WO2012029468A1 - 硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板 - Google Patents
硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板 Download PDFInfo
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- WO2012029468A1 WO2012029468A1 PCT/JP2011/067293 JP2011067293W WO2012029468A1 WO 2012029468 A1 WO2012029468 A1 WO 2012029468A1 JP 2011067293 W JP2011067293 W JP 2011067293W WO 2012029468 A1 WO2012029468 A1 WO 2012029468A1
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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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
- C08F299/0485—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations
- C08F299/0492—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention provides a curable (photocurable and / or thermosetting) resin composition containing a curable resin derived from a specific polyester polyol and a layered double hydroxide, particularly a recovered polyester.
- the present invention relates to an alkali-developable photocurable resin composition containing a curable resin and a layered double hydroxide, a dry film and a cured product thereof, and a printed wiring board using them.
- Patent Document 3 discloses a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, and a diluent. And a solder resist composition comprising an epoxy compound is disclosed. Japanese Patent Laid-Open No.
- Patent Document 4 adds (meth) acrylic acid to an epoxy resin obtained by reacting a reaction product of salicylaldehyde with a monohydric phenol with epichlorohydrin. Furthermore, a solder resist composition comprising a photosensitive resin obtained by reacting a polybasic carboxylic acid or an anhydride thereof, a photopolymerization initiator, an organic solvent and the like is disclosed. These epoxy acrylate modified resins contain halogen ions because epichlorohydrin is used as a raw material, and it has been difficult to make them halogen-free.
- Examples of new methods for reclaiming waste polyester include the production of coating alkyd resins using a depolymerization reaction with glycols (see Patent Document 7), and the production of paint polyester resins using recycled polyester (Patent Documents 8 and 9). Further, the use of recycled polyester as a raw material for a photocurable urethane resin (see Patent Document 10) and the like has been studied, all of which are intended for use in coating compositions.
- the present invention has been made in view of the prior art as described above, is halogen-free, and has high sensitivity, excellent solder heat resistance, electroless gold plating resistance, moisture resistance, electrode corrosion resistance, and environmental problems. It aims at providing the curable resin composition in consideration. Furthermore, an object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a curable resin composition, and a cured film such as a solder resist by the dry film and the cured product. It is in providing the printed wiring board formed by.
- a curable resin derived from a compound including a structure represented by the following general formula (1), and (B) a layered double hydroxide is contained.
- a curable resin composition is provided.
- R 1 represents an (m + 1) -valent polyhydric alcohol derivative
- m and n are an integer of 1 or more and less than 10
- l is an integer of 0 or 1
- R 2 is CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , any of a substituted or unsubstituted aromatic ring
- R 3 represents a substituted or unsubstituted aromatic ring.
- the compound having the structure represented by the general formula (1) is a polyol obtained by depolymerizing (a) polyester with (b) a polyol having two or more hydroxyl groups in one molecule.
- Resin More preferably, the polyester of (a) is a recovered polyester, particularly polyethylene terephthalate (PET), and the polyol of (b) is trimethylolpropane, trimethylolethane, pentaerythritol, dipenta It is at least one selected from the group consisting of erythritol, ditrimethylolpropane, vegetable oil and glycerin, and trimethylolpropane is particularly preferable.
- it further contains a thermosetting component, and preferably further contains a colorant.
- Such a curable resin composition, particularly a curable resin composition containing a thermosetting component can be suitably used as a solder resist.
- a cured product obtained by photocuring on copper and a cured product obtained by photocuring in a pattern are also provided.
- a printed wiring board characterized by having a cured film obtained by photocuring the photocurable resin composition or dry film in a pattern and then thermosetting.
- the curable resin used in the curable resin composition of the present invention has a thermosetting property, a photocurable property, or a photocurable and thermosetting property. Further, since this curable resin is derived from a polyester polyol having a structure represented by the general formula (1), unlike a conventional epoxy acrylate-modified resin, a raw material not containing a halogen ion can be used. Therefore, it can be made halogen-free, and a cured film excellent in electrical insulation, heat resistance, and dryness to touch can be formed. Moreover, since a layered double hydroxide is contained together with the curable resin derived from the polyester polyol having the structure represented by the general formula (1), a cured film having extremely excellent electrode corrosion resistance can be formed.
- the compound having the structure represented by the general formula (1) is produced by depolymerization of polyester, since the polyester recovered as a starting material can be used as a raw material from which waste polyester is recovered, it is possible to effectively use resources. Can contribute. Furthermore, the depolymerized product obtained by depolymerizing the polyester with the polyol can be used for the next reaction as it is without separation, so that the recycled resin utilization rate is increased and the aroma in the recovered polyester depolymerized product is increased.
- Carboxylic acid having a ring (benzene ring), particularly terephthalic acid can contribute to solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc. of the cured coating film of the curable resin composition.
- thermosetting resin it is possible to form a cured film having further excellent solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like. Therefore, the curable resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.
- the curable resin composition of the present invention is characterized by (A) a curable resin derived from a compound containing a structure represented by the following general formula (1), and (B) a layered double hydroxide. It is in use.
- R 1 represents an (m + 1) -valent polyhydric alcohol derivative
- m and n are an integer of 1 or more and less than 10
- l is an integer of 0 or 1
- R 2 is CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , any of a substituted or unsubstituted aromatic ring
- R 3 represents a substituted or unsubstituted aromatic ring.
- such a resin composition can form a cured film excellent in electrode corrosion resistance, heat resistance, and touch dryness, and the polyester is recovered from waste materials such as PET bottles.
- waste materials such as PET bottles.
- recycled polyester and recycled polyester it is possible to provide an environmentally friendly composition.
- the polyester is depolymerized with a polyol component according to a known method, a mixture of a component having a carboxyl group and a component having a hydroxyl group generated by depolymerization of the polyester, or a mixture further containing a remaining polyol component depending on the amount of the polyol component added. Any of these can be used for the reaction with an alicyclic polybasic acid or an anhydride thereof or the reaction with a compound having one or more ethylenically unsaturated groups in the molecule.
- the curable resin (A) derived from the compound having the structure represented by the general formula (1) used in the present invention is a carboxylic acid resin, (a) polyester (b) two or more in one molecule It is obtained by depolymerizing with a polyol having a hydroxyl group and reacting the depolymer with (c) an alicyclic polybasic acid or an anhydride thereof.
- the curable resin (A) derived from the compound containing the structure represented by the general formula (1) used in the present invention is a photosensitive resin
- (a) polyester (b) two or more in one molecule It is obtained by depolymerizing with a polyol having a hydroxyl group and reacting the depolymer with a functional group capable of reacting with a hydroxyl group or a carboxyl group in the molecule and a compound having one or more ethylenically unsaturated groups. It is done.
- the curable resin (A) derived from the compound having the structure represented by the general formula (1) used in the present invention is a carboxyl group-containing photosensitive resin capable of alkali development
- the ratio of the polyester and the polyol having two or more hydroxyl groups in one molecule is the ratio of the number of moles of repeating units ( ⁇ ) of the polyester and the number of moles of polyol having two or more hydroxyl groups in one molecule ( ⁇ ).
- ( ⁇ ) / ( ⁇ ) 0.5 to 3 is appropriate, and preferably within the range of 0.8 to 2.
- the ratio is less than 0.5, the polyol component is excessively contained, the ratio of the aromatic ring derived from the polyester is decreased, and the effect of improving heat resistance and chemical resistance is decreased, which is not preferable.
- the ratio is greater than 3, the depolymerized product is crystallized in most cases and is insoluble in the solvent, which is not preferable.
- the polyester (a) may be any conventionally known polyester, and examples thereof include polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene phthalate, and liquid crystal polymer.
- PET polyethylene terephthalate
- Recycled PET and recycled PET recovered from waste such as PET bottle waste are more preferable from the viewpoint of environmental protection.
- the collected PET can be crushed and washed, and the recycled PET can be obtained from the market after being washed and pelletized.
- the shape of the polyester is not particularly limited, but is preferably in the form of pellets and / or flakes. Moreover, although it is not necessary to grind
- any bifunctional polyol or trifunctional or higher polyol can be used, and these can be used alone or in combination of two or more. .
- bifunctional polyol examples include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, Neopentyl glycol, spiro glycol, dioxane glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol 1, Bifunctional phenols such as 3,3-methylpentanediol 1,5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A Ethylene oxide modified compound of
- Examples of commercially available products of the above hydroxyl group-terminated polyalkanediene diols include EPOL (registered trademark; hydrogenated polyisoprene diol, molecular weight). 1,860, average polymerization degree 26, manufactured by Idemitsu Kosan Co., Ltd.), PIP (polyisoprene diol, molecular weight 2,200, average polymerization degree 34, manufactured by Idemitsu Kosan Co., Ltd.), polytail H (hydrogenated polybutadiene diol, molecular weight) 2,200, average degree of polymerization 39, Mitsubishi Chemical Corporation And R-45HT (polybutanediol, molecular weight 2,270, average polymerization degree 42, manufactured by Idemitsu Kosan Co., Ltd.).
- EPOL registered trademark; hydrogenated polyisoprene diol, molecular weight
- 1,860 average polymerization degree 26, manufactured by Idemitsu Kosan Co., Ltd.
- PIP polyis
- tri- or higher functional polyol examples include glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, polycaprolactone triol (for example, plaxel 303, plaxel 305, Plaxel 308, Plaxel 312, Plaxel L312AL, Plaxel 320ML, Plaxel L320AL; all of which are manufactured by Daicel Chemical Industries, Ltd .; trade names), and those having aromatic rings include ethylene oxides and propylene oxides of trifunctional or higher phenol compounds Sake manufactured by Shikoku Kasei Kogyo Co., Ltd.
- amorphous semi-solid fluid product that does not become turbid when obtained as a depolymerized product is obtained and the solubility in a solvent is further increased.
- alicyclic polybasic acid or its anhydride (c) a conventionally known polybasic acid or its anhydride can be used.
- aromatic polycarboxylic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrabromophthalic anhydride, methyl hymic anhydride, tetrachlorophthalic anhydride, and anhydrides thereof, hexahydrophthalic anhydride Acid, tetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and other alicyclic carboxylic acids and their anhydrides, maleic anhydride, fumaric acid, succinic anhydride, adipic acid, sebacine Examples thereof include aliphatic polyvalent carboxylic acids such as acid and azelaic acid, and anhydrides thereof, pyromellitic anhydride, trimellitic anhydride
- Compound (d) having a functional group capable of reacting with a hydroxyl group or a carboxyl group in the molecule and one or more ethylenically unsaturated groups is a compound having one carboxyl group and one or more ethylenically unsaturated groups
- Compounds having one carboxyl group and one or more ethylenically unsaturated groups include acrylic acid, dimer of acrylic acid, methacrylic acid, ⁇ -styrylacrylic acid, ⁇ -furfurylacrylic acid, crotonic acid, ⁇ -Cyanocinnamic acid, cinnamic acid, (meth) acrylic acid caprolactone adduct, and half ester compounds of saturated or unsaturated dibasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule, etc. Can be mentioned.
- Examples of (meth) acrylates having a hydroxyl group for producing a half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and phenylglycidyl (meth) acrylate.
- dibasic acid anhydride for producing the half ester compound examples include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydro Phthalic anhydride etc. are mentioned, It can use individually or in combination of 2 or more types.
- (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
- the (meth) acrylic monomer having an isocyanate group is not particularly limited as long as it is an isocyanate compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule.
- Specific examples include, for example, (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloxymethyl) ethyl isocyanate, or modified products thereof, alone or in combination of two or more. Can be used in combination.
- a half urethane compound of a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule and a diisocyanate such as isophorone diisocyanate, toluylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate is also used. can do.
- Compounds having one cyclic ether group and one or more ethylenically unsaturated groups in one molecule include 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxy Propyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl
- Examples include ether or glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like can be used alone or in combination of two or more.
- Examples of the compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meta ) Hydroxyalkyl (meth) acrylates such as acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like, and may be used alone or in combination of two or more.
- the (meth) acrylic monomer having a functional group capable of reacting with a hydroxyl group or a carboxyl group as described above can be used alone or in combination of two or more.
- a depolymerization catalyst can be used.
- the depolymerization catalyst include monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc acetate, manganese acetate, cobalt acetate, and calcium acetate. , Lead acetate, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate and the like.
- the amount of these depolymerization catalysts used is usually in the range of 0.005 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polyester and polyhydric alcohol. is there.
- water is a compound that promotes depolymerization. This is present as an impurity in, for example, recycled PET, and causes a decrease in molecular weight when PET is recycled. Therefore, it is usually necessary to remove it by a very energy-consuming process such as drying. is there.
- it is not necessary. Rather, the use of recycled PET pellets once melted and kneaded in a pellet manufacturing machine such as an extruder with water added has a lower molecular weight of the recycled PET. Since the reaction temperature at the time of superposition
- polyester pellets In general, commercially available polyester pellets (virgin) have an IV value (intrinsic viscosity) of about 1.0 to 1.2, but recycled PET and recycled PET have an IV value of 0.6 to 0.7. For this reason, there is an effect that the time required for depolymerization can be shortened when recycled PET and recycled PET are used. Further, when the PET was regenerated without repelling moisture with an extruding machine, the IV value was low and around 0.1, but there was no particular problem when used in the present invention.
- IV value intrinsic viscosity
- the layered double hydroxide (B) used in the present invention is known as an ion adsorbent. It is also known as an antacid in the pharmaceutical field.
- the inventors of the present invention have found that the curable resin composition of the present invention containing a layered double hydroxide is remarkably excellent in electrode corrosion resistance as compared with the case of not containing a layered double hydroxide.
- the effect that the layered double hydroxide improves the electrode corrosion resistance of the composition containing it is thought to be due to the layered double hydroxide adsorbing halogen, and therefore usually contains halogen. Even when layered double hydroxide was added to the composition that did not, there was no effect of improving electrode corrosivity.
- layered double hydroxide (B) used in the present invention include Indigirite Mg 2 Al 2 [(CO 3 ) 4 (OH) 2 ] ⁇ 15H 2 O, Fe 2+ 4 Al 2 [(OH) 12 CO 3 ] ⁇ 3H 2 O, Quintinite Mg 4 Al 2 (OH) 12 CO 3 ⁇ H 2 O, Manasseite Mg 6 Al 2 [(OH) 16 CO 3 ] ⁇ 4H 2 O, SjOegrenite Mg 6 Fe 3 + 2 [(OH ) 16 CO 3] ⁇ 4H 2 O, Zaccagnaite Zn 4 Al 2 (CO 3) (OH) 12 ⁇ 3H 2 O, Desautelsite Mg 6 Mn 3+ 2 [(OH) 16 CO 3] ⁇ 4H 2 O, hydrotalcite Mg 6 Al 2 [(OH) 16 CO 3 ] ⁇ 4H 2 O, Pyroaurite Mg 6 Fe 3 + 2 [(OH) 16 CO 3 ] ⁇ 4H 2 O, Reevesite Ni 6
- hydrotalcites having an average particle size of 2 ⁇ m or less, more preferably 1 ⁇ m or less. Further, these hydrotalcites can be used in the anhydrous state as they are in the form of hydrates or after baking.
- the compounding amount of the layered double hydroxide (B) is preferably 0.1 to 30 wt% of the total amount of the composition. A range of preferably 0.5 to 30 wt%, more preferably 0.1 to 25 wt% is appropriate. If the blended amount of the layered double hydroxide (B) is more than the above range, the viscosity and thixotropy of the composition will be too high, the printability may be lowered, and the cured product may be brittle. Absent. On the other hand, if it is less than 0.1 wt%, the effect of electrode corrosion resistance is impaired, which is not preferable.
- the composition further contains a photopolymerization initiator.
- the photopolymerization initiator used in the present invention is at least selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator.
- One type of photoinitiator can be used.
- oxime ester photopolymerization initiator examples include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, and the like as commercially available products. .
- numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.
- X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms).
- Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon atom having 1 carbon atom), substituted with an alkyl group having a C 1-8 alkyl group or a dialkylamino group.
- X and Y are each a methyl group or an ethyl group
- Z is a methyl group or a phenyl group
- p is 0,
- Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable that
- the blending amount of such an oxime ester photopolymerization initiator is preferably 0.02 to 10 wt% of the total amount of the composition.
- it is less than 0.02 wt%, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated.
- it exceeds 10 wt% light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered.
- ⁇ -aminoacetophenone photopolymerization initiator examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like can be mentioned.
- Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.
- acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6- And dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
- examples of commercially available products include Lucilin TPO manufactured by BASF Japan and Irgacure 819 manufactured by BASF Japan.
- the blending amount of these ⁇ -aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.5 to 15 wt% of the total amount of the composition. If it is less than 0.5 wt%, the photocurability on copper is similarly insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when it exceeds 15 wt%, the effect of reducing the outgas cannot be obtained, and the light absorption on the surface of the solder resist coating film becomes intense and the deep curability tends to be lowered.
- examples of the photopolymerization initiator, photoinitiator assistant, and sensitizer that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. Compounds, tertiary amine compounds, and xanthone compounds.
- benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
- anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
- thioxanthone compound examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.
- ketal compound examples include acetophenone dimethyl ketal and benzyl dimethyl ketal.
- benzophenone compound examples include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyl. And diphenyl sulfide.
- tertiary amine compound examples include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.) as a commercially available product.
- a compound having a dialkylaminobenzene structure such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.) as a commercially available product.
- Dialkylaminobenzophenone such as 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4 Dimethylamino group-containing coumarin compounds such as -methylcoumarin), ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd.
- Kayacure (registered trademark) EPA), ethyl 2-dimethylaminobenzoate (International Bio-Synthetics) Quantacu e DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), Examples include 4-ethylhexyl 4-dimethylaminobenzoate (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.
- thioxanthone compounds and tertiary amine compounds are preferred.
- the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability.
- thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.
- the blending amount of such a thioxanthone compound is preferably 15 wt% or less of the total amount of the composition.
- the blending amount of the thioxanthone compound exceeds 15 wt%, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 wt% or less.
- a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
- dialkylaminobenzophenone compound 4,4′-diethylaminobenzophenone is preferable because of its low toxicity.
- the dialkylamino group-containing coumarin compound has a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, and therefore is less colored and uses not only a colorless and transparent photosensitive composition but also a colored pigment to reflect the color of the colored pigment itself.
- a colored solder resist film can be provided.
- 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
- the blending amount of such a tertiary amine compound is preferably 0.1 to 15 wt% of the total amount of the composition.
- the compounding amount of the tertiary amine compound is less than 0.1 wt%, a sufficient sensitizing effect tends not to be obtained. If it exceeds 15 wt%, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to be lowered.
- photopolymerization initiators can be used alone or as a mixture of two or more.
- the total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the curable resin of the present invention. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
- these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.
- the curable resin composition of the present invention can further contain a compound having a carbodiimide group.
- a compound having a carbodiimide group By containing the compound which has a carbodiimide group, it can bridge
- the compound having a carbodiimide group used in the present invention can be easily obtained from the market.
- Specific examples include Carbodilite V-03, Carbodilite V-06, Carbodilite 10M-SP, Carbodilite 9010, etc., manufactured by Nisshinbo Co., Ltd.
- the compounding amount of the compound having a carbodiimide group is 0.5 to 40 wt%, preferably 1 to 30 wt% of the total amount of the composition.
- the compounding quantity of the compound which has a carbodiimide group is too much than the said range, since the intensity
- it is less than 0.5 wt% the effect of hydrolysis resistance is impaired, which is not preferable.
- N-phenylglycines phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as chain transfer agents in order to improve sensitivity.
- chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo
- heterocyclic compound having a mercapto group acting as a chain transfer agent examples include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto.
- mercaptobenzothiazole 3-mercapto-4-methyl-4H-1,2,4-triazole is a heterocyclic compound having a mercapto group which is a chain transfer agent that does not impair the developability of the photocurable resin composition.
- 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred.
- These chain transfer agents can be used alone or in combination of two or more.
- a conventionally known carboxyl group-containing photosensitive resin may be added to the photocurable resin composition of the present invention for the purpose of improving photosensitivity, developability, heat resistance, and electrical characteristics.
- carboxyl group-containing photosensitive resin compounds listed below (any of oligomers and polymers) may be preferable.
- a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
- a carboxyl group-containing photosensitive resin obtained by reacting a compound having one or more ethylenically unsaturated groups and one epoxy group in a molecule.
- Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
- carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
- bisphenol A type epoxy resin hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
- one isocyanate group and one or more (meth) acryl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
- a carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.
- a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
- a cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and a polybasic acid is added to the remaining hydroxyl group.
- a carboxyl group-containing photosensitive resin obtained by reacting an anhydride.
- a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resins (1) to (8).
- the resins mentioned in (1), (2), modified products thereof (4) and (5), and (8) can be used without using an epoxy compound (resin) made of epichlorohydrin as a raw material.
- an epoxy compound (resin) made of epichlorohydrin
- a carboxylic acid-containing resin it is particularly preferable from the viewpoint of halogen-free.
- halogen-free can also be achieved by using the epoxy compound (resin) which does not use epichlorohydrin.
- the isocyanate compound used in the resin synthesis is possible, one using an isocyanate which is not a phosgene method as a raw material is preferable.
- the carboxyl group-containing photosensitive resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
- the acid value of the carboxyl group-containing photosensitive resin is suitably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g.
- the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
- the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary.
- the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.
- the weight-average molecular weight of the carboxyl group-containing photosensitive resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000.
- weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior.
- weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.
- the amount of such carboxyl group-containing photosensitive resin is 50 wt% or less, preferably 10 to 40 wt% of the total composition.
- These carboxyl group-containing photosensitive resins are not limited to those listed above, and can be used singly or in combination of two or more.
- the curable resin composition of the present invention can contain a thermosetting component in order to impart heat resistance or to form a thermosetting resin composition.
- thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, bismaleimides, and oxazine compounds.
- a known and commonly used thermosetting resin such as an oxazoline compound can be used.
- a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups hereinafter abbreviated as “cyclic (thio) ether groups” in the molecule.
- thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule.
- a compound having a plurality of epoxy groups in the molecule that is, a polyfunctional epoxy compound
- a compound having a plurality of oxetanyl groups in the molecule that is, a polyfunctional oxetane compound, a plurality of thioether groups in the molecule
- the compound which has this, ie, an episulfide resin etc. are mentioned.
- polyfunctional epoxy compounds examples include epoxidized vegetable oils such as Adeka Sizer O-130P, Adeka Sizer O-180A, Adeka Sizer D-32, and Adeka Sizer D-55 manufactured by ADEKA; jER828, jER834, and jER1001 manufactured by Mitsubishi Chemical Corporation. , JER1004, EHPE3150 manufactured by Daicel Chemical Industries, Epicron (registered trademark) 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo (registered trademark) YD-011, YD-013 manufactured by Nippon Steel Chemical Co., Ltd. YD-127, YD-128, D.C. E. R. 317, D.E. E.
- E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical, Epotot YDF-170, YDF-175, YDF manufactured by Nippon Steel Chemical Co., Ltd. -2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by BASF Japan (all trade names); water such as Epotot ST-2004, ST-2007, ST-3000 (trade names) manufactured by Nippon Steel Chemical Co., Ltd.
- Bisphenol A type epoxy resin jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH-434 manufactured by Nippon Steel Chemical Co., Ltd., Araldide MY720 manufactured by BASF Japan, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Product name) glycidylamine type epoxy resin; Araf made by BASF Japan Hydantoin type epoxy resin such as Dydo CY-350 (trade name); Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, Ltd., Araldide CY175, CY179 manufactured by BASF Japan, etc. (all trade names) YL-933 manufactured by Mitsubishi Chemical Co., Ltd. E. N.
- EPPN-501, EPPN-502, etc. trihydroxyphenylmethane type epoxy resin
- Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 all trade names), etc.
- Type or biphenol type epoxy resin or a mixture thereof Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name), etc .
- bisphenol S type epoxy resin Bisphenol A novolac type epoxy resin such as jER157S (trade name); tetraphenylolethane type epoxy resin such as jERYL-931 manufactured by Mitsubishi Chemical Corporation, Araldide 163 manufactured by BASF Japan Ltd. (all trade names); manufactured by BASF Japan Ltd.
- Araldide PT810 (trade name), Nissan Chemical Industries Heterocyclic epoxy resins such as TEPIC (registered trademark) manufactured by Nippon Oil & Fats Co., Ltd. diglycidyl phthalate resins such as Blemmer (registered trademark) DGT; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Nippon Steel Chemical Naphthalene group-containing epoxy resins such as Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700, etc .; DIC Corporation HP-7200, HP-7200H, etc.
- TEPIC registered trademark
- Blemmer registered trademark
- Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Nippon Steel Chemical Naphthalene group-containing epoxy resins such as Nippon Steel Chemical Co., Ltd.
- Epoxy resin having a cyclopentadiene skeleton Epoxy resin copolymerized with glycidyl methacrylate such as CP-50S and CP-50M manufactured by NOF Corporation; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivative ( For example, manufactured by Daicel Chemical Industries B-3600, etc.), CTBN modified epoxy resin (e.g., Nippon Steel Chemical Co. YR-102, YR-450, etc.) and others as mentioned, is not limited thereto. These epoxy resins can be used alone or in combination of two or more.
- epoxide-modified compounds by the peracetic acid method such as EHPE3150, PB-3600, and Celoxide 2021 (all manufactured by Daicel Chemical Industries, Ltd.) are preferable because they do not contain halogen ions as impurities.
- epoxidized vegetable oils such as Adeka Sizer D-32, Adeka Sizer D-55, Adeka Sizer O-130P, Adeka Sizer O-180A (all manufactured by ADEKA) and the like are also preferable because they do not contain halogen.
- polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl)
- polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene
- Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
- the amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably, relative to 1 equivalent of carboxyl groups in the composition. A range of 0.8 to 2.0 equivalents is appropriate.
- the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is less than 0.6 equivalent, the carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, etc. Since it falls, it is not preferable.
- the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
- thermosetting component a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added.
- a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule.
- the compound which has, ie, a blocked isocyanate compound, etc. are mentioned.
- polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
- aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer.
- aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
- alicyclic polyisocyanate examples include bicycloheptane triisocyanate.
- adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.
- the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily inactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
- a blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
- the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type.
- aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example.
- Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.
- isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam.
- Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol Mercaptan blocking agents such as methylthiophenol and ethylthi
- the blocked isocyanate compound may be commercially available, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS- 2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (above, manufactured by Sumitomo Bayer Urethane Co., Ltd., product name), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (above, manufactured by Nippon Polyurethane Industry Co., Ltd., product) Name), B-830, B-815, B-846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (Asahi Kasei) Chemicals, product name) . Sumijoules BL-3175
- the compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
- the compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is suitably 1 wt% to 50 wt%, more preferably 2 to 40 wt% of the total amount of the composition.
- the blending amount is less than 1 wt%, it is not preferable because sufficient toughness of the coating film cannot be obtained.
- it exceeds 50 wt% storage stability falls and it is not preferable.
- thermosetting components examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
- the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group.
- the type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.
- a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.
- thermosetting component can be used individually or in combination of 2 or more types.
- thermosetting component having a plurality of cyclic (thio) ether groups in the molecule
- thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
- Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
- Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like.
- thermosetting catalyst for epoxy resins or oxetane compounds or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.
- the amount of these thermosetting catalysts to be blended is a normal quantitative ratio.
- the amount is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.
- an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate.
- Specific examples include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione.
- a compound having a plurality of ethylenically unsaturated groups in the molecule can be blended.
- the compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays, and the curable resin of the present invention or the carboxyl group-containing photosensitivity.
- the insoluble resin is insolubilized in the alkaline aqueous solution, or assists insolubilization.
- polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate can be used.
- Hydroxyalkyl acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide, N Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate Aminoalkyl acrylates such as hexanes; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol,
- an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
- a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
- a hydroxy acrylate such as pentaerythritol triacrylate
- a diisocyanate such as isophorone diisocyanate
- the compounding amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is 1 to 70 wt%, more preferably 5 to 60 wt%, based on the solid content of the composition.
- a proportion of 5 to 100 parts by mass, more preferably 5 to 70 parts by mass is appropriate for 100 parts by mass of the carboxyl group-containing photosensitive resin.
- the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable.
- the amount exceeds 100 parts by mass the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.
- the curable resin composition of the present invention can contain a colorant.
- a colorant conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
- Red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.
- -Indexes (CI; issued by The Society of Dyers and Colorists) are listed.
- Monoazo Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
- Disazo Pigment Red 37, 38, 41.
- Monoazo lakes Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
- Benzimidazolone series Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
- Perylene series Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
- Diketopyrrolopyrrole series Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
- Condensed azo series Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
- Anthraquinone series Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
- Kinacridone series Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.
- Blue colorant include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds such as Pigment Blue 15 and Pigment Blue 15 are listed below. : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
- the dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used.
- a metal-substituted or unsubstituted phthalocyanine compound can also be used.
- Green colorant examples include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
- Yellow colorant examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
- Anthraquinone series Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
- Isoindolinone type Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
- Condensed azo series Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
- Benzimidazolone series Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
- Monoazo Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
- Disazo Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.
- a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
- the blending ratio of the colorant as described above is not particularly limited, but 5 wt% or less, more preferably 0.1 to 3 wt% is sufficient in the solid content of the composition.
- the curable resin composition of the present invention has a ( 1) Radical scavengers that invalidate the generated radicals and / or (2) Oxidation of peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals.
- An inhibitor can be added.
- the radical scavenger may be commercially available, for example, ADK STAB (registered trademark) AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (all manufactured by ADEKA), IRGANOX (registered trademark) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, , TINUVIN 5100 (both manufactured by BASF Japan) and the like.
- ADK STAB registered trademark
- AO-30 ADK STAB AO-330
- ADK STAB AO-20 ADK STAB LA-77
- ADK STAB LA-57 ADK STAB LA-67
- the peroxide decomposing agent may be commercially available, for example, Adeka Stub TPP (manufactured by ADEKA), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd.), Sumilyzer (registered trademark) TPS (manufactured by Sumitomo Chemical) Etc.
- the above antioxidants can be used individually by 1 type or in combination of 2 or more types.
- the curable resin composition of the present invention can use an ultraviolet absorber in addition to the antioxidant.
- ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
- benzophenone derivatives examples include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2 , 4-dihydroxybenzophenone and the like.
- benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl- Examples thereof include 4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.
- benzotriazole derivatives examples include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2′- Hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, Examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole.
- triazine derivative examples include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
- Ultraviolet absorbers may be commercially available, for example, TINUVI PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460 TINUVIN 479 (both manufactured by BASF Japan Ltd.) and the like.
- the ultraviolet absorbers as described above can be used singly or in combination of two or more. By using in combination with an antioxidant, the stability of the molded product obtained from the curable resin composition of the present invention can be improved. Can be achieved.
- a filler can be blended as necessary in order to increase the physical strength of the coating film.
- known and commonly used inorganic or organic fillers can be used.
- barium sulfate, spherical silica and talc are preferably used.
- metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers.
- the blending amount of the filler is preferably 75 wt% or less, more preferably 0.1 to 60 wt% of the total amount of the composition. When the blending amount of the filler exceeds 75 wt% of the total amount of the composition, the viscosity of the insulating composition becomes high, the coating and moldability are lowered, and the cured product becomes brittle.
- the curable resin composition of the present invention is a viscosity adjustment for the synthesis of the curable resin of the present invention and the carboxyl group-containing photosensitive resin, for the preparation of the composition, or for application to a substrate or a carrier film. Therefore, an organic solvent can be used.
- organic solvents examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether a
- the curable resin composition of the present invention may be a known thermal polymerization inhibitor, a known conventional thickener such as finely divided silica, organic bentonite, or montmorillonite, a silicone type, a fluorine type, a polymer type, or the like.
- Known additives such as antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, and the like can be blended.
- the thermal polymerization inhibitor can be used to prevent thermal polymerization or polymerization with time of the polymerizable compound.
- the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, ⁇ -naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
- the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, for example, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing method,
- a tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. and performing volatile drying (temporary drying) at a temperature of about 60 to 100 ° C.
- a resin insulation layer can be formed by apply
- a contact method or non-contact method
- exposure is selectively performed with an active energy ray through a photomask on which a pattern is formed, or direct pattern exposure is performed with a laser direct exposure machine, and an unexposed portion.
- a dilute alkali aqueous solution for example, 0.3 to 3 wt% sodium carbonate aqueous solution
- a composition containing a thermosetting component for example, by heating to a temperature of about 140 to 180 ° C.
- thermosetting the curable resin of the present invention or the carboxyl group-containing photosensitive resin carboxyl
- a cured coating film can be formed.
- heat treatment thermosetting may be performed depending on the purpose and application.
- the base material examples include a printed circuit board and a flexible printed circuit board in which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin. , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4, etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.
- Volatile drying performed after the application of the curable resin composition of the present invention includes a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven, etc. (with a heat source of an air heating method using steam) It is possible to use a method in which hot air is brought into countercurrent contact and a method in which a hot air is blown onto a support.
- the obtained coating film is exposed (irradiated with active energy rays).
- the exposed portion (the portion irradiated by the active energy ray) is cured.
- a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
- an exposure apparatus equipped with a metal halide lamp and an (ultra) high pressure mercury lamp.
- a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used.
- the amount of exposure varies depending on the film thickness and the like, but can generally be in the range of 5 to 800 mJ / cm 2 , preferably 5 to 500 mJ / cm 2 .
- the direct drawing apparatus for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .
- the developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
- the curable resin composition of the present invention is in the form of a dry film having a solder resist layer formed by applying and drying a solder resist in advance on a film of polyethylene terephthalate or the like, in addition to a method of directly applying to a substrate in a liquid state. It can also be used.
- the case where the curable resin composition of this invention is used as a dry film is shown below.
- the dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order.
- the solder resist layer is a layer obtained by, for example, applying and drying an alkali-developable photocurable resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.
- the carrier film a thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
- the solder resist layer is formed by uniformly applying an alkali-developable photocurable resin composition to a carrier film or a cover film with a thickness of 10 to 150 ⁇ m using a blade coater, lip coater, comma coater, film coater, and the like, and then drying.
- the cover film a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.
- a protective film permanent protective film
- peel off the cover film layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc.
- a solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed.
- the carrier film may be peeled off either before exposure or after exposure.
- Carboxyl group-containing acrylate synthesis example 1 Charged 384 parts of recycled PET flakes having an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen introducing tube, and cooling tube, and the atmosphere in the flask was changed to 300 ° C. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 1.30 parts of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
- the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature inside the flask was kept at 220 ° C. ⁇ 10 ° C. and reacted for 5 hours.
- 150 parts of this reaction product was placed in a 500 mL four-necked flask equipped with a stirrer, an air introduction tube, a fractionation tube, and a cooling tube, and 31.2 parts of acrylic acid, 1.82 parts of paratoluenesulfonic acid, paramethoxy 0.17 parts of phenol, 76 parts of methyl isobutyl ketone and 38 parts of toluene were added and dissolved uniformly by stirring, then immersed in an oil bath heated to 115 ° C.
- reaction solution was transferred to a beaker, the oil phase was stirred with hexane in the beaker, and the supernatant was discarded after standing. Finally, it concentrated by the evaporator and PET containing acrylate resin A was obtained.
- 50 parts of PET-containing acrylate resin A and 30 parts of carbitol acetate were charged into a 300 mL four-necked round bottom flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the atmosphere in the flask was changed to a nitrogen atmosphere. It was immersed in an oil bath heated to ⁇ 5 ° C.
- Carboxyl group-containing acrylate synthesis example 2 Recycled PET flakes with an IV value of 0.6 to 0.7 were charged in a 1000 ml four-necked round bottom separable lasco fitted with a stirrer, nitrogen inlet tube, and cooling tube, and the atmosphere in the flask was changed to a nitrogen atmosphere. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 1.6 parts of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
- reaction solution was transferred to a beaker, the oil phase was stirred with hexane in the beaker, and the supernatant was discarded after standing. Finally, it concentrated by the evaporator and PET containing acrylate resin B was obtained.
- 50 parts of PET-containing acrylate resin B and 27 parts of carbitol acetate were charged into a 300 mL four-necked round bottom flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the flask was filled with nitrogen atmosphere. It was immersed in an oil bath heated to + 5 ° C.
- Carboxyl group-containing acrylate synthesis example 3 Orthocresol novolak epoxy resin (600 parts by diethylene glycol monoethyl ether acetate, DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 parts (number of glycidyl groups (total number of aromatic rings) ): 5.0 moles), 360 parts (5.0 moles) of acrylic acid, and 1.5 parts of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 parts of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours.
- Orthocresol novolak epoxy resin 600 parts by diethylene glycol monoethyl ether acetate, DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6
- Example of Carboxylic Acid Resin Synthesis 192 parts of recycled PET flakes having an IV value of 0.6 to 0.7 were charged into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the flask was filled with a nitrogen atmosphere. Then, it was immersed in a salt bath heated to 300 ° C. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
- Example of photosensitive resin synthesis 192 parts of recycled PET flakes having an IV value of 0.6 to 0.7 were charged in a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the flask was filled with a nitrogen atmosphere. Then, it was immersed in a salt bath heated to 300 ° C. When the PET flakes were dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased.
- the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature inside the flask was kept at 220 ° C. ⁇ 5 ° C. and reacted for 5 hours.
- the reaction product was transparent yellow and soft viscous at room temperature.
- To 100 parts of the obtained reaction product 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed.
- 65 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid, and 0.26 part of paramethoxyphenol were added and reacted at 110 ° C. for 100 hours, and cooled to room temperature.
- the acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, 50 parts of brine was added and stirred. Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is Resin E
- ⁇ Optimum exposure amount> A circuit pattern substrate having a copper thickness of 35 ⁇ m was polished with buffalo, washed with water and dried, and then the photo-curable thermosetting resin compositions of the examples and comparative examples were applied to the entire surface by a screen printing method, and hot air at 80 ° C. It was dried for 60 minutes in a circulation drying oven. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na 2 CO 3 aqueous solution) is performed at 60. When the pattern of the step tablet remaining when performing in seconds was 7 steps, the optimum exposure amount was set.
- ⁇ Developability> The photocurable thermosetting resin compositions of the examples and comparative examples were applied to a solid copper substrate by a screen printing method so that the film thickness after drying was about 25 ⁇ m, and a hot air circulation drying oven at 80 ° C. For 30 minutes. After drying, development was performed with a 1 wt% Na 2 CO 3 aqueous solution, and the time until the dried coating film was removed was measured with a stopwatch.
- a circuit pattern substrate having a line / space of 300/300 and a copper thickness of 35 ⁇ m was coated with the photocurable thermosetting resin compositions of Examples and Comparative Examples by buffing, washing with water and drying, followed by screen printing. , And dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp. For the exposure pattern, a negative was used to draw a 20/30/40/50/60/70/80/90/100 ⁇ m line in the space. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition.
- a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and cured at 150 ° C. for 60 minutes to obtain a cured coating film. It determined using the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photosensitive resin composition for solder resists 200 times, and made this resolution.
- compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature.
- This substrate is exposed to a solder resist pattern at an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed with a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 0.2 MPa. And a resist pattern was obtained.
- This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes.
- the characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
- ⁇ Electroless gold plating resistance> Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 ⁇ m and gold 0.03 ⁇ m, and the tape peeling causes the presence or absence of resist layer peeling or plating penetration. After evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows. A: No soaking or peeling is observed. ⁇ : Slight penetration is confirmed after plating, but does not peel off after tape peeling. ⁇ : Slight penetration after plating and peeling after tape peel. X: There is peeling after plating.
- ⁇ Alkali resistance> The evaluation substrate was immersed in a 10 wt% NaOH aqueous solution at room temperature for 30 minutes, and soaking, dissolution of the coating film, and peeling by tape beer were confirmed. The judgment criteria are as follows. ⁇ : No soaking, melting or peeling. ⁇ : Slight penetration, dissolution or peeling is confirmed. X: Significant infiltration, dissolution or peeling.
- the curable resin composition of the present invention is excellent in electrode corrosion resistance, and can reduce the burden on the environment by using PET bottle waste as a raw material. In particular, it was found to be useful as a solder resist.
- the curable resin composition of the present invention or its dry film can be advantageously applied to the formation of a cured film or prepreg such as a solder resist of a printed wiring board or a flexible printed wiring board.
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Abstract
Description
例えば、プリント配線板用組成物の難燃材料のノンハロゲン化については、これまでも種々検討が行われている(例えば特許文献1など参照)。しかし、環境問題への関心の高まりから更なる環境への配慮を求められている。
その一方で、プリント配線板は電子機器に用いられることから、絶縁性が要求される。また、プリント配線板の層間樹脂絶縁層には、電子部品が高温で取り付けられることから、耐熱性が要求される。
しかしながら、従来のソルダーレジストに用いられていたカルボキシル基含有樹脂としては、エポキシ樹脂の変性により誘導されたエポキシアクリレート変性樹脂が一般的に用いられている。例えば、特開昭61-243869号公報(特許文献3)には、ノボラック型エポキシ化合物と不飽和一塩基酸の反応生成物に酸無水物を付加した感光性樹脂、光重合開始剤、希釈剤及びエポキシ化合物からなるソルダーレジスト組成物が開示されている。また、特開平3-250012号公報(特許文献4)には、サリチルアルデヒドと一価フェノールとの反応生成物にエピクロロヒドリンを反応させて得られたエポキシ樹脂に(メタ)アクリル酸を付加し、さらに多塩基性カルボン酸又はその無水物を反応させて得られる感光性樹脂、光重合開始剤、有機溶剤等からなるソルダーレジスト組成物が開示されている。これら、エポキシアクリレート変性樹脂では、エピクロロヒドリンを原料に使用しているためハロゲンイオンを含有しており、ハロゲンフリー化が困難であった。
さらに本発明の目的は、このような硬化性樹脂組成物を用いることによって得られる上記のような諸特性に優れたドライフィルム及び硬化物、並びに該ドライフィルムや硬化物によりソルダーレジスト等の硬化皮膜が形成されてなるプリント配線板を提供することにある。
別の好適な態様においては、さらに熱硬化性成分を含有し、好ましくはさらに着色剤を含有する。このような硬化性樹脂組成物、特に熱硬化性成分を含有する硬化性樹脂組成物は、ソルダーレジストとして好適に用いることができる。
さらに本発明によれば、前記光硬化性樹脂組成物又はドライフィルムをパターン状に光硬化させた後、熱硬化して得られる硬化皮膜を有することを特徴とするプリント配線板も提供される。
また、前記一般式(1)で示される構造を含む化合物がポリエステルの解重合により製造される場合、出発材料のポリエステルとして、廃ポリエステルを回収したものを原料として利用できるので、資源の有効活用に貢献できる。さらに、ポリエステルをポリオールで解重合させた解重合物は、分離することなくそのまま次の反応に供することができるので、再生樹脂利用率が高くなると共に、回収されたポリエステルの解重合物中の芳香環(ベンゼン環)を有するカルボン酸、特にテレフタル酸は、硬化性樹脂組成物の硬化塗膜のはんだ耐熱性、無電解金めっき耐性、耐湿性、電気絶縁性等に寄与できる。
さらに、熱硬化性樹脂を含むことで、はんだ耐熱性、無電解金めっき耐性、耐湿性、電気絶縁性等がさらに優れた硬化皮膜を形成できる。
従って、本発明の硬化性樹脂組成物は、プリント配線板やフレキシブルプリント配線板のソルダーレジスト等の硬化皮膜の形成に有利に適用できる。
以下、本発明の硬化性樹脂組成物の各構成成分について詳しく説明する。
なお、本明細書において、(メタ)アクリレートとは、アクリレート、メタクリレート及びそれらの混合物を総称する用語であり、他の類似の表現についても同様である。
前記したような水酸基もしくはカルボキシル基と反応し得る官能基を有する(メタ)アクリル系単量体は、単独で又は2種類以上を組み合わせて使用することができる。
本発明で用いる光重合開始剤としては、オキシムエステル基を有するオキシムエステル系光重合開始剤、α-アミノアセトフェノン系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤からなる群から選択される少なくとも1種の光重合開始剤を使用することができる。
このような光重合開始剤、光開始助剤、及び増感剤の総量は、本発明の硬化性樹脂100質量部に対して35質量部以下であることが好ましい。35質量部を超えると、これらの光吸収により深部硬化性が低下する傾向にある。
これらカルボキシル基含有感光性樹脂は、前記列挙したものに限らず使用することができ、1種類でも2種以上を混合しても使用することができる。
このような1分子内に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物の配合量は、組成物全体量の1wt%~50wt%、より好ましくは2~40wt%の割合が適当である。前記配合量が、1wt%未満の場合、十分な塗膜の強靭性が得られず、好ましくない。一方、50wt%を超えた場合、保存安定性が低下して、好ましくない。
赤色着色剤としてはモノアゾ系、ジズアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系などがあり、具体的には以下のようなカラ-インデックス(C.I.;ザ ソサイエティ オブ ダイヤーズ アンド カラリスツ(The Society of Dyers and Colourists)発行)番号が付されているものが挙げられる。
モノアゾ系:Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269。
ジスアゾ系:Pigment Red 37, 38, 41。
モノアゾレーキ系:Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1,68。
ベンズイミダゾロン系:Pigment Red 171、Pigment Red 175、Pigment Red 176、Pigment Red 185、Pigment Red 208。
ぺリレン系:Solvent Red 135、Solvent Red 179、Pigment Red 123、Pigment Red 149、Pigment Red 166、Pigment Red 178、Pigment Red 179、Pigment Red 190、Pigment Red 194、Pigment Red 224。
ジケトピロロピロール系:Pigment Red 254、Pigment Red 255、Pigment Red 264、Pigment Red 270、Pigment Red 272。
縮合アゾ系:Pigment Red 220、Pigment Red 144、Pigment Red 166、Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 242。
アンスラキノン系:Pigment Red 168、Pigment Red 177、Pigment Red 216、Solvent Red 149、Solvent Red 150、Solvent Red 52、Solvent Red 207。
キナクリドン系:Pigment Red 122、Pigment Red 202、Pigment Red 206、Pigment Red 207、Pigment Red 209。
青色着色剤としてはフタロシアニン系、アントラキノン系があり、顔料系はピグメント(Pigment)に分類されている化合物、具体的には、下記のようなものを挙げることができる:Pigment Blue 15、Pigment Blue 15:1、Pigment Blue 15:2、Pigment Blue 15:3、Pigment Blue 15:4、Pigment Blue 15:6、Pigment Blue 16、Pigment Blue 60。
染料系としては、Solvent Blue 35、Solvent Blue 63、Solvent Blue 68、Solvent Blue 70、Solvent Blue 83、Solvent Blue 87、Solvent Blue 94、Solvent Blue 97、Solvent Blue 122、Solvent Blue 136、Solvent Blue 67、Solvent Blue 70等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。
緑色着色剤としては、同様にフタロシアニン系、アントラキノン系、ペリレン系があり、具体的にはPigment Green 7、Pigment Green 36、Solvent Green 3、Solvent Green 5、Solvent Green 20、Solvent Green 28等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。
黄色着色剤としてはモノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等があり、具体的には以下のものが挙げられる。
アントラキノン系:Solvent Yellow 163、Pigment Yellow 24、Pigment Yellow 108、Pigment Yellow 193、Pigment Yellow 147、Pigment Yellow 199、Pigment Yellow 202。
イソインドリノン系:Pigment Yellow 110、Pigment Yellow 109、Pigment Yellow 139、Pigment Yellow 179、Pigment Yellow 185。
縮合アゾ系:Pigment Yellow 93、Pigment Yellow 94、Pigment Yellow 95、Pigment Yellow 128、Pigment Yellow 155、Pigment Yellow 166、Pigment Yellow 180。
ベンズイミダゾロン系:Pigment Yellow 120、Pigment Yellow 151、Pigment Yellow 154、Pigment Yellow 156、Pigment Yellow 175、Pigment Yellow 181。
モノアゾ系:Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183。
ジスアゾ系:Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198。
具体的に例示すれば、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet 13、36、C.I.ピグメントオレンジ1、C.I.ピグメントオレンジ5、C.I.ピグメントオレンジ13、C.I.ピグメントオレンジ14、C.I.ピグメントオレンジ16、C.I.ピグメントオレンジ17、C.I.ピグメントオレンジ24、C.I.ピグメントオレンジ34、C.I.ピグメントオレンジ36、C.I.ピグメントオレンジ38、C.I.ピグメントオレンジ40、C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ46、C.I.ピグメントオレンジ49、C.I.ピグメントオレンジ51、C.I.ピグメントオレンジ61、C.I.ピグメントオレンジ63、C.I.ピグメントオレンジ64、C.I.ピグメントオレンジ71、C.I.ピグメントオレンジ73、C.I.ピグメントブラウン23、C.I.ピグメントブラウン25、C.I.ピグメントブラック1、C.I.ピグメントブラック7等がある。
過酸化物分解剤は市販のものであってもよく、例えば、アデカスタブTPP(ADEKA社製)、マークAO-412S(アデカ・アーガス化学社製)、スミライザー(登録商標)TPS(住友化学社製)等が挙げられる。
上記のような酸化防止剤は、1種を単独で又は2種以上を組み合わせて用いることができる。
このような紫外線吸収剤としては、ベンゾフェノン誘導体、ベンゾエート誘導体、ベンゾトリアゾール誘導体、トリアジン誘導体、ベンゾチアゾール誘導体、シンナメート誘導体、アントラニレート誘導体、ジベンゾイルメタン誘導体等が挙げられる。
ソルダーレジスト層は、アルカリ現像性光硬化性樹脂組成物をブレードコーター、リップコーター、コンマコーター、フィルムコーター等でキャリアフィルム又はカバーフィルムに10~150μmの厚さで均一に塗布し乾燥して形成される。
カバーフィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム等を使用することができるが、ソルダーレジスト層との接着力が、キャリアフィルムよりも小さいものが良い。
攪拌機、窒素導入管、冷却管を取り付けた500ミリリットルの四口丸底セパラブルラスコにIV値0.6~0.7のリサイクルPETフレーク384部を仕込み、フラスコ内を窒素雰囲気とした後、300℃に昇温させた塩浴に浸した。PETが溶解したところで、攪拌を開始するとともに、酸化ジブチルスズ1.30部を添加した。次いで、予め130℃で加温し溶解させたトリメチロールプロパン134部をPETが固化しないよう注意しながら少量ずつ添加した。この間、粘度が低下した段階で攪拌速度を150rpmに高めた。次に、塩浴から予め240℃へ昇温した油浴に交換し、フラスコ内温を220℃±10℃に保ち、5時間反応させた。次に、この反応物を攪拌機、空気導入管、分留管、冷却管を取り付けた500mLの四口フラスコに150部取り、アクリル酸31.2部、パラトルエンスルホン酸1.82部、パラメトキシフェノール0.17部、メチルイソブチルケトン76部、トルエン38部を仕込み、攪拌して均一に溶解させた後、115℃±5℃に昇温させた油浴に浸し、所定時間反応を続けた。反応終了後、反応液の酸価を測定し、酸当量のアルカリ水溶液をフラスコ内に加えて攪拌し、中和した。次いで、食塩水(20wt%)を加え攪拌した。その後、溶液を分液漏斗に移し、反応液と同量のメチルエチルケトンを加え、水相を捨てた。油相を2回食塩水(5wt%)にて洗い、水相を捨てた。さらに、油相を少量の水道水で2回洗い、水相を捨てた。次に、反応液をビーカーに移し、ビーカー中で油相をヘキサンと攪拌し、静置後に上澄みを捨てた。最後に、エバポレーターにて濃縮を行い、PET含有アクリレート樹脂Aを得た。次に攪拌機、窒素導入管、冷却管を取り付けた300mLの四口丸底フラスコにPET含有アクリレート樹脂Aを50部、カルビトールアセテートを30部を仕込み、フラスコ内を窒素雰囲気とした後、80℃±5℃に昇温させた油浴に浸した。次に、トリフェニルホスフィン0.8部とメトキノン0.4部を7.8部のカルビトールアセテートに溶解させたカルビトールアセテート溶液を徐々に滴下しつつ、テトラヒドロ無水フタル酸20部を2.5時間毎に4回に分けて添加しながら10時間反応させ、固形分65%、固形分酸価119mgKOH/gのカルボキシル基含有アクリレートの樹脂溶液を得た。この樹脂溶液をワニスAとする。
攪拌機、窒素導入管、冷却管を取り付けた1000ミリリットルの四口丸底セパラブルラスコにIV値0.6~0.7のリサイクルPETフレーク384部を仕込み、フラスコ内を窒素雰囲気とした後、300℃に昇温させた塩浴に浸した。PETが溶解したところで、攪拌を開始するとともに、酸化ジブチルスズ1.6部を添加した。次いで、予め130℃で加温し溶解させたトリメチロールプロパン134部をPETが固化しないよう注意しながら少量ずつ添加した。この間、粘度が低下した段階で攪拌速度を150rpmに高めた。次に、塩浴から予め240℃へ昇温した油浴に交換し、フラスコ内温を220℃±10℃に保ち、5時間反応させた。次に、この反応物を攪拌機、空気導入管、分留管、冷却管を取り付けた1000mLの四口フラスコに518部取り、アクリル酸81部、パラトルエンスルホン酸2.4部、パラメトキシフェノール0.8部、メチルイソブチルケトン212部、トルエン112部を仕込み、攪拌して均一に溶解させた後、115℃±5℃に昇温させた油浴に浸し、所定時間反応を続けた。反応終了後、反応液の酸価を測定し、酸当量のアルカリ水溶液をフラスコ内に加えて攪拌し、中和した。次いで、食塩水(20wt%)を加え攪拌した。その後、溶液を分液漏斗に移し、反応液と同量のメチルエチルケトンを加え、水相を捨てた。油相を2回食塩水(5wt%)にて洗い、水相を捨てた。さらに、油相を少量の水道水で2回洗い、水相を捨てた。次に、反応液をビーカーに移し、ビーカー中で油相をヘキサンと攪拌し、静置後に上澄みを捨てた。最後に、エバポレーターにて濃縮を行い、PET含有アクリレート樹脂Bを得た。次に、攪拌機、窒素導入管、冷却管を取り付けた300mLの四口丸底フラスコにPET含有アクリレート樹脂Bを50部、カルビトールアセテートを27部を仕込み、フラスコ内を窒素雰囲気とした後、80℃±5℃に昇温させた油浴に浸した。次に、トリフェニルホスフィン0.8部とメトキノン0.4部を10部のカルビトールアセテートに溶解させたカルビトールアセテート溶液を徐々に滴下しつつ、テトラヒドロ無水フタル酸20部を2.5時間毎に4回に分けて添加しながら10時間反応させ、固形分65%、固形分酸価128mgKOH/gのカルボキシル基含有アクリレートの樹脂溶液を得た。この樹脂溶液をワニスBとする。
ジエチレングリコールモノエチルエーテルアセテート600部にオルソクレゾールノボラック型エポキシ樹脂(DIC株式会社製、EPICLON N-695、軟化点95℃、エポキシ当量214、平均官能基数7.6)1070部(グリシジル基数(芳香環総数):5.0モル)、アクリル酸360部(5.0モル)、及びハイドロキノン1.5部を仕込み、100℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン4.3部を仕込み、110℃に加熱して2時間反応後、120℃に昇温してさらに12時間反応を行った。得られた反応液に芳香族系炭化水素(ソルベッソ150)415部、テトラヒドロ無水フタル酸(THPA)456.0部(3.0モル)を仕込み、110℃で4時間反応を行い、冷却後、固形分酸価89mgKOH/g、固形分65%の樹脂溶液を得た。この樹脂溶液をワニスCとする。
攪拌機、窒素導入管、冷却管を取り付けた500ミリリットルの四口丸底セパラブルラスコにIV値0.6~0.7のリサイクルPETフレーク192部を仕込み、フラスコ内を窒素雰囲気とした後、300℃に昇温させた塩浴に浸した。PETが溶解したところで、攪拌を開始するとともに、酸化ジブチルスズ0.65部を添加した。次いで、予め130℃で加温し溶解させたトリメチロールプロパン134部をPETが固化しないよう注意しながら少量ずつ添加した。この間、粘度が低下した段階で攪拌速度を150rpmに高めた。次に、塩浴から予め240℃へ昇温した油浴に交換し、フラスコ内温を220℃±10℃に保ち、5時間反応させた後、室温まで冷却した。次に、THPAを121.6部、カルビトールアセテートを240部仕込み、フラスコ内を窒素雰囲気とした後、125±5℃に昇温させた油浴に浸した。攪拌を徐々に開始し3時間反応を行い、不揮発分65%、固形分酸価103mgKOH/gのカルボン酸樹脂ワニスを得た。これをワニスDとする。
攪拌機、窒素導入管、冷却管を取り付けた500ミリリットルの四口丸底セパラブルラスコにIV値0.6~0.7のリサイクルPETフレーク192部を仕込み、フラスコ内を窒素雰囲気とした後、300℃に昇温させた塩浴に浸した。PETフレークが溶解したところで、攪拌を開始するとともに、酸化ジブチルスズ0.65部を添加した。
次いで、予め130℃で加温し溶解させたトリメチロールプロパン134部をPETが固化しないよう注意しながら少量ずつ添加した。この間、粘度が低下した段階で攪拌速度を150rpmに高めた。次に、塩浴から予め240℃へ昇温した油浴に交換し、フラスコ内温を220℃±5℃に保ち、5時間反応させた。反応物は常温で黄色透明、軟質粘調状であった。
得られた反応物100部にトルエン37部、メチルイソブチルケトン74部を導入し、混合した。次にアクリル酸65部、パラトルエンスルホン酸1.94部、パラメトキシフェノール0.26部を加えて110℃で100時間反応させ、室温まで冷却した。得られた反応液の酸価を測定し、酸当量のアルカリ水溶液をフラスコ内に加え攪拌し、中和した。次いで、食塩水50部を加え攪拌した。
その後、溶液を分液ロートに移して水相を捨て、油相を5wt%のNaCl溶液100部にて2回洗った。洗浄後、エバポレーターにて溶剤分を留去し、不揮発分100%の反応物を得た。得られた反応物は常温で褐色透明の軟質液状であった。これを樹脂Eとする
上記各合成例で得られた樹脂を用い、下記表1に示す種々の成分と共に表1に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、ソルダーレジスト用感光性樹脂組成物を調製した。
*1 ハイドロタルサイト化合物:アルカマイザー 協和化学工業(株)製
*2 ジペンタエリスリトールヘキサアクリレート:日本化薬(株)製
*3 イルガキュアOXE02 BASFジャパン社製
*4 カルボジイミド化合物:カルボジライト10M-SP 日清紡(株)製
*5 EHPE3150(ダイセル化学工業(株)製)
*6 ブロックイソシアネート(TPA-B80E;旭化成ケミカルズ(株)製)
*7 トリグリシジルイソシアヌレート
*8 メラミン
*9 Irganox1010(BASFジャパン社製)
*10 2-メルカプトベンゾチアゾール(アクセルM;川口化学工業(株)製)
*11 C.I.Pigment Blue 15:3
*12 C.I.Pigment Yellow 147
*13 硫酸バリウム(B-30:堺化学(株)製)
*14 KS-66(信越シリコーン(株)製)
*15 ジプロピレングリコールモノメチルエーテル
<再生ポリエステル含有率>
前記実施例及び比較例の組成物において、硬化塗膜中の全有機物に対する再生ポリエステル樹脂の含有率を算出した。
銅厚35μmの回路パターン基板をバフロール研磨後、水洗し、乾燥してから、前記実施例及び比較例の光硬化性熱硬化性樹脂組成物をスクリーン印刷法により全面に塗布し、80℃の熱風循環式乾燥炉で60分間乾燥させた。乾燥後、高圧水銀灯(ショートアークランプ)搭載の露光装置を用いてステップタブレット(Kodak No.2)を介して露光し、現像(30℃、0.2MPa、1wt%Na2CO3水溶液)を60秒で行った際に残存するステップタブレットのパターンが7段の時を最適露光量とした。
前記実施例及び比較例の光硬化性熱硬化性樹脂組成物を、銅ベタ基板上にスクリーン印刷法により乾燥後の膜厚が約25μmになるように塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させた。乾燥後、1wt%Na2CO3水溶液によって現像を行い、乾燥塗膜が除去されるまでの時間をストップウォッチにより計測した。
前記実施例及び比較例の光硬化性熱硬化性樹脂組成物をそれぞれパターン形成された銅箔基板上にスクリーン印刷で全面塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させ、室温まで放冷した。この基板にPETフィルムを押し当て、その後、ネガフィルムを剥がしたときのフィルムの張り付き状態を評価した。判定基準は以下のとおりである。
◎:フィルムを剥がすときに、全く抵抗が無く、塗膜に跡が残らない。
○:フィルムを剥がす時に、全く抵抗が無いが、塗膜に跡が少しついている。
△:フィルムを剥がす時に、僅かに抵抗があり、塗膜に跡が少しついている。
×:フィルムを剥がす時に、抵抗があり、塗膜にはっきり跡がついている。
実施例及び比較例の光硬化性熱硬化性樹脂組成物を、ライン/スペースが300/300、銅厚35μmの回路パターン基板をバフロール研磨後、水洗し、乾燥してからスクリーン印刷法により塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させた。乾燥後、高圧水銀灯を搭載した露光装置を用いて露光した。露光パターンはスペース部に20/30/40/50/60/70/80/90/100μmのラインを描画させるネガを使用した。露光量は感光性樹脂組成物の最適露光量となるように活性エネルギー線を照射した。露光後、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、150℃×60分の熱硬化をすることにより硬化塗膜を得た。得られたソルダーレジスト用感光性樹脂組成物の硬化塗膜の最小残存ラインを200倍に調整した光学顕微鏡を用いて求め、これを解像性とした。
上記各合成例で得られた樹脂溶液を用い、前記表1に示す種々の成分と共に表1に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、光硬化性熱硬化性樹脂組成物を調製した。得られた光硬化性熱硬化性樹脂組成物をJPCA規格に基づくフラスコ燃焼処理イオンクロマトグラフ法を用いることにより、ハロゲンイオン不純物含有量(塩素物と臭素物の合計)を定量した。結果を表2に示す。尚、ハロゲン濃度が20ppm以下のものに関しての表記は[-]とする。
前記各実施例及び比較例の組成物を、パターン形成された銅箔基板上にスクリーン印刷で全面塗布し、80℃で30分乾燥し、室温まで放冷した。この基板に高圧水銀灯(ショートアークランプ)搭載の露光装置を用いて最適露光量でソルダーレジストパターンを露光し、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、レジストパターンを得た。この基板を、UVコンベア炉にて積算露光量1000mJ/cm2の条件で紫外線照射した後、150℃で60分加熱して硬化した。得られたプリント基板(評価基板)に対して以下のように特性を評価した。
ロジン系フラックスを塗布した評価基板を、予め260℃に設定した、はんだ槽に浸漬し、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれについて評価した。判定基準は以下のとおりである。
◎:10秒間浸漬を6回以上繰り返しても剥がれが認められない。
○:10秒間浸漬を3回以上繰り返しても剥がれが認められない。
△:10秒間浸漬を3回以上繰り返すと少し剥がれる。
×:10秒間浸漬を3回以内にレジスト層に膨れ、剥がれがある。
市販品の無電解ニッケルめっき浴及び無電解金めっき浴を用いて、ニッケル0.5μm、金0.03μmの条件でめっきを行い、テープピーリングにより、レジスト層の剥がれの有無やめっきのしみ込みの有無を評価した後、テープピーリングによりレジスト層の剥がれの有無を評価した。判定基準は以下のとおりである。
◎:染み込み、剥がれが見られない。
○:めっき後に少し染み込みが確認されるが、テープピール後は剥がれない。
△:めっき後にほんの僅かしみ込みが見られ、テープピール後に剥がれも見られる。
×:めっき後に剥がれが有る。
評価基板を10wt%NaOH水溶液に室温で30分間浸漬し、染み込みや塗膜の溶け出し、さらにテープビールによる剥がれを確認した。判定基準は以下のとおりである。
○:染み込み、溶け出し、剥がれなし。
△:染み込み、溶け出し、もしくは剥がれが少し確認される。
×:染み込み、溶け出し、もしくは剥がれが大きく確認される。
銅箔基板に代えてライン/スペース=50/50μmのクシ型電極パターンを用い、上記の条件で評価基板を作製し、このクシ型電極を121℃、97%R.H.の加温加湿条件下でDC305Vのバイアス電圧を印加し、100時間後の電極周辺の塗膜の変色度合いを評価した。判定基準は以下のとおりである。
○:塗膜の変色無し。
△:塗膜の変色が僅かに確認される。
×:塗膜の変色有り。
実施例1及び比較例2のソルダーレジスト用感光性樹脂組成物をそれぞれメチルエチルケトンで適宜希釈した後、アプリケーターを用いて、乾燥後の膜厚が30μmになるようにPETフィルム(東レ製 FB-50:16μm)に塗布し、40~100℃で乾燥させドライフィルムを得た。
回路形成された基板をバフ研磨した後、上記方法にて作製したドライフィルムを真空ラミネーター(名機製作所製 MVLP-500)を用いて加圧度:0.8MPa、70℃、1分、真空度:133.3Paの条件で加熱ラミネートして、未露光のソルダーレジスト層を有する基板(未露光の基板)を得た。得られた基板を前記評価方法と同様にして、最適露光量、現像性、解像性、はんだ耐熱性、金めっき耐性、耐アルカリ性の各試験を行った。
評価結果を表2に示す。
Claims (7)
- 前記一般式(1)で示される構造を含む化合物が、(a)ポリエステルを(b)1分子内に2個以上の水酸基を有するポリオールで解重合させることにより得られるポリオール樹脂であることを特徴とする請求項1に記載の硬化性樹脂組成物。
- 前記ポリエステル(a)が、再生ポリエステルであることを特徴とする請求項2に記載の硬化性樹脂組成物。
- カルボジイミド基を有する化合物をさらに含有することを特徴とする請求項1に記載の硬化性樹脂組成物。
- 請求項1~4のいずれか一項に記載の硬化性樹脂組成物を、フィルム上に塗布・乾燥させて得られる硬化性ドライフィルム。
- 請求項1~4のいずれか一項に記載の硬化性樹脂組成物、又は前記硬化性樹脂組成物をフィルム上に塗布・乾燥させて得られる硬化性ドライフィルムを、パターン状に硬化させて得られる硬化物。
- 請求項1~4のいずれか一項に記載の硬化性樹脂組成物、又は前記硬化性樹脂組成物をフィルム上に塗布・乾燥させて得られる光硬化性のドライフィルムを、パターン状に光硬化させた後、熱硬化して得られる硬化皮膜を有するプリント配線板。
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---|---|---|---|---|
JP6329334B1 (ja) * | 2017-02-07 | 2018-05-23 | 株式会社有沢製作所 | 感光性樹脂組成物、該感光性樹脂組成物を用いたソルダーレジストフィルム、フレキシブルプリント配線板及び画像表示装置 |
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Families Citing this family (2)
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Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06279662A (ja) * | 1993-03-29 | 1994-10-04 | Dainippon Ink & Chem Inc | 熱可塑性難燃ポリエステル樹脂組成物 |
JP2000159859A (ja) * | 1998-11-30 | 2000-06-13 | Hitachi Chem Co Ltd | 感光性樹脂組成物 |
JP2002060632A (ja) * | 2000-08-16 | 2002-02-26 | Sakai Chem Ind Co Ltd | 熱硬化性樹脂組成物 |
JP2002080706A (ja) * | 2000-09-07 | 2002-03-19 | Sakai Chem Ind Co Ltd | 不飽和ポリエステル性樹脂組成物 |
JP2002293910A (ja) * | 2001-03-28 | 2002-10-09 | Mitsui Chemicals Inc | アミド基含有芳香族ポリエステルポリオールおよびその製造方法 |
JP2002327055A (ja) * | 2001-05-02 | 2002-11-15 | Wakayama Prefecture | ポリエステルマクロモノマーおよびその製造方法 |
JP2004012810A (ja) * | 2002-06-06 | 2004-01-15 | Showa Denko Kk | 硬化性難燃組成物、その硬化物及びその製造方法 |
JP2006219567A (ja) * | 2005-02-09 | 2006-08-24 | Mitsui Chemicals Inc | ポリエステル樹脂組成物 |
JP2006233148A (ja) * | 2005-02-28 | 2006-09-07 | Wakayama Prefecture | ポリエステルマクロモノマーおよびその製造方法 |
WO2008013316A1 (fr) * | 2006-07-28 | 2008-01-31 | Teijin Limited | Composition de résine, son procédé de fabrication et article moulé |
JP2010224169A (ja) * | 2009-03-23 | 2010-10-07 | Taiyo Ink Mfg Ltd | 硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板 |
WO2010119494A1 (ja) * | 2009-04-14 | 2010-10-21 | 太陽インキ製造株式会社 | ポリオール化合物及びそれを含有する熱硬化性組成物 |
WO2010119493A1 (ja) * | 2009-04-14 | 2010-10-21 | 太陽インキ製造株式会社 | 感光性化合物及びそれを含有する光硬化性樹脂組成物 |
JP2010237270A (ja) * | 2009-03-30 | 2010-10-21 | Taiyo Ink Mfg Ltd | 感光性樹脂組成物、それを用いたドライフィルム及びプリント配線板 |
WO2010131649A1 (ja) * | 2009-05-12 | 2010-11-18 | 太陽インキ製造株式会社 | 感光性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板 |
WO2011021370A1 (ja) * | 2009-08-19 | 2011-02-24 | 太陽ホールディングス株式会社 | 光硬化性樹脂組成物 |
WO2011027695A1 (ja) * | 2009-09-01 | 2011-03-10 | 太陽インキ製造株式会社 | アルカリ現像性の光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1072624A3 (en) * | 1999-07-28 | 2001-02-07 | Dainippon Ink And Chemicals, Inc. | Process for producing unsaturated polyester and unsaturated polyester resin composition |
-
2010
- 2010-08-30 JP JP2010192193A patent/JP5734604B2/ja active Active
-
2011
- 2011-07-28 KR KR1020137008024A patent/KR101529799B1/ko active IP Right Grant
- 2011-07-28 CN CN201180042123.6A patent/CN103080236B/zh active Active
- 2011-07-28 WO PCT/JP2011/067293 patent/WO2012029468A1/ja active Application Filing
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06279662A (ja) * | 1993-03-29 | 1994-10-04 | Dainippon Ink & Chem Inc | 熱可塑性難燃ポリエステル樹脂組成物 |
JP2000159859A (ja) * | 1998-11-30 | 2000-06-13 | Hitachi Chem Co Ltd | 感光性樹脂組成物 |
JP2002060632A (ja) * | 2000-08-16 | 2002-02-26 | Sakai Chem Ind Co Ltd | 熱硬化性樹脂組成物 |
JP2002080706A (ja) * | 2000-09-07 | 2002-03-19 | Sakai Chem Ind Co Ltd | 不飽和ポリエステル性樹脂組成物 |
JP2002293910A (ja) * | 2001-03-28 | 2002-10-09 | Mitsui Chemicals Inc | アミド基含有芳香族ポリエステルポリオールおよびその製造方法 |
JP2002327055A (ja) * | 2001-05-02 | 2002-11-15 | Wakayama Prefecture | ポリエステルマクロモノマーおよびその製造方法 |
JP2004012810A (ja) * | 2002-06-06 | 2004-01-15 | Showa Denko Kk | 硬化性難燃組成物、その硬化物及びその製造方法 |
JP2006219567A (ja) * | 2005-02-09 | 2006-08-24 | Mitsui Chemicals Inc | ポリエステル樹脂組成物 |
JP2006233148A (ja) * | 2005-02-28 | 2006-09-07 | Wakayama Prefecture | ポリエステルマクロモノマーおよびその製造方法 |
WO2008013316A1 (fr) * | 2006-07-28 | 2008-01-31 | Teijin Limited | Composition de résine, son procédé de fabrication et article moulé |
JP2010224169A (ja) * | 2009-03-23 | 2010-10-07 | Taiyo Ink Mfg Ltd | 硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板 |
JP2010237270A (ja) * | 2009-03-30 | 2010-10-21 | Taiyo Ink Mfg Ltd | 感光性樹脂組成物、それを用いたドライフィルム及びプリント配線板 |
WO2010119494A1 (ja) * | 2009-04-14 | 2010-10-21 | 太陽インキ製造株式会社 | ポリオール化合物及びそれを含有する熱硬化性組成物 |
WO2010119493A1 (ja) * | 2009-04-14 | 2010-10-21 | 太陽インキ製造株式会社 | 感光性化合物及びそれを含有する光硬化性樹脂組成物 |
WO2010131649A1 (ja) * | 2009-05-12 | 2010-11-18 | 太陽インキ製造株式会社 | 感光性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板 |
WO2011021370A1 (ja) * | 2009-08-19 | 2011-02-24 | 太陽ホールディングス株式会社 | 光硬化性樹脂組成物 |
WO2011027695A1 (ja) * | 2009-09-01 | 2011-03-10 | 太陽インキ製造株式会社 | アルカリ現像性の光硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板 |
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WO2018092330A1 (ja) * | 2016-11-18 | 2018-05-24 | 株式会社有沢製作所 | 感光性樹脂組成物、該感光性樹脂組成物を用いたソルダーレジストフィルム、フレキシブルプリント配線板及び画像表示装置 |
CN109983403B (zh) * | 2016-11-18 | 2023-02-17 | 株式会社有泽制作所 | 感光性树脂组合物、使用该感光性树脂组合物的阻焊膜、柔性印刷布线板及图像显示装置 |
US11402754B2 (en) | 2016-11-18 | 2022-08-02 | Arisawa Mfg. Co., Ltd. | Photosensitive resin composition, solder resist film using said photosensitive resin composition, flexible printed wiring board, and image display device |
CN109983403A (zh) * | 2016-11-18 | 2019-07-05 | 株式会社有泽制作所 | 感光性树脂组合物、使用该感光性树脂组合物的阻焊膜、柔性印刷布线板及图像显示装置 |
WO2018147295A1 (ja) * | 2017-02-07 | 2018-08-16 | 株式会社有沢製作所 | 感光性樹脂組成物、該感光性樹脂組成物を用いたソルダーレジストフィルム、フレキシブルプリント配線板及び画像表示装置 |
CN110268325A (zh) * | 2017-02-07 | 2019-09-20 | 株式会社有泽制作所 | 感光性树脂组合物、使用该感光性树脂组合物的阻焊膜、柔性印刷布线板及图像显示装置 |
CN110268323A (zh) * | 2017-02-07 | 2019-09-20 | 株式会社有泽制作所 | 感光性树脂组合物、使用该感光性树脂组合物的阻焊膜、柔性印刷布线板及图像显示装置 |
US10627716B2 (en) | 2017-02-07 | 2020-04-21 | Arisawa Mfg. Co., Ltd. | Photosensitive resin composition, solder resist film using said photosensitive resin composition, flexible printed circuit and image display device |
JP6329334B1 (ja) * | 2017-02-07 | 2018-05-23 | 株式会社有沢製作所 | 感光性樹脂組成物、該感光性樹脂組成物を用いたソルダーレジストフィルム、フレキシブルプリント配線板及び画像表示装置 |
WO2018146821A1 (ja) * | 2017-02-07 | 2018-08-16 | 株式会社有沢製作所 | 感光性樹脂組成物、該感光性樹脂組成物を用いたソルダーレジストフィルム、フレキシブルプリント配線板及び画像表示装置 |
US11609493B2 (en) | 2017-02-07 | 2023-03-21 | Arisawa Mfg. Co., Ltd. | Photosensitive resin composition, solder resist film using said photosensitive resin composition, flexible printed circuit and image display device |
CN110268325B (zh) * | 2017-02-07 | 2023-06-06 | 株式会社有泽制作所 | 感光性树脂组合物及使用其的阻焊膜、柔性印刷布线板 |
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KR101529799B1 (ko) | 2015-06-17 |
JP2012046691A (ja) | 2012-03-08 |
CN103080236A (zh) | 2013-05-01 |
JP5734604B2 (ja) | 2015-06-17 |
KR20130048792A (ko) | 2013-05-10 |
CN103080236B (zh) | 2015-09-30 |
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