts by mass of the photocurable resin (a). (E) When the amount of titanium oxide added exceeds 350 parts by mass, the viscosity becomes too high, and printing becomes difficult. On the other hand, when the amount is less than 100 parts by mass, it may be difficult to obtain a cured product having a high reflectance.
(coloring agent)
In the present invention, (E) a colorant other than rutile titanium oxide may be used as needed within a range not impairing the effects of the present invention. For example, a black colorant may be added to produce a gray photocurable composition.
As the other coloring agent, there may be used conventionally known coloring agents such as red, blue, green, yellow, white, black, violet, orange, brown and the like, and any of pigments, dyes and pigments may be used. Specific examples thereof include those numbered with The dye index (C.I.; issued by The Society of dyers and Colourists). However, from the viewpoint of reducing environmental load and influence on the human body, it is preferable that no halogen is contained.
Examples of the red colorant include monoazo-based, disazo-based, azo lake-based, benzimidazolone-based, perylene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, and quinacridone-based compounds.
Examples of the blue colorant include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds.
Examples of the green colorant include metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based compounds.
Examples of the yellow coloring agent include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based compounds.
Examples of the black coloring agent include carbon black.
The amount of the other colorant is not particularly limited, but is preferably 0 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (a).
[ other ingredients ]
the photocurable composition of the present invention may further contain known additives other than the above-mentioned components within a range not impairing the effects of the present invention. Examples of the additives include a thermal polymerization inhibitor, an ultraviolet absorber, a silane coupling agent, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, an antibacterial/antifungal agent, a defoaming agent, a leveling agent, a filler, a thickener, an adhesion imparting agent, and a thixotropy imparting agent. When the surface of the substrate is coated with a solder resist, dried, and then photo-cured, a solvent may be used. When used as a solder resist, it is preferable to blend a thermosetting resin such as an epoxy compound. The above-mentioned preferably being free of, preferably not being compounded with, means that the composition does not exclude a trace amount of such components.
The photocurable composition of the present invention is applied to a substrate or the like by, for example, the following coating method, and then cured by irradiation with ultraviolet rays, preferably ultraviolet rays having a wavelength of 10 to 400 nm.
Examples of the ultraviolet radiation light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, a laser, and a UV-LED.
as the coating method, any method such as a dip coating method, a flow coating method, a roll coating method, a bar coating method, a screen printing method, a curtain coating method, a gravure printing method, an offset printing method, an inkjet printing method, or the like can be applied.
the solder resist of the present invention is obtained by applying the photocurable composition of the present invention to a substrate and curing the composition.
The coating and curing method may be a known method as described below.
If necessary, the composition is diluted with a solvent to adjust the viscosity suitable for the coating method, and the composition is applied to a printed wiring board having a circuit formed thereon by a method such as screen printing, curtain coating, spray coating, roll coating, or ink jet printing, and the organic solvent contained in the composition is evaporated and dried at a temperature of, for example, about 60 to 100 ℃. Then, the cured product is cured by directly irradiating the cured product with an active energy ray such as a laser beam in accordance with a pattern or by selectively exposing the cured product with ultraviolet light through a photomask having a pattern formed thereon. When the photocurable composition is of an alkali development type, a resist pattern can be formed by developing the unexposed portion with a dilute aqueous alkali solution. Further, if desired, a cured film (cured product) is formed by heating or final curing (complete curing) after irradiation with ultraviolet rays.
Among these, the inkjet printing method using the photocurable composition is preferable because the step of removing the organic solvent by drying after printing and the step of developing with an aqueous alkali solution are not required, and the pattern forming step can be simplified.
The photocurable composition of the present invention can be applied to an insulating material such as an interlayer insulating material or a cover lay layer, in addition to a solder resist layer. The photocurable composition of the present invention can also be used as a solder dam (solder dam).
Examples
The present invention will be described in further detail below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.
The components described in tables 1 to 4 below were kneaded by a three-roll mill to prepare a photocurable composition.
Next, each photocurable composition was applied onto a substrate by screen printing, and then irradiated with ultraviolet light in a high-pressure mercury lamp UV conveyor oven so that the cumulative light amount on the composition was 1500mJ/cm2, thereby obtaining a test piece. The test piece thus obtained was evaluated by the following evaluation method.
The photocurable composition of example 12 was coated on a substrate using an inkjet Printer (Materials Printer DMP-2831 manufactured by FUJIFILM Global Graphic Systems Co., Ltd.), and then the cumulative light amount on the composition in a UV transport furnace of a high-pressure mercury lamp was 1500mJ/cm2the test piece was obtained by curing the resin composition by irradiation with ultraviolet light. The test piece thus obtained was evaluated by the following evaluation method.
(printability)
The viscosity at 25 ℃ of each of the obtained compositions was measured using a cone and plate viscometer TVE-33H (cone rotor 3 ℃ R9.7, 5rpm) manufactured by Toyobo industries, Ltd.
(reflectance)
The reflectance (Y value) of the obtained test piece was measured by using a spectrocolorimeter CM-2600d manufactured by Konica Minolta, inc.
(Adhesivity)
The obtained test pieces were cut into 100 grids in accordance with JIS K5400-8.5 with a cutter knife, and the adhesion of the coating film was evaluated by peeling with a transparent tape.
o: the number of the residual lattices is more than 80
and (delta): the number of the residual lattices is more than 70 and less than 80
X: the number of the residual lattices is less than 70
[ TABLE 1 ]
[ TABLE 2 ]
[ TABLE 3 ]
In addition, the method is as follows: EBECRYL8402 manufactured by Daicel-Cytec co., ltd., 2-functional urethane acrylate, photocurable oligomer
In addition, 2: ARONIX M-6200, 2-functional polyester acrylate manufactured by TOYA SYNTHESIS CO., LTD, and photocurable oligomer
and (2) in color: 2-Ethylanthraquinone, photopolymerization initiator
In addition, 4: irgacure819 manufactured by BASF corporation, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, a photopolymerization initiator
In addition, the method is as follows: KAYAME RPM-2, bis (2-methacryloyloxyethyl) acid phosphate manufactured by Nippon Kabushiki Kaisha, methacrylate ester monomer having phosphate ester Structure
in addition, 6: LIGHT ESTER P-1M mono (2-methacryloyloxyethyl) acid phosphate manufactured by Kyoeisha chemical Co., Ltd., methacrylate ester monomer having phosphate ester structure
In addition, the color is 7: HOA-MPL (N) manufactured by Kyoeisha chemical Co., Ltd, 2-acryloyloxyethyl phthalate, and an acrylate monomer having no phosphate ester structure
In addition, the color is 8: 4HBA manufactured by Nippon chemical Co., Ltd., 4-hydroxybutyl acrylate, and acrylate monomer having no phosphate ester structure
In addition, the color is 9: LIGHT ESTER HO-250(N) manufactured by Kyoeisha chemical Co., Ltd, 2-methylol methacrylate, and methacrylate ester monomer having no phosphate ester structure
In addition, the color is 10: LIGHT ESTER2EG manufactured by Kyoeisha chemical Co., Ltd, diethylene glycol dimethacrylate, and a methacrylate monomer having no phosphate ester structure
The method is characterized in that: TIPAQUE CR-97-Super70, rutile titanium oxide, available from Shidai Kagaku K.K
The method is characterized by being in color in 12: KRONOS titanium oxide KA-15, anatase-type titanium oxide manufactured by Titan Kogyo, Ltd
[ TABLE 4 ]
The color is as follows: 1, 6-hexanediol diacrylate manufactured by Daicel-Cytec Co., Ltd
[ TABLE 5 ]
[ TABLE 6 ]
[ TABLE 7 ]
[ TABLE 8 ]
As shown in tables 5, 6 and 8, examples 1 to 12 contain a photocurable resin, a photopolymerization initiator, a (meth) acrylate monomer having a phosphate ester structure, a (meth) acrylate monomer having no phosphate ester structure, and rutile titanium oxide, and thus have low viscosity, high reflectance, and high adhesion. On the other hand, as shown in table 7, comparative examples 1 to 3 did not contain a (meth) acrylate monomer having a phosphate ester structure, and therefore had low adhesion, although having low viscosity and high reflectance. Further, since the titanium oxide of comparative example 4 was anatase type instead of rutile type, the viscosity was high and the reflectance was low although the adhesiveness was good. In addition, comparative example 5 does not contain a (meth) acrylate monomer having no phosphate ester structure, and therefore has a high viscosity.
Claims (4)
1. A photocurable composition, comprising:
(A) A photocurable resin,
(B) A photopolymerization initiator,
(C) A (meth) acrylate monomer having a phosphate ester structure,
(D) A (meth) acrylate monomer having no phosphate ester structure, and
(E) The titanium oxide of the rutile type is,
The photocurable resin (A) comprises a urethane (meth) acrylate and/or a polyester (meth) acrylate,
The amount of (C) a (meth) acrylate monomer having a phosphate ester structure is 1 to 20 parts by mass per 100 parts by mass of (A) the photocurable resin,
The amount of (D) the (meth) acrylate monomer having no phosphate structure is 5 to 300 parts by mass per 100 parts by mass of (A) the photocurable resin.
2. The photocurable composition according to claim 1, which is for inkjet printing.
3. A solder resist layer obtained by curing the photocurable composition according to claim 1 or 2.
4. A printed circuit board comprising the solder resist layer according to claim 3.
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| JP2012270654 | 2012-12-11 | ||
| JP2012-270654 | 2012-12-11 | ||
| JP2013117812A JP6209365B2 (en) | 2012-12-11 | 2013-06-04 | Photocurable resin composition, solder resist and printed wiring board |
| JP2013-117812 | 2013-06-04 |
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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 |
| 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 |
| EP4198097B1 (en) * | 2021-12-15 | 2024-05-29 | Ricoh Company, Ltd. | Image forming method and active energy ray-curable composition set |
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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 |
| JP2011145640A (en) * | 2009-12-16 | 2011-07-28 | Ricoh Co Ltd | Developing device, process unit, and image forming apparatus |
| 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 a threaded joint for steel pipes |
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| JP3911728B2 (en) * | 1996-08-07 | 2007-05-09 | 住友化学株式会社 | Resin composition for protective coating and adhesion of digital video disk |
| JP4700924B2 (en) | 2004-04-26 | 2011-06-15 | 太陽ホールディングス株式会社 | Solder resist composition and printed wiring board having solder resist formed therefrom |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 a threaded joint for steel pipes |
| JP2011145640A (en) * | 2009-12-16 | 2011-07-28 | Ricoh Co Ltd | Developing device, process unit, and image forming apparatus |
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| CN103869615A (en) | 2014-06-18 |
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