Composition

Abstract

To provide a composition capable of yielding a cured product having superior adhesion to a substrate, while inhibiting bleed-out.SOLUTION: One embodiment of the present invention is a composition. The composition contains a polybutadiene resin. The polybutadiene resin is in an amount of 1 mass% or more and 10 mass% or less based on the total solid content of the composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition. [Background technology]

[0002] Conventionally, various curable resin compositions suitable for forming solder resists have been developed.

[0003] For example, Patent Document 1 discloses that a solder resist is formed using a resin composition containing a specified modified urethane resin and a specified defoaming agent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2011 / 040560 DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0005] However, when using resin compositions according to conventional technology, it was sometimes difficult to obtain a cured product that had excellent adhesion to a substrate made of engineering plastic (engineering plastic substrate) while suppressing bleed-out.

[0006] Therefore, an object of the present invention is to provide a composition which is capable of producing a cured product having excellent adhesion to engineering plastic substrates while suppressing bleed-out. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by combining specific components, and have completed the present invention.

[0008] One aspect of the present invention is a composition. The composition includes an epoxy resin, a polybutadiene resin, a filler, and a curing agent. The polybutadiene resin is present in an amount of 1% by mass or more and 10% by mass or less based on the total solid content of the composition.

[0009] The composition preferably has a viscosity of 100 dPa·s or more and 500 dPa·s or less, measured at 5 rpm and 25° C. using a cone-plate viscometer, and a thixotropy index of 1.0 or more and 1.6 or less. The epoxy resin preferably includes a liquid epoxy resin. In the composition, the ratio of the solid content of the liquid epoxy resin to the total amount of the solid content of the epoxy resin and the solid content of the polybutadiene resin ([amount of liquid epoxy resin] / [amount of epoxy resin+amount of polybutadiene resin]×100) is preferably 45 mass% or less. The content of the organic solvent in the composition is preferably less than 25% by mass. The polybutadiene resin preferably includes an epoxidized polybutadiene resin. The composition is preferably used to form a solder resist. The composition is preferably used for forming a solder resist in a three-dimensional circuit board. The composition is preferably for syringe application. Effect of the Invention

[0010] According to the present invention, there is provided a resin composition which is capable of producing a cured product having excellent adhesion to engineering plastic substrates while suppressing bleed-out. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] When isomers exist in the described compounds, all possible isomers can be used in the present invention unless otherwise specified.

[0012] In this specification, when the upper limit and the lower limit of a numerical range are separately described, all combinations of the lower limit and the upper limit are substantially described, provided that there is no contradiction.

[0013] In this specification, unless otherwise specified, various measurements are performed at room temperature (25° C.).

[0014] In this specification, the number average molecular weight and weight average molecular weight are values ​​measured by gel permeation chromatography (GPC) and converted using a calibration curve prepared using standard polystyrene.

[0015] In this specification, there may be cases where the components contained in the composition (curable resin composition) and the components contained in a resin layer or the like which is a dried coating film of the composition (curable resin composition) are described without distinction.

[0016] In this specification, the term "solid content" refers to components other than volatile components such as organic solvents, etc. Therefore, liquid components such as liquid epoxy resins, which will be described later, are also treated as solid contents.

[0017] The composition, physical properties / properties, production method, and applications / method of use of the composition (curable resin composition) according to the present disclosure will be described below, but the present invention is not limited to the following in any way.

[0018] <<<Composition>>> The composition according to the present disclosure preferably includes an epoxy resin, a polybutadiene resin, a filler, and a curing agent. In addition, the composition according to the present disclosure preferably contains a colorant. Furthermore, the composition according to the present disclosure may contain other components to the extent that the effects of the present disclosure are not impaired. Each component will be described below.

[0019] <<Epoxy resin>> The epoxy resin may be a known, commonly used compound having one or more epoxy groups, and preferably has two or more epoxy groups.

[0020] Examples of epoxy resins include bisphenol type epoxy resins (bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol E type epoxy resins, bisphenol M type epoxy resins, bisphenol P type epoxy resins, bisphenol Z type epoxy resins, etc.), novolac type epoxy resins (bisphenol A novolac type epoxy resins, phenol novolac type epoxy resins, cresol novolac epoxy resins, etc.), biphenyl type epoxy resins, biphenyl novolac type epoxy resins, biphenyl aralkyl type epoxy resins, aryl alkylene type epoxy resins, tetraphenylol ethane type epoxy resins, Examples of the epoxy resins include naphthalene type epoxy resins, anthracene type epoxy resins, phenoxy type epoxy resins, dicyclopentadiene type epoxy resins, norbornene type epoxy resins, trihydroxyphenylmethane type epoxy resins, hydantoin type epoxy resins, tetraphenylolethane type epoxy resins, brominated epoxy resins, glycidylamine type epoxy resins, alicyclic epoxy resins, diglycidyl phthalate resins, tetraglycidylxylenoylethane resins, glycidyl methacrylate copolymer epoxy resins, copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, epoxy modified polybutadiene rubber derivatives, and CTBN modified epoxy resins.

[0021] The epoxy resin preferably contains at least one selected from bisphenol type epoxy resins, novolac type epoxy resins, and phenol novolac type epoxy resins. By using a polybutadiene resin (e.g., an epoxidized polybutadiene resin) in combination with such an epoxy resin, the adhesion between the obtained cured product and a substrate (especially an engineering plastic substrate) can be further improved.

[0022] The epoxy resin may include a liquid epoxy resin. The liquid epoxy resin is an epoxy resin that is liquid at 25°C.

[0023] The content of the epoxy resin based on the total solid content of the composition is preferably 5% by mass or more, or 10% by mass or more, and preferably 30% by mass or less, or 25% by mass or less. By setting the content of the polybutadiene resin within such a range, it is possible to improve the adhesion between the obtained cured product and the substrate (especially the engineering plastic substrate) and to easily suppress bleeding out.

[0024] The epoxy resin content based on the total solid content of the composition excluding the filler is preferably 10.0 mass% or more, or 20.0 mass% or more, and is preferably 50.0 mass% or less, or less than 40.0 mass%.

[0025] When the composition contains a liquid epoxy resin, the ratio of the solid content of the liquid epoxy resin to the total amount of the solid content of the epoxy resin and the solid content of the polybutadiene resin in the composition ([liquid epoxy resin amount] / [epoxy resin amount+polybutadiene resin amount]×100) is preferably 45% by mass or less, 43% by mass or less, or 40% by mass or less. The lower limit of the solid content of the liquid epoxy resin is not particularly limited, and is, for example, 1% by mass, 5% by mass, 10% by mass, 15% by mass, or 20% by mass. By setting the content of the liquid epoxy resin within such a range, the adhesion between the obtained cured product and the substrate (particularly, the engineering plastic substrate) can be improved.

[0026] <<Polybutadiene resin>> The polybutadiene resin may be any known one, and the ratio of the cis 1,4 structural unit, trans 1,4 structural unit, 1,2 structural unit, etc. constituting the polybutadiene resin may be any ratio.

[0027] The polybutadiene resin preferably contains an epoxidized polybutadiene resin. The epoxidized polybutadiene resin can be obtained by epoxidizing a part of the above-mentioned polybutadiene resin with, for example, hydrogen peroxide or peracids. The epoxidized polybutadiene may be a polybutadiene resin containing an internal epoxy group as disclosed in JP-A-2002-293878. The epoxidized polybutadiene resin is a component different from the epoxy resin.

[0028] The polybutadiene resin and the epoxidized polybutadiene resin may be commercially available products. Commercially available polybutadiene resins include, for example, "B-1000", "B-2000", and "B-3000" manufactured by Nippon Soda Co., Ltd. Commercially available epoxidized polybutadiene resins include, for example, "Epolead PB3600", "Epolead PB4700", "Epofriend CT310", and "Epofriend AT501" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd., and "Ricon 657" manufactured by Cray Valley Chemical Industries, Ltd.

[0029] The number average molecular weight (Mn) of the polybutadiene resin is not particularly limited, but is preferably 1,500 or more and 10,000 or less, and more preferably 2,000 or more and 4,000 or less.

[0030] The content of the polybutadiene resin (preferably the content of the epoxidized polybutadiene resin) based on the total solid content of the composition is preferably 1 mass% or more, 2 mass% or more, or 3 mass% or more, and preferably 10 mass% or less, 8 mass% or less, 6 mass% or less, or 5 mass% or less. By setting the content of the polybutadiene resin within such a range, it is easy to suppress bleeding out while improving the adhesion between the obtained cured product and the substrate (particularly, the engineering plastic substrate).

[0031] The content of polybutadiene resin (preferably the content of epoxidized polybutadiene resin) based on the total solid content excluding the filler of the composition is preferably 2.0 mass% or more, 4.0 mass% or more, or 5.0 mass% or more, and is preferably less than 17.0 mass%, 15.0 mass% or less, 12.0 mass% or less, or 9.5 mass% or less.

[0032] In addition, the ratio of the epoxy resin content to the polybutadiene resin content in the composition (epoxy resin / polybutadiene resin) is preferably 1.00 or more, 1.50 or more, or 2.00 or more, and is preferably 15.00 or less, 12.00 or less, 8.00 or less, or 5.00 or less.

[0033] <<Filler>> Examples of the filler include inorganic fillers and organic fillers.

[0034] Examples of inorganic fillers that can be used include metal oxides such as silica, alumina, and titanium oxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; clay minerals such as talc and mica; fillers having a ferovskite crystal structure such as barium titanate and strontium titanate; boron nitride, aluminum borate, barium sulfate, and calcium carbonate.

[0035] Examples of organic fillers that can be used include fluororesin fillers such as polytetrafluoroethylene (PTFE), tetrafluoroethylene / ethylene copolymer (ETFE), tetrafluoroethylene / perfluoroalkylvinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF); and hydrocarbon resin fillers such as cycloolefin polymer (COP) and cycloolefin copolymer (COC).

[0036] The filler content based on the total solid content of the composition is preferably 10 mass % or more, 20 mass % or more, or 40 mass % or more, and is preferably 80 mass % or less, 75 mass % or less, or 70 mass % or less.

[0037] <<Hardening agent>> The curing agent is not particularly limited as long as it can be used in combination with the epoxy resin. Some curing agents act as both a curing agent and a curing catalyst, but in the present disclosure, a component that has both functions is considered to be a curing agent.

[0038] Examples of the curing agent include compounds having a curing group such as an amino group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, a thiol group, and an active ester group. More specifically, examples of the curing agent include amide-based curing agents, amine-based curing agents, phenol-based curing agents, imidazole-based curing agents, acid anhydride-based curing agents, and active ester-based curing agents. These may be used alone or in combination in any ratio.

[0039] Examples of the amide-based curing agent include dicyandiamide and aliphatic polyamide.

[0040] Examples of the amine curing agent include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, metaxylenediamine, isophoronediamine, norbornenediamine, 1,3-bisaminomethylcyclohexane, N-aminoethylpiperazine, diaminodiphenylmethane, m-phenylenediamine, p-phenylenediamine, ammonia, triethylamine, diethylamine, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl ether.

[0041] Examples of the phenol-based hardener include bisphenol A, bisphenol F, phenol novolac resin, cresol novolac resin, and p-xylene novolac resin.

[0042] Specific examples of imidazole-based curing agents include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, and 4-butyl-(2-hydroxyphenyl)-5-methylimidazole.

[0043] Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, chlorendic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis(anhydrotrimate), and methylcyclohexene tetracarboxylic anhydride.

[0044] The active ester curing agent can be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound.

[0045] Examples of the carboxylic acid compound used in the preparation of the active ester-based curing agent include acetic acid, propionic acid, fluoroacetic acid, benzoic acid, nitrobenzoic acid, chlorobenzoic acid, thiobenzoic acid, adipic acid, sebacic acid, succinic acid, maleic acid, itaconic acid, 1,2,3,4-butanetetracarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, benzenetricarboxylic acid, and benzenetetracarboxylic acid.

[0046] The hydroxy compound used in the preparation of the active ester-based curing agent is preferably a phenol compound or a naphthol compound. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac.

[0047] As the active ester curing agent, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters which are heterocyclic hydroxy compounds, etc., are preferably used. Commercially available active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol condensation structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, active ester compounds containing a benzoylated product of phenol novolac, etc.

[0048] As the curing agent, an imidazole-based curing agent is preferred from the viewpoints of low-temperature curing property, storage stability, and curing speed. In particular, when a substrate having low heat resistance such as a polycarbonate substrate is used as the engineering plastic substrate, low-temperature curing at or below the heat resistance temperature of the substrate is required, so that it is particularly preferred to use an imidazole-based curing agent having excellent low-temperature curing property.

[0049] The content of the curing agent in the composition can be appropriately adjusted depending on the type of the curing agent.

[0050] When an imidazole-based curing agent is used as the curing agent, the content of the curing agent based on the total solid content of the composition is preferably 0.01 mass % or more, 0.05 mass % or more, or 0.1 mass % or more, and is preferably 20 mass % or less, 10 mass % or less, or 5 mass % or less.

[0051] <<Coloring agent>> The composition of the present disclosure may contain a suitable colorant depending on the application of the composition. As the colorant, a color pigment or dye having a suitable color tone may be used. As the colorant, a red colorant, a blue colorant, a green colorant, a yellow colorant, a white colorant, a black colorant, a purple colorant, an orange colorant, a brown colorant, or the like may be used.

[0052] Examples of red colorants include monoazos, diazos, azo lakes, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azos, anthraquinones, and quinacridones. Blue colorants include phthalocyanine and anthraquinone types, and the pigment type can be a compound classified as a pigment. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used. Green colorants include phthalocyanine-based, anthraquinone-based, and perylene-based compounds, and may also include metal-substituted or unsubstituted phthalocyanine compounds. Yellow colorants include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based agents. Examples of black colorants include carbon black, graphite, iron oxide, titanium black, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, molybdenum sulfide, and bismuth sulfide.

[0053] The colorants may be used alone or in combination in any desired ratio.

[0054] <<Other ingredients>> Other components include additives such as defoamers, dispersants (wetting dispersants, etc.), resin components other than those mentioned above, crosslinking agents, crosslinking assistants, rust inhibitors, catalysts, antioxidants, leveling agents, sensitizers, adhesion assistants, surfactants, plasticizers, flame retardants, cellulose nanofibers, and adhesion promoters.

[0055] Examples of resin components other than those mentioned above include phenolic resins. The phenolic resin is not particularly limited, and may be bifunctional or trifunctional or more. Examples of the phenolic resin include phenolic novolac resins, alkylphenolic novolac resins, triazine structure-containing phenolic novolac resins, bisphenol A novolac resins, dicyclopentadiene structure-containing phenolic resins, Xylok-type phenolic resins, terpene-modified phenolic resins, polyvinylphenols, naphthalene structure-containing phenolic resins, and fluorene structure-containing phenolic resins. By including such a phenolic resin, the curability of the composition can be improved.

[0056] When the composition contains a resin component other than those mentioned above (e.g., a phenolic resin), the content of the phenolic resin based on the total solid content of the composition is preferably 1 mass % or more, 5 mass % or more, or 8 mass % or more, and is preferably 40 mass % or less, 20 mass % or less, or 15 mass % or less.

[0057] The composition may also contain an organic solvent as another component.

[0058] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc.; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc.; cellosolves such as cellosolve and butyl cellosolve, carbitols such as carbitol and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and other organic solvents such as dimethylformamide and dimethylacetamide, etc.

[0059] When the composition contains an organic solvent, the content of the organic solvent in the composition is preferably 40% by mass or less, 30% by mass or less, or less than 25% by mass (or 24% by mass or less). By setting the content of the organic solvent in such a range, it is possible to improve the workability when the composition is made into a composition for a syringe or dispenser described later. When the composition contains an organic solvent, the lower limit of the content of the organic solvent in the composition is not particularly limited, and may be 0.1% by mass, 1% by mass, or 3% by mass.

[0060] <<<Physical properties / properties>>> <<Viscosity, Thixotropy Index (TI)>> The viscosity of the composition of the present disclosure is preferably 100 dPa·s or more, 150 dPa·s or more, 200 dPa·s or more, or 220 dPa·s or more, and is preferably 500 dPa·s or less, 400 dPa·s or less, or 300 dPa·s or less. The viscosity in the present disclosure is a value measured at 5 rpm and 25°C using a cone-plate viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.) and a cone rotor of 1°34'×R24 in accordance with JIS Z 8803:2011, section 10, "Method of measuring viscosity using a cone-plate rotational viscometer", at 5 rpm, 25°C, and 10 seconds.

[0061] The thixotropy index (TI) of the composition of the present disclosure is preferably 1.0 or more, or 1.1 or more, and preferably 1.6 or less, or 1.5 or less. The thixotropy index in the present disclosure is a value calculated by the following formula using a cone-plate viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.) and a 1°34'×R24 cone rotor to measure viscosity at 5 rpm, 25° C., and 10 seconds (the viscosity at 5 rpm) and viscosity at 50 rpm, 25° C., and 10 seconds (the viscosity at 50 rpm) in accordance with JIS Z 8803:2011, section 10 "Method of measuring viscosity using a cone-plate rotational viscometer."

number

[0062] By setting the viscosity and thixotropy index within the above ranges, it is possible to form thin lines and improve liquid drainage, particularly when the composition is used as a composition for a syringe or dispenser (particularly a composition for a syringe or dispenser for a three-dimensional circuit board) as described below.

[0063] The viscosity and thixotropy index of the composition can be adjusted by changing the amount of organic solvent, the amount and particle size of the filler, the type and amount of wetting and dispersing agent, etc., taking into consideration the physical properties of each raw material.

[0064] <<<Manufacturing method>>> The composition of the present disclosure can be produced by mixing and stirring the above-mentioned components in a predetermined mixing ratio using a known and commonly used method.

[0065] <<<Application / How to use>>> The composition according to the present disclosure is preferably used as a composition for solder resist (solder resist composition) or a composition for forming a solder dam (solder dam composition) because it is easy to obtain a cured product having excellent adhesion to a substrate and excellent insulation. In particular, the composition according to the present disclosure is preferably used for a solder resist or a solder dam constituting a circuit board or a three-dimensional circuit board using an engineering plastic substrate. A solder dam is a solder resist formed of thin lines so as to surround a certain area, and functions as a dam to prevent molten solder from flowing out from the area. For example, the solder dam is formed so as to surround the periphery of a mounting part (such as a pad part on which solder is placed). The composition according to the present disclosure is easily applied in a thin line shape, and therefore can be preferably used for forming such a solder dam. In the present disclosure, the "solder resist" also includes such a form of solder dam. The composition according to the present disclosure can also be preferably used as an interlayer insulating material for circuit boards and three-dimensional circuit boards, a filling material for through holes and via holes, an insulating layer constituting an inductor, a coverlay, and the like.

[0066] <<For dispensers / syringes>> The composition of the present disclosure is preferably applied using a dispenser to a printed wiring board, a three-dimensional circuit board, etc. Application of the composition using a dispenser is carried out by filling a syringe with the composition of the present disclosure, attaching the syringe to the dispenser, and applying the composition to a desired location while adjusting the amount of the composition discharged.

[0067] In other words, the composition of the present disclosure is preferably a composition for syringe application (curable resin composition for syringe application).

[0068] The composition for syringe application or the composition for dispenser application according to the present disclosure can be suitably used for fine application using a nozzle having an inner diameter of 100 μm or less, 80 μm or less, or 50 μm or less.

[0069] <<Dry film>> The composition of the present disclosure can be applied to a dry film. The dry film has a resin layer obtained by applying the composition of the present disclosure to at least one surface of a first film (substrate film) and then drying it. The dry film is used by laminating the resin layer so as to be in contact with the substrate.

[0070] The dry film can be produced by uniformly applying the composition onto a first film by an appropriate method such as a blade coater, lip coater, comma coater, or film coater, and drying to form the above-mentioned resin layer. The dry film is preferably produced by laminating a second film (protective film) onto the resin layer. The first film and the second film may be made of the same film material or different film materials.

[0071] The film materials for the first film and the second film may be any of those known to be used for dry films.

[0072] As the first film, for example, a thermoplastic film such as a polyester film made of polyethylene terephthalate or the like having a thickness of 2 to 150 μm is used.

[0073] The second film may be a polyethylene film, a polypropylene film, or the like, but it is preferable that the adhesive strength with the resin layer is smaller than that of the first film.

[0074] The thickness of the resin layer on the first film is preferably 100 μm or less, and more preferably in the range of 5 to 50 μm.

[0075] <<Cured product>> A cured product can be obtained by curing the resin layer of the composition or dry film of the present disclosure. When a composition is used, the composition is applied to a desired object, dried, and heated at a temperature of 100°C or more and 150°C or less to obtain a cured product. The heating time can be set appropriately, for example, 5 minutes or more and 180 minutes or less. When a dry film is used, the resin layer obtained by laminating the dry film on a desired object is heated at a temperature of 100°C or more and 150°C or less to obtain a cured product. The heating time can be set appropriately, for example, 5 minutes or more and 180 minutes or less.

[0076] The cured product can be used for circuit boards, adhesives, paints, printing inks, coating materials, molding materials, pattern forming materials, building materials, optical parts, semiconductor devices, display devices, etc.

[0077] <<Three-dimensional circuit board>> As described above, the composition of the present disclosure can be suitably used for three-dimensional circuit boards (circuit boards whose coated surface has a three-dimensional structure). The three-dimensional structure includes polyhedrons and spheres.

[0078] As electronic devices such as mobile phones and copiers become smaller and more multifunctional, there is a demand for compactly accommodating circuit boards in their housings, and three-dimensional circuit boards are attracting attention. These three-dimensional circuit boards have conductor circuits formed directly on the inner or outer surfaces of three-dimensional housings or electronic components with a three-dimensional structure, and are superior in terms of space efficiency, improved design, and a reduction in the number of parts by integrating parts and circuits. In particular, a method of forming circuits directly on a three-dimensional substrate molded into a three-dimensional structure, known as a molded interconnect device (MID), has attracted attention.

[0079] Here, from the viewpoint of mechanical properties and heat resistance, the materials used for the three-dimensional substrate include polyphenylene sulfide, polyether ether ketone, polycarbonate, polyamide, and engineering plastics (also simply called "engineering plastics") such as polyacetal, polybutylene terephthalate, and ABS resin.

[0080] On the other hand, when mounting components on a circuit board such as a three-dimensional circuit board, a solder paste or the like is applied to the connection points of the circuit conductors, and then the electronic components are placed on the circuit board and electrically connected to the electronic components by performing a reflow process. During this reflow process, mounting defects may occur, such as the molten solder paste adhering to unexpected locations. For this reason, circuit boards are generally permanently protected with an insulating film such as a solder resist to prevent the solder paste from adhering to the circuit conductors other than the mounting area.

[0081] In addition, in three-dimensional circuit boards and the like, the above-mentioned form of forming a solder dam is also preferably applied. The specific pattern of the solder dam is not particularly limited, and it can be an appropriate pattern such as a groove-shaped dam or a protruding dam. The width and depth (height) of the dam can also be appropriately changed depending on the solder used, the melting conditions, and the like.

[0082] The composition according to the present disclosure is suitable for use in producing a solder resist or a solder dam for such a three-dimensional circuit board. More specifically, for example, the composition can be applied along the surface of a three-dimensional circuit board using the above-mentioned dispenser or the like, and then cured to produce a solder resist for the three-dimensional circuit board.

[0083] Such a three-dimensional circuit board is made of a resin molded product, and it is preferable to use a thermoplastic resin that is light in mass and easy to mold. In particular, when the components of the three-dimensional circuit board are mounted by soldering, fluororesins having excellent heat resistance called engineering plastics, polycarbonate, polyacetal, polyamide, polyphenylene ether, amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, liquid crystal polymer, polybutylene terephthalate, and ABS resin are suitable. Furthermore, since the composition of the present disclosure has particularly excellent adhesion to polyetheretherketone substrates, polyetheretherketone can be preferably used.

[0084] In the case of a three-dimensional circuit board, a method for forming a circuit on the surface of the three-dimensional board can be a known method, and can be appropriately selected according to the purpose. For example, a non-conductive metal complex is dispersed in a molding resin, which is the material of the three-dimensional board, and the three-dimensional board is molded using this molding resin. After that, a laser beam is irradiated in accordance with the circuit pattern to generate metal cores, and then plating is performed to form a circuit on the surface of the three-dimensional circuit board.

[0085] The non-conductive metal complex is not particularly limited, but a non-conductive metal complex capable of precipitating a metal by light irradiation can be preferably used. Examples of the central metal of such a non-conductive metal complex include copper (Cu), nickel (Ni), palladium (Pd), silver (Ag), gold (Au), platinum (Pt), tin (Sn), iron (Fe), cobalt (Co), chromium (Cr), rhodium (Rh), and ruthenium (Ru). Examples of the ligand of the non-conductive metal complex include organic carbonyl compounds such as β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane, and β-ketocarboxylic acid esters such as ethyl acetoacetate; organic nitrogen compounds such as organic nitrogen compounds having an -N=N- bond, organic nitrogen compounds having an -C=N- and OH bond, and organic nitrogen compounds having an -N< and -OH bond; organic sulfur compounds such as organic sulfur compounds having an >C=S bond, and organic sulfur compounds having a -C-SH bond; and the like.

[0086] The light irradiation for precipitating the metal from the non-conductive metal complex is preferably a laser light. The laser light is not particularly limited as long as it can precipitate the metal by irradiating the non-conductive metal complex. The wavelength of the laser light can be, for example, 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm, and 10600 nm. EXAMPLES

[0087] The present disclosure will be described in more detail using examples, but the present disclosure is not limited to the examples.

[0088] <<Preparation of Composition>> Compositions (curable resin compositions) according to Examples 1-12 and Comparative Examples 1-3 were prepared so as to have the blending amounts shown in Table 1. Table 1 shows the solid content (parts by mass) of each raw material, excluding the organic solvent.

[0089] <<Physical Properties>> The compositions according to the examples and comparative examples were measured for viscosity at 25° C. and thixotropy index (TI) according to the following methods. The measurement results are shown in Table 1. ·25℃ viscosity The viscosity was measured at 5 rpm, 25°C, and 10 seconds using a cone-plate viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.) and a cone rotor of 1°34'×R24 in accordance with JIS Z 8803:2011, Clause 10, "Method of viscosity measurement using a cone-plate rotational viscometer." -Thixitropy Index (TI) In accordance with JIS Z 8803:2011, Section 10 "Method of viscosity measurement using a cone-plate type rotational viscometer," a cone-plate viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.) and a cone rotor of 1°34'×R24 were used to measure the viscosity at 5 rpm, 25°C, and 10 seconds (referred to as the viscosity at 5 rpm) and the viscosity at 50 rpm, 25°C, and 10 seconds (referred to as the viscosity at 50 rpm). The thixotropy index (TI) was calculated using the following formula.

number

[0090] <<Evaluation>> Furthermore, the compositions according to each of the Examples and Comparative Examples were evaluated for adhesion, bleed-out, and coatability according to the following evaluation methods. The evaluation results are shown in Table 1.

[0091] <Applicability> The compositions (curable resin compositions) according to Examples 1-12 and Comparative Examples 1-3 were dispensed with an air dispenser (ML-808GX, manufactured by Musashi Engineering Co., Ltd.) and a nozzle (FN-0.04ND, manufactured by Musashi Engineering Co., Ltd.) with an inner diameter of 40 μm was attached to a syringe, and a line of 50 mm in length was formed on a PEEK substrate (TECACOMP PEEK LDS black 1047045, manufactured by Ensinger Co., Ltd.) with a size of 80 mm × 50 mm and a thickness of 2 mm at a discharge pressure of 100 kPa and a speed of 15 mm / sec., and then dried at 80 ° C. for 30 minutes, and then heated at 150 ° C. for 30 minutes to harden, thereby obtaining each evaluation substrate. The width of the formed line was measured at a measurement magnification of 100 times using a digital microscope (VHX-5000, manufactured by Keyence Co., Ltd.). The measured line width was evaluated according to the following criteria to evaluate the coatability. A: The line width was 150 μm or less. ×: The line width was more than 150 μm, or it was impossible to form a line.

[0092] <Bleed out> The width of the exudation of each of the evaluation substrates obtained above was measured at a measurement magnification of 100 times using a digital microscope (Keyence Corporation, VHX-5000). The measured width of the exudation was evaluated according to the following criteria. ◯: The width of the bleeding is within 5% of the line width. △: The width of the bleeding is more than 5% and 10% or less of the line width. ×: The width of the bleeding exceeds 10% of the line width.

[0093] <Adhesion> The compositions (curable resin compositions) according to Examples 1-12 and Comparative Examples 1-3 are applied to the entire surface of a PEEK substrate (TECACOMP PEEK LDS black 1047045, manufactured by Ensinger) measuring 80 mm x 50 mm and 2 mm in thickness by screen printing so that the film thickness after drying is 20 μm, and the composition is dried at 80° C. for 30 minutes, and then heated at 150° C. for 30 minutes to prepare a resin cured layer (cured coating). The surface of the cured coating is cut with a cutter knife to a thickness of 1 mm. 2After forming a grid so that there were 100 squares, a 18 mm wide cellophane tape (CT-405AP-18, manufactured by Nichiban Co., Ltd., adhesive strength of 10±1 N per 25 mm width) was applied, and the cellophane tape was firmly rubbed with a fingertip. The cellophane tape was applied and within 5 minutes, the edge of the cellophane tape was grasped at an angle close to 60° and instantly peeled off, and the number of grids remaining on the substrate (number of remaining grids) was counted to evaluate the adhesion between the substrate and the cured coating. The evaluation criteria were as follows. 〇: Remaining grid count is 90 or more △: Number of remaining lattices is 70 or more but less than 90 ×: Less than 70 remaining lattices

[0094] [Table 1]

[0095] *1 EPICLON N-695, novolac epoxy resin, manufactured by DIC Corporation *2 DIC Corporation, EPICLON N-770, phenol novolac type epoxy resin, epoxy equivalent 183-193 *3 Mitsubishi Chemical Corporation, jER834, liquid epoxy resin *4 EOCN-104S, novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd. *5 B-3000 polybutadiene resin, manufactured by Nippon Soda Co., Ltd. *6 Daicel Corporation, PB3600, epoxy polybutadiene *7 Daicel Corporation, PB4700, epoxy polybutadiene, Mn: 2000-3500 *8 Nippon Soda Co., Ltd., JP-200, epoxy polybutadiene, Mn:2200 *9 Sakai Chemical Industry Co., Ltd., BARIACE B-30, barium sulfate, filler *10 Tatsumori Co., Ltd., CRS-1103WX, fused silica, filler *11 Shikoku Chemical Industry Co., Ltd., Curesol 2E4MZ, imidazole-based curing agent *12 Mitsubishi Chemical Corporation, MA-100, carbon black, black colorant *13 Pigment Yellow, colorant, manufactured by Nikko Vicks Co., Ltd. *14 Copper phthalocyanine blue, colorant, manufactured by Nikko Vicks Co., Ltd. *15 Shin-Etsu Chemical Co., Ltd., KS-66, silicone defoamer *16 BYK, DISPERBYK-111, wetting and dispersing agent *17 Meiwa Kasei Co., Ltd., HF-1M, phenolic resin *18 Dow Chemical Company's Jukisol CA (Carbitol acetate)

Claims

1. A composition comprising an epoxy resin, a polybutadiene resin, a filler, and a curing agent, The polybutadiene resin is present in an amount of from 1% by mass to 10% by mass, based on a total solids content of the composition.

2. 2. The composition according to claim 1, having a viscosity of 100 dPa·s or more and 500 dPa·s or less, measured at 5 rpm and 25° C. using a cone-plate viscometer, and a thixotropy index of 1.0 or more and 1.6 or less.

3. The epoxy resin includes a liquid epoxy resin, 2. The composition according to claim 1, wherein a ratio of a solid content of the liquid epoxy resin to a total amount of a solid content of the epoxy resin and a solid content of the polybutadiene resin in the composition ([amount of liquid epoxy resin] / [amount of epoxy resin+amount of polybutadiene resin]×100) is 45 mass% or less.

4. The composition according to claim 1 , wherein the content of organic solvent in the composition is less than 25% by weight.

5. The composition of claim 1 , wherein the polybutadiene resin comprises an epoxidized polybutadiene resin.

6. The composition according to any one of claims 1 to 5, which is used for forming a solder resist.

7. The composition according to any one of claims 1 to 5, which is used for forming a solder resist in a three-dimensional circuit board.

8. The composition according to any one of claims 1 to 5, which is for syringe application.

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