JP5916399B2 - UV curable transparent resin composition - Google Patents

Description

  The present invention relates to a transparent ultraviolet curable resin composition suitable for various resists, such as a solder resist of a wiring board such as a flexible wiring board and a printed wiring board, and a wiring board coated with a cured product obtained by curing the same. is there.

  Conventionally, an ultraviolet curable resin composition may be used as a solder resist film of a flexible wiring board, for example. The flexible wiring board may be used as a mounting substrate for a light emitting diode element (LED) or the like. In this case, the solder resist film formed on the mounting surface has a function of improving the reflectance of light from the light source. It has been demanded. And in order to raise the reflectance of the cured film of an ultraviolet curable resin composition, mixing an inorganic white pigment is known.

  On the other hand, the solder resist film formed on the mounting surface may be required to be transparent depending on the use of the wiring board. Moreover, since it is strongly desired that the electrode substrate for a touch panel incorporated in the front surface of a display body such as a liquid crystal display does not deteriorate its visibility, a highly transparent electrode protective film material is required. Therefore, Patent Document 1 discloses a reactive epoxycarboxylate compound and a reactive polysiloxane which provide a cured product having transparency, little deterioration with respect to light, and excellent balance of toughness, heat resistance, and moisture resistance. Carboxylic acid compounds have been proposed.

  However, conventionally, a cured product having transparency has a problem that transparency is not sufficient, defoaming during coating is not smooth, and coating properties need to be improved.

WO2006 / 109572

  In view of the above circumstances, an object of the present invention is to provide an ultraviolet curable transparent resin composition excellent in transparency and defoaming property during coating without impairing mechanical properties such as bending resistance. Objective.

Aspect of the present invention, (A) (meth) acrylic monomer, (B) a photopolymerization initiator, (C) the average primary particle diameter, insulated wiring board you containing silica particles is 1.0nm~3000nm a ultraviolet-curable transparent resin composition is for coating, the (C) silica particles, contain fumed silica or fused silica, the (a) (meth) 100 parts by mass of the acrylic monomer to It is an ultraviolet curable transparent resin composition characterized by containing 0.1 mass part-10 mass parts . In the present invention, (C) silica particles are blended as the filler. The present invention is a transparent resin composition as long as it does not contain a colorant that loses transparency (for example, a white pigment that loses transparency), and its cured product has transparency.

  In an aspect of the present invention, the (C) silica particles are contained in an amount of 0.1 to 40 parts by mass with respect to 100 parts by mass of the (A) (meth) acrylic monomer. It is a transparent resin composition.

  An aspect of the present invention is the ultraviolet curable transparent resin composition, wherein the (C) silica particles are fumed silica or fused silica.

  Fumed silica means dry silica produced by a so-called pyrolysis method in which vaporized silicon chloride undergoes a gas phase reaction in a high-temperature hydrogen flame. Fumed silica includes not only fumed silica whose surface is not hydrophobized by a surface treatment agent (hydrophilic fumed silica) but also fumed silica whose surface is hydrophobized by a surface treatment agent such as dimethyldichlorosilane. Silica (hydrophobic fumed silica) is also included.

  The fused silica means dry silica produced from a molten state by the above pyrolysis method.

The aspect of this invention is the hardened | cured material of the said ultraviolet curable transparent resin composition. Also, aspects of the present invention is a wiring board having a hard involved film of the ultraviolet-curable transparent resin composition.

  According to the aspect of the present invention, an ultraviolet curable resin composition capable of forming a cured product having excellent transparency can be obtained without impairing mechanical properties such as bending resistance. Moreover, according to the aspect of this invention, the ultraviolet curable transparent resin composition excellent in the defoaming property at the time of coating can be obtained. Further, according to the embodiment of the present invention, a cured product excellent in transparency and defoaming property and a wiring having a film excellent in transparency and defoaming property without impairing mechanical properties such as bending resistance. A substrate can be obtained.

  Next, the ultraviolet curable transparent resin composition of the present invention will be described. The ultraviolet curable transparent resin composition of the present invention contains (A) (meth) acrylic monomer, (B) photopolymerization initiator, and (C) silica particles, and each of the above components is as follows. It is.

(A) (Meth) acrylic monomer The (meth) acrylic monomer is not particularly limited. For example, acrylic acid, methacrylic acid, phenoxyethyl methacrylate, diethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy- 3-phenoxypropyl acrylate, ditrimethylolpropane tetraacrylate, phenol EO modified (meth) acrylate, nonylphenol PO modified (meth) acrylate, isobornyl (meth) acrylate, octyl (meth) acrylate, ethoxylated (meth) acrylate, dipropylene Glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, ethoxylated O-phenylphenol (meth) acrylate, phenoxypolyethylene Glycol (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzyl (meth) acrylate , Phenoxyethyl (meth) acrylate, N-acryloyloxyethyl hexahydrophthalimide, monohydroxyethyl (meth) acrylate phthalate, tricyclodecane dimethylol di (meth) acrylate, bisphenol F EO modified di (meth) acrylate, 9 , 9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, isocyanuric acid-modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, triethyleneglycol Rudi (meth) acrylate, neopentyl di (meth) acrylate, isocyanuric acid modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Examples include hexa (meth) acrylate. These may be used alone or in combination of two or more.

(B) Photopolymerization initiator The photopolymerization initiator is not particularly limited as long as it is generally used. For example, oxime initiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin -N-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy -2-propyl ) Ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2 -Ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4 diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, P-dimethylaminobenzoic acid ethyl ester and the like. These may be used alone or in combination of two or more.

  When the ultraviolet curable transparent resin composition of the present invention is irradiated with ultraviolet light having a wavelength of 300 to 400 nm, the photopolymerization initiator promotes photocuring of the ultraviolet curable transparent resin composition. The compounding quantity of a photoinitiator can be selected suitably, for example, 5-20 mass parts is preferable with respect to 100 mass parts of (meth) acrylic-type monomers, and 6-15 mass parts is especially preferable.

(C) Silica particle Silica particle is mix | blended as a filler of an ultraviolet curable transparent resin composition. By using silica particles as the filler, it is possible to improve the defoaming property during coating while reducing haze and improving transparency without impairing mechanical properties such as bending resistance.

The type of silica particles is not particularly limited. For example, silica produced from a molten state by a pyrolysis method (fused silica), silica produced by a pyrolysis method (fumed silica), silica produced by a sol-gel method Etc. Among these, fumed silica produced by a thermal decomposition method is preferable in terms of excellent dispersibility. Of the fumed silica, fumed silica whose surface is hydrophobized with a surface treatment agent (for example, dimethyldichlorosilane) is particularly preferable because it is more excellent in dispersibility. In the present invention, a mixture of fused silica and fumed silica may be used. The silica particles used in the present invention are fine particles. That is, the lower limit of the primary average particle diameter of the silica particles is 1.0 nm from the viewpoint of defoaming property, and 3.0 nm is preferable from the viewpoint of reducing haze by improving dispersibility. To 5.0 nm is particularly preferred. On the other hand, the upper limit of the primary average particle diameter of the silica particles is 3000 nm, preferably 400 nm from the viewpoint of reducing haze, and particularly preferably 30 nm from the viewpoint of coatability. The specific surface area of the silica particles is preferably 50 to 500 m ² / g, for example.

  The blending amount of the silica particles is not particularly limited, but the lower limit thereof is preferably 0.1 parts by mass, particularly 1.0 part by mass with respect to 100 parts by mass of the (meth) acrylic monomer from the defoaming point. preferable. On the other hand, the upper limit of the compounding amount of the silica particles is preferably 40 parts by mass from the viewpoint of surely reducing haze with respect to 100 parts by mass of the (meth) acrylic monomer, and particularly 10 parts by mass from the viewpoint of coatability. preferable.

  Examples of fused silica include “FB-3SDC”, “FB-3SDX”, “SFP-30M”, “SFP-20M”, “SFP-30MHE”, “SFP-130MC” from Denki Kagaku Kogyo Co., Ltd. Examples of fumed silica include Tokuyama Corporation's “Leoroseal QS-09”, “Leoloseal QS-10”, “Leoloseal QS-102”, “Leoloseal CP-102”, “Leoloseal QS- `` 20 '', `` Leolo Seal QS-20L '', `` Leolo Seal QS-30 '', `` Leolo Seal QS-30C '', `` Leolo Seal QS-40 '', `` Leolo Seal MT-10 '', `` Leolo Seal MT-10C '', `` Leolo Seal DM-10 '' ", Leoroseal DM-10C", "Leoloseal DM-20S", "Leoloseal DM-30", "Leoloseal DM-30S", "Leoloseal KS-20SC", "Leoloseal HM-20L", "Leoloseal HM-30S" , “Leolo Seal PM-20”, “Leolo Seal PM-20L”, “Excelica UF-103”, “Excelica UF-103A, Excelica UF-305, Excelica UF-310, Excelica UF-320, Nippon Aerosil Co., Ltd. AEROSIL OX50, AEROSIL 50, AEROSIL 90G, AEROSIL 130 , AEROSIL 150, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL R972, AEROSIL R974, AEROSIL R976, AEROSIL R976S, AEROSIL RX50, AEROSIL NAX50 , AEROSIL NX90, AEROSIL RX200, AEROSIL RX300, AEROSIL R812, AEROSIL R812S, AEROSIL RY50, AEROSIL NY50, AEROSIL RY200S, AEROSIL R202, AEROSIL RY200 , AEROSIL RY300, AEROSIL R104, AEROSIL R106, AEROSIL NA50H, AEROSIL NA50Y, AEROSIL RA200H, AEROSIL RA200HS, AEROSIL R805, AEROSIL R816, AEROSIL RM50 ”,“ AEROSIL R711 ”,“ AEROSIL R7200 ”,“ AEROSIL R8200 ”,“ AEROSIL R9200 ”and the like.

  The silica particles may be used alone or in combination of two or more.

  In the ultraviolet curable transparent resin composition of the present invention, in addition to the above components, (D) a phosphorus compound, (E) (meth) acrylated epoxy resin, and (F) (meth) acrylated urethane resin are appropriately blended. May be.

(D) Phosphorus compound When a phosphorus compound is blended in the ultraviolet curable transparent resin composition of the present invention, flame retardancy can be imparted. Examples of phosphorus compounds include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate, tris (bromochloropropyl) Halogen-containing phosphates such as phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate; trimethyl Non-halogen aliphatic phosphates such as phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triallyl phosphine; Sulfate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, tris (isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, diisopropylphenylphenyl phosphate, tris (trimethylphenyl) Phosphate, tris (t-butylphenyl) phosphate, hydroxyphenyl diphenyl phosphate, octyl diphenyl phosphate, 3-glycidyloxypropylene diphenylphosphine oxide, 3-glycidyloxydiphenylphosphine oxide, diphenylvinylphosphine oxide, 2- (9,10-dihydro -9-oxa-10-oxide-10-fo Non-halogen aromatic phosphoric acid ester such as phaphenanthrene-10-yl) methyl succinic acid bis- (2-hydroxyethyl) -ester polymer; aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, Zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate And metal salts of phosphinic acid such as titanium tetrakisdiphenylphosphinate.

  Among these, non-halogen phosphates and metal salts of phosphinic acid are preferable from the viewpoint of preventing dioxin generation and reducing environmental impact, and in a small amount, not only flame resistance but also solder heat resistance, with metal A metal salt of phosphinic acid is particularly preferable from the standpoint of effective heat resistance.

  When using phosphate ester as a phosphorus compound, the lower limit of the compounding quantity of a phosphorus compound is 5 mass parts with respect to 100 mass parts of (meth) acrylic-type monomers, and 10 from the point which ensures sufficient flame retardance. A mass part is preferable, and the upper limit is 50 parts by mass with respect to 100 parts by mass of the (meth) acrylic monomer, and 40 parts by mass is preferable from the viewpoint of reliably suppressing a decrease in mechanical strength of the cured film. On the other hand, when a metal salt of phosphinic acid is used as the phosphorus element-containing organic compound, the lower limit of the blending amount is 3 parts by mass with respect to 100 parts by mass of the (meth) acrylic monomer, and sufficient flame retardancy is achieved. 4 parts by mass is preferable from the viewpoint of securing, and the upper limit is 25 parts by mass with respect to 100 parts by mass of the (meth) acrylic monomer, and 20 from the point of reliably suppressing the decrease in mechanical strength of the cured film. Part by mass is preferred.

(E) (Meth) acrylated epoxy resin (Meth) acrylated epoxy resin is obtained by esterifying (meth) acrylic acid to an epoxy resin having two or more epoxy groups in one molecule. Partially esterified epoxy (meth) acrylate. The (meth) acrylated epoxy resin has a (meth) acryl group that can be radically polymerized by ultraviolet irradiation. Therefore, when a (meth) acrylated epoxy resin is blended with the ultraviolet curable transparent resin composition of the present invention, (meth) acrylated epoxy resins undergo a crosslinking reaction by ultraviolet irradiation, and the crosslinking density of the cured product is increased and the curability is increased. Can be further improved, and bending resistance can be imparted to the cured product. The (meth) acrylated epoxy resin is not particularly limited, but is 50 to 100% equivalent of (meta) to the epoxy group of the epoxy resin with respect to the epoxy resin having at least two epoxy groups in one molecule. ) A (meth) acrylated epoxy resin obtained by esterifying acrylic acid is preferred, and (meth) acrylic obtained by esterifying 80 to 100% equivalent of (meth) acrylic acid from the viewpoint of photosensitivity. Epoxy resins are particularly preferred.

  Examples of the epoxy resin that is a synthetic raw material for the (meth) acrylated epoxy resin include bisphenol A type epoxy resins (bisphenol A type liquid epoxy resin, bisphenol A type modified flexible epoxy resin, nuclear hydrogenated bisphenol A type liquid epoxy resin). ), Novolak type epoxy resins (phenol novolak type epoxy resins, o-cresol novolak type epoxy resins, p-tert-butylphenol novolak type, etc.), bisphenol F type obtained by reacting bisphenol F or bisphenol S with epichlorohydrin, Bisphenol S type epoxy resin, cycloaliphatic epoxy resin having cyclohexene oxide group, tricyclodecane oxide group, cyclopentene oxide group, tris (2,3-epoxypropyl) iso Cyanurate, may be mentioned triglycidyl tris (2-hydroxyethyl) triglycidyl isocyanurate having a triazine ring such as isocyanurate, dicyclopentadiene type epoxy resins, adamantane type epoxy resin. Among these, bisphenol A type epoxy resin is preferable from the viewpoint of bending resistance. These compounds may be used alone or in combination of two or more.

  The compounding amount of the (meth) acrylated epoxy resin is 1 to 75 parts by mass from the viewpoint of imparting sufficient curability and bending resistance to 100 parts by mass of the (meth) acrylic monomer. 50 parts by mass is preferred.

(F) (Meth) acrylated urethane resin The (meth) acrylated urethane resin may be a urethane (meth) acrylate obtained by reacting (meth) acrylic acid with a urethane resin, and is not limited to a specific compound. When a (meth) acrylated urethane resin is contained in an ultraviolet curable transparent resin composition, a cured coating film excellent in extensibility and bending resistance can be formed. For example, to a wiring board, particularly a flexible wiring board. Effective for application.

  The urethane resin is obtained by reacting a compound having two or more isocyanate groups in one molecule with a polyol compound having two or more hydroxyl groups in one molecule.

  The compound having two or more isocyanate groups in one molecule is not particularly limited, and examples thereof include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), methylenebiscyclohexyl isocyanate, and trimethyl. Examples of the diisocyanate include hexamethyl diisocyanate, hexamethylamine diisocyanate, methylenebiscyclohexyl isocyanate, toluene diisocyanate, 1,2-diphenylethane diisocyanate, 1,3-diphenylpropane diisocyanate, diphenylmethane diisocyanate, and dicyclohexylmethyl diisocyanate. These compounds may be used alone or in combination of two or more.

The polyol compound having two or more hydroxyl groups in one molecule is not particularly limited. For example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2 -Butylene glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,2- C ₂ − such as diethyl-1,3-propanediol, 3,3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol, etc. C ₂₂ or alkane diol, 2-butene-1,4-diol, 2,6-dimethyl-1-o Aliphatic diols such as alkene diols such as ten-3,8-diol; alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; glycerin, 2-methyl-2-hydroxymethyl-1 , 3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol Aliphatic triols such as 2,4-dihydroxy-3- (hydroxymethyl) pentane and 2,2-bis (hydroxymethyl) -3-butanol; and hydroxyl groups such as tetramethylolmethane, pentaerythritol, dipentaerythritol and xylitol Such as polyols with 4 or more It is. These compounds may be used alone or in combination of two or more.

  Examples of commercially available (meth) acrylated urethane resins include “purple light UV-1400B”, “purple light UV-1700B”, “purple light UV-6300B”, and “purple light UV” manufactured by Nippon Synthetic Chemical Co., Ltd. -7510B "," purple light UV-7600B "," purple light UV-7605B "," purple light UV-7610B "," purple light UV-7620EA "," purple light UV-7630B "and" purple light UV-7640B ", Negami Industrial Co., Ltd. "Art Resin UN-9000H", "Art Resin UN-3320HA", "Art Resin UN-3320HC", "Art Resin UN-3320HS" and "Art Resin UN-901T", Shin-Nakamura Chemical Co., Ltd. “NK Oligo U-4HA”, “NK Oligo U-6HA”, “NK Oligo U-6LPA”, “NK Oligo U” 15HA ”,“ NK Oligo UA-32P ”,“ NK Oligo U-324A ”and“ NK Oligo U-6H ”,“ EBECRYL1204 ”,“ EBECRYL1205 ”,“ EBECRYL215 ”,“ EBECRYL230 ”manufactured by Daicel-Cytec Co., Ltd. , “EBECRYL244”, “EBECRYL245”, “EBECRYL264”, “EBECRYL265”, “EBECRYL1280”, “EBECRYL285”, “EBECRYL8200”, “EBECRYL8405”, “EBECRYL8405”, “EBECRYL8405”, “EBECRYL8405” KRM8296 "," EBECRYL1290 "," EBECRYL1290K "," EBECRYL5129 "," EBE “RYL210”, “EBECRYL220”, “EBECRYL284”, “EBECRYL8210”, “EBECRYL8402” and “EBECRYL9260”, “UX-2201”, “UX-2301”, “UX-3204”, “UX-3204” manufactured by Nippon Kayaku Co., Ltd. “UX-3301”, “UX-4101”, “UX-0937”, “UX-5000”, “UX-5001”, “UX-5002”, “Beamset 575” manufactured by Arakawa Chemical Industries, Ltd., Tojo Examples thereof include “M-313”, “M-315” and “M-1200” manufactured by Synthetic Co., Ltd., “AH-600” manufactured by Kyoeisha Chemical Co., Ltd., and the like.

  The skeleton of the (meth) acrylated urethane resin is not particularly limited, but those having a large number of (meth) acryl functional groups may cure and shrink and the elongation may decrease, so the number of (meth) acryl functional groups in one molecule Is preferably 2-4. Moreover, since the weight average molecular weight tends to easily adhere to the substrate of the artwork film at the time of exposure when the value is small, it becomes difficult to obtain the intended cured coating film, so the lower limit is preferably 1500, Since the bending resistance tends to decrease when the weight average molecular weight is large, the upper limit is preferably 3000.

  The blending amount of the (meth) acrylated urethane resin is 1 to 40 parts by mass with respect to 100 parts by mass of the (meth) acrylic monomer, and 2 to 25 from the point of being excellent in the balance between high elongation and bending resistance. Part by mass is preferred. In addition, in order to obtain the cured coating film excellent in bending resistance, you may mix | blend (meth) acrylate urethane resin with the said (meth) acrylate epoxy resin.

  The ultraviolet curable transparent resin composition of the present invention may further contain various additive components, for example, various additives, solvents, and the like as necessary in addition to the above-described components. In addition, the ultraviolet curable transparent resin composition of the present invention does not contain a colorant in order to prevent the transparency from being impaired, but when coloring in a desired color, a coloring pigment is appropriately used. You may mix | blend coloring agents, such as. In addition, since the ultraviolet curable transparent resin composition of this invention is excellent in defoaming property, it is not necessary to mix | blend an antifoamer.

  Various additives include defoaming agents such as vinyl polymers and acrylic polymers, and leveling agents that are mixtures of polyether-modified polydimethylsiloxane and polyether.

  The solvent is used to adjust the viscosity and drying property of the ultraviolet curable transparent resin composition. Examples of the solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, Petroleum solvents such as petroleum ether and petroleum naphtha, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol mono Examples thereof include acetates such as ethyl ether acetate and butyl carbitol acetate. As for the compounding quantity in the case of using a solvent, 1-500 weight part is preferable with respect to 100 weight part of (meth) acrylic-type monomers.

  The colorant is not particularly limited as long as it does not lose transparency, and when it is colored white, black, blue, yellow, etc., the white colorant, black colorant, blue You may mix | blend a coloring agent, a yellow coloring agent, etc.

  Although the manufacturing method of the above-mentioned ultraviolet curable transparent resin composition of this invention is not limited to a specific method, For example, after mix | blending said component (A)-(C) and other components in a predetermined ratio as needed. It can be produced by kneading or mixing at room temperature with a kneading means such as a three-roll, ball mill or sand mill, or a stirring means such as a super mixer or a planetary mixer. Further, prior to the kneading or mixing, if necessary, preliminary kneading or premixing may be performed.

  Next, the coating method of the above-mentioned ultraviolet curable transparent resin composition of the present invention will be described. Here, a method of forming a film by coating the ultraviolet curable transparent resin composition of the present invention on a flexible substrate, more specifically, on a flexible wiring board having a circuit pattern formed by etching a copper foil Next, a method for forming a solder resist film by applying the ultraviolet curable transparent resin composition of the present invention will be described as an example. On a flexible wiring board having a circuit pattern formed by etching a copper foil, the ultraviolet curable transparent resin composition produced as described above is formed to a desired thickness using a method such as a screen printing method or a spray coating method. Apply.

  Then, the target cured coating film can be formed on a flexible wiring board by irradiating an ultraviolet-ray from on the apply | coated ultraviolet curable transparent resin composition.

  Next, examples of the present invention will be described. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Examples 1-22, Comparative Examples 1-5
The components shown in Table 1 below are blended in the proportions shown in Table 1 below, mixed and dispersed at room temperature using three rolls, and used in Examples 1-22 and Comparative Examples 1-5. A curable transparent resin composition was prepared. And the prepared ultraviolet curable transparent resin composition was applied as follows, and the test piece was created. In addition, the numerical value of the mixture ratio in Table 1 shows a mass part.

The details of each component in Table 1 are as follows.
(A) (Meth) acrylic monomer / light ester PO: manufactured by Kyoeisha Chemical Co., Ltd., phenoxyethyl methacrylate.
Light ester 2EG: Diethylene glycol dimethacrylate manufactured by Kyoeisha Chemical Co., Ltd.
GE-610: 2-hydroxyethyl methacrylate manufactured by Mitsubishi Gas Chemical Company, Inc.
M-5700: 2-hydroxy-3-phenoxypropyl acrylate manufactured by Toagosei Chemical Co., Ltd.
M-408: Ditrimethylolpropane tetraacrylate manufactured by Toagosei Chemical Co., Ltd.

(B) Photopolymerization initiator Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by Ciba Specialty Chemicals Co., Ltd.
Irgacure 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one manufactured by Ciba Specialty Chemicals.
Irgacure 2529: 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one manufactured by Ciba Specialty Chemicals Co., Ltd.

(C) Silica particles / AEROSIL 380: manufactured by Nippon Aerosil Co., Ltd., hydrophilic fumed silica, primary average particle diameter of 7 nm.
AEROSIL R974: manufactured by Nippon Aerosil Co., Ltd., hydrophobic fumed silica (surface treatment agent is dimethylsilane).
-Leolosil DM-20S: hydrophilic fumed silica manufactured by Tokuyama Corporation.

(D) Phosphorus compound / diphenylvinylphosphine oxide: manufactured by Katayama Chemical Co., Ltd.
ME-P8: Sanko Co., Ltd., 2- (9,10-Dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid bis- (2-hydroxyethyl) -ester Polymer.
・ Triallylphosphine: manufactured by Toyo Science Co., Ltd.

(E) (Meth) acrylated epoxy resin / EBECRYL 3708: manufactured by Daicel-Cytec Co., Ltd., a mixture of epoxy acrylate and 2-hydroxyethyl acrylate.
-Miramer PE110: manufactured by MIWON, phenyl epoxy acrylate.
-Miramer PE250: manufactured by MIWON, bisphenol A type epoxy dimethacrylate.

(F) (Meth) acrylated urethane resin. EBECRYL 8405: Urethane acrylate, manufactured by Daicel-Cytec.
-M-1200: Toagosei Co., Ltd. urethane acrylate.
AH-600: Kyoeisha Chemical Co., Ltd. product, phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer.

Filler B-30: Sakai Chemical Industry Co., Ltd. barium sulfate.
LMS-200: manufactured by Fuji Talc Kogyo Co., Ltd., hydrous magnesium silicate.
-CR-80: Titanium oxide manufactured by Ishihara Sangyo Co., Ltd.
Additive: UVX-189: A vinyl polymer produced by Enomoto Chemical Co., Ltd.
・ Polyflow No. 90: Acrylic polymer manufactured by Kyoeisha Chemical Co., Ltd.
-BYK-361N: manufactured by Big Chemie Japan, Inc., acrylic polymer.
BYK-307: A mixture of polyether-modified polydimethylsiloxane and polyether, manufactured by Big Chemie Japan Co., Ltd.
Silicone antifoaming agent KS-66: manufactured by Shin-Etsu Chemical Co., Ltd., silicone resin.
Coloring pigment, Lionol Blue FG-7351: manufactured by Toyo Ink Co., Ltd., a phthalocyanine compound.
Chromophthal yellow AGR: Anthraquinone compound manufactured by Ciba Specialty Chemicals.

Test piece preparation process The surface of a polyethylene terephthalate film (PET film) (manufactured by Teijin DuPont, 25 μm thick) was degreased with isopropyl alcohol, and then the ultraviolet light prepared as described above by screen printing on the degreased surface. A curable transparent resin composition was applied. Then, ultraviolet rays (300 to 400 nm) were exposed to 1000 mJ / cm ² using an exposure apparatus (UB093-5AM, manufactured by Eye Graphic). The thickness of the cured coating film was 15 to 20 μm.

Evaluation (1) Haze (cloudiness value) (%)
Instead of the PET film, a cured coating film was formed on the surface of a quartz glass substrate (50 mm × 50 mm, thickness 1 mm) by the same method as in the above test piece preparation step to obtain a test piece. The haze of the test piece was measured using a U-3310 spectrophotometer manufactured by Hitachi High-Tech, in accordance with JIS-K-7105 and JIS-K-7136.
(2) Total light transmittance (%)
Instead of a PET film, a cured coating film was formed on the surface of a quartz glass substrate (50 × 50 × 1 mm) by the same method as in the above-mentioned test piece preparation step to obtain a test piece. The total light transmittance was measured with respect to this test piece according to JIS-K-7105 and JIS-K-7136 using a U-3310 spectrophotometer manufactured by Hitachi High-Tech.
(3) Antifoaming property
The ultraviolet curable transparent resin composition was applied by the method of the above test piece preparation step, and the defoaming property after coating was evaluated according to the following.
○: Defoamed within 1 minute after coating.
Δ: Defoaming after coating for more than 1 minute to 5 minutes.
X: No defoaming even after standing for 5 minutes after coating.
(4) Bending resistance
For the test piece created in the above-mentioned test piece creation step, 180 ° bending is repeated several times by goby folding, and the crack occurrence state in the transparent cured coating at that time is observed visually and with a × 200 optical microscope, The number of times that no crack occurred was measured.
(5) Insulation resistance (Ω)
Instead of the PET film, a comb-like test pattern (line width: 100 μm, line spacing: 100 μm) was applied by the same method as in the test piece preparation step to form a cured coating film, which was used as a test piece. The test piece was applied with a direct current of 50 V in an atmosphere having a temperature of 85 ° C. and a humidity of 85% and left for 1000 hours.

  The evaluation results are shown in Table 2.

  As shown in the evaluation results of each example in Table 2 above, when silica fine particles are blended with the (meth) acrylic monomer, haze is reduced without sacrificing bending resistance and total light transmittance, and transparency is improved. Improved. Moreover, even if it did not use an antifoamer, it was excellent in defoaming property and, as a result, the finished appearance of the coating film improved. Furthermore, from Examples 11 to 13 and Examples 14 to 16, when (meth) acrylated epoxy resin and (meth) acrylated urethane resin were blended, the bending resistance was further improved. Moreover, in the Examples, the insulation resistance value was not impaired and the insulation property was good regardless of the presence or absence of blending of silica particles, phosphorus compound, (meth) acrylated epoxy resin, and (meth) acrylated urethane resin.

  On the other hand, from the results of the comparative examples, when a material other than silica fine particles was used as the filler, haze was increased, the total light transmittance was also decreased, and good transparency was not obtained. Moreover, in a comparative example, it was inferior to defoaming property and it was necessary to mix | blend an antifoamer in order to provide favorable defoaming property.

  In the ultraviolet curable transparent resin composition of the present invention, it is possible to obtain a cured product having excellent transparency without impairing mechanical properties such as bending resistance, and furthermore, excellent defoaming properties during coating. For example, the utility value is high in fields such as an insulating coating on a wiring board, a solder resist film, and a protective film for a touch panel.

Claims (3)

(A) (meth) acrylic monomer, (B) a photopolymerization initiator, (C) the average primary particle diameter, ultraviolet is insulating film of the wiring board you containing silica particles is 1.0nm~3000nm A curable transparent resin composition ,
The (C) silica particles contain fumed silica or fused silica, and are contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) (meth) acrylic monomer. UV curable transparent resin composition . Hardened | cured material of the ultraviolet curable transparent resin composition of Claim 1 . Wiring board having a hard involved film of the UV curable transparent resin composition of claim 1.