Thermosetting resin composition

Abstract

A thermosetting resin composition for a resin molded body whose surface can be plated, the thermosetting resin composition comprising component (A): a thermosetting resin and component (B): core-shell type elastomer particles.

Description

Technical Field

[0001] The invention relates to a thermosetting resin composition. Background Art

[0002] As a technology for improving the adhesion between a thermosetting resin molded body and a plated film, there is a technology disclosed in Patent Document 1 (Japanese Patent Publication No. 2018-58960). In Patent Document 1, a sealing resin composition containing an epoxy resin, a phenol compound, and an aromatic monocarboxylic acid having a specific electron-withdrawing functional group is disclosed, and a sealing material made from the composition is disclosed that can have high adhesion with a plated lead frame at high temperature.

[0003] In addition, as a document disclosing a method for plating plastics, Patent Document 2 (Japanese Patent Publication No. 5-59587) can be cited. Patent Document 2 discloses that calcium carbonate microparticles with a particle size of 10 μ or less are mixed into a resin that is difficult to plate, such as a polyethylene resin or a polypropylene resin, and then molded, and then the molded product is treated using a common plating process for ABS resin including a chemical etching process, thereby making it possible to directly use a common plating process and equipment for ABS resin to adhere a plating layer to a polyethylene resin, a polypropylene resin, etc. that is difficult to plate.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2018-58960

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 5-59587 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] The inventors of the present invention have studied the techniques disclosed in the above-mentioned patent documents and have found that there is still room for improvement in terms of improving the adhesion between a resin molded body and a plating film when a surface of a resin molded body is plated.

[0010] Means for solving technical problems

[0011] According to the present invention, a thermosetting resin composition is provided for a resin molded body whose surface can be plated. The thermosetting resin composition is characterized in that it contains the following components (A) and (B): (A) a thermosetting resin; and (B) core-shell elastomer particles.

[0012] According to the present invention, there is provided a molded body comprising: a cured product of the thermosetting resin composition of the present invention; and a plating layer provided in contact with a surface of the cured product.

[0013] Effects of the Invention

[0014] According to the present invention, it is possible to improve the adhesion between a resin molded body and a plating film when a plating treatment is applied to the surface of the resin molded body. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a cross-sectional view showing a structural example of a molded body in the embodiment. DETAILED DESCRIPTION

[0016] Hereinafter, the embodiments of the present invention will be described using the accompanying drawings. In addition, in all the drawings, the same reference numerals are used for the same components, and the description is appropriately omitted. In addition, unless otherwise specified, the "~" of the numerical range means from above the lower limit to below the upper limit, and the values ​​at both ends are included. In addition, in the present embodiment, the composition may contain each component alone or in combination of two or more components.

[0017] (Thermosetting resin composition)

[0018] A thermosetting resin composition (hereinafter also appropriately referred to as "resin composition") is used for a resin molded body whose surface can be plated, and the thermosetting resin composition comprises the following components (A) and (B): (A) a thermosetting resin; and (B) core-shell elastomer particles.

[0019] In the present embodiment, the resin composition is specifically a thermosetting resin composition.

[0020] Hereinafter, the constituent components of the resin composition will be described with reference to specific examples.

[0021] (ingredient (A))

[0022] Component (A) is a thermosetting resin.

[0023] Component (A) may be any component that can be used for molding materials. Specific examples of component (A) include phenolic resins, epoxy resins, urea-formaldehyde (urea) resins, melamine resins and other resins having a triazine ring, bismaleimide resins, unsaturated polyester resins, polyurethane resins, diallyl phthalate resins, silicone resins, cyanate resins, polyimide resins, polyamide-imide resins, benzocyclobutene resins, resins having a benzoxazine ring, polyvinyl butyral resins and polyvinyl acetate resins.

[0024] More specifically, component (A) contains one or more selected from epoxy resins and phenolic resins, preferably contains phenolic resins, more preferably phenolic resins, or epoxy resins and phenolic resins. Furthermore, the resin composition is preferably a phenolic resin composition.

[0025] (Phenolic resin)

[0026] As the phenolic resin, for example, there can be mentioned phenolic novolac resins represented by phenol novolac resins and cresol novolac resins, which are obtained by condensing or co-condensing phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, α-naphthol, β-naphthol, dihydroxynaphthalene and the like with formaldehyde or ketones in the presence of an acidic catalyst; phenolic aralkyl resins having a phenylene skeleton synthesized from the above phenols and dimethoxy-p-xylene or bis(methoxymethyl)biphenyl; phenolic aralkyl resins such as phenolic aralkyl resins having a biphenylene skeleton; and phenolic resins having a triphenylmethane skeleton.

[0027] The phenolic resin preferably contains one or more selected from the group consisting of resol-type phenolic resins and novolac-type phenolic resins.

[0028] From the viewpoint of improving the adhesion with the plating film formed on the surface of the resin molded body, the component (A) more preferably contains a resol type phenolic resin and a novolac type phenolic resin, and even more preferably a resol type phenolic resin and a novolac type phenolic resin.

[0029] Among them, since component (A) contains a resol-type phenolic resin, the adhesion with the plating film formed on the surface of the resin molded body can be improved, and the crosslinking density of the resin molded body can be appropriately increased, thereby improving the toughness of the resin molded body and improving the mechanical strength. In addition, since the crosslinking density can be appropriately increased as described above, the dimensional change of the resin molded body due to water absorption / moisture absorption can be effectively suppressed.

[0030] The resol type phenolic resin can be obtained, for example, by reacting phenols and aldehydes in the presence of a basic catalyst, usually at a molar ratio of aldehydes to phenols (aldehydes / phenols) of 1.3 to 1.7.

[0031] Examples of the phenols used in the production of the resol-type phenolic resin include one or more phenol compounds selected from phenol, o-cresol, m-cresol, p-cresol, xylenol, alkylphenols, catechol, and resorcinol.

[0032] Examples of aldehydes used in the production of the resol-type phenolic resin include aldehyde compounds such as formaldehyde, paraformaldehyde, and benzaldehyde, and substances that are sources of these aldehyde compounds or solutions of these aldehyde compounds.

[0033] When component (A) contains a resol-type phenolic resin, from the viewpoint of improving the heat resistance of the resin molded body and suppressing the dimensional change of the resin molded body by water absorption / moisture absorption, the content of the resol-type phenolic resin relative to the entire component (A) contained in the resin composition exceeds 0% by mass, preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and further preferably 75% by mass or more.

[0034] In addition, from the viewpoint of suppressing the dimensional change of the resin molded body due to heating, the content of the resol-type phenolic resin is 100% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, and even more preferably 80% by mass or less, relative to the total amount of component (A) contained in the resin composition.

[0035] Furthermore, when the component (A) contains a novolac-type phenolic resin, adhesion with a plating film formed on the surface of the resin molded body can be improved, and the mechanical strength of the resin molded body can be improved.

[0036] Examples of the novolac-type phenolic resin include phenol novolac resins, cresol novolac resins, and bisphenol novolac resins.

[0037] From the viewpoint of improving the adhesion with the plating film formed on the surface of the resin molded body and improving the mechanical strength of the resin molded body, the novolac-type phenolic resin preferably contains one or more resins selected from the group consisting of a resin represented by the following general formula (1) and a resin represented by the following general formula (2).

[0038]

[0039] (In the above general formula (1), R 1 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 10 carbon atoms, or an aryl group or a substituted aryl group having 6 to 10 carbon atoms, and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 10 carbon atoms, or an aryl group or substituted aryl group having 6 to 10 carbon atoms, and 1 is a number of 1 to 10.)

[0040] The resin represented by the general formula (1) can be appropriately selected from resins obtained by reacting phenols and aldehydes in the absence of a catalyst or in the presence of an acidic catalyst, depending on the application. More specifically, as the resin represented by the general formula (1), a phenolic resin of a random novolac type or a high-ortho-novolac type can be used.

[0041] The novolac-type phenol resin can be generally obtained by controlling the molar ratio of aldehydes to phenols (aldehydes / phenols) to be 0.7 to 0.9 and then reacting them.

[0042] Specific examples of the phenols used in the preparation of the resin represented by the general formula (1) include phenol, o-cresol, m-cresol, p-cresol, xylenol, alkylphenols, catechol, and resorcinol.

[0043] Examples of aldehydes used in the preparation of the resin represented by the general formula (1) include aldehyde compounds such as formaldehyde, paraformaldehyde, and benzaldehyde, and substances serving as sources of these aldehyde compounds or solutions of these aldehyde compounds.

[0044]

[0045] (In the above general formula (2), R 1 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 10 carbon atoms, or an aryl group or a substituted aryl group having 6 to 10 carbon atoms, and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 10 carbon atoms, or an aryl group or substituted aryl group having 6 to 10 carbon atoms, the group X is a divalent group selected from the groups represented by the following general formulae (3) to (5), m is a number of 1 to 10, and n is a number of 1 to 10.)

[0046]

[0047] (In the above general formulas (3) to (5), R 3 Each of them is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 1 to 10 carbon atoms.)

[0048] When giving a specific example of the method for preparing the resin represented by the general formula (2), the following are the corresponding R 3 The benzene-modified phenolic resin in which all the atoms are hydrogen atoms can be prepared, for example, by reacting p-xylene dimethyl ether and phenols in the presence of an acidic catalyst. 3 In the case of a substituted benzene-modified phenolic resin having an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 1 to 10 carbon atoms, it can be prepared by first reacting the substituted benzene with an aldehyde in the presence of an acidic catalyst, and reacting the obtained polymer with phenols, or phenols and aldehydes in the presence of an acidic catalyst.

[0049] Thereby, the structural unit derived from benzene or substituted benzene can be included in the repeating unit of the novolac-type phenol resin.

[0050] In general formula (2), no terminal structural unit is shown, but as the structural unit, both a structural unit derived from phenols and a structural unit derived from benzene or substituted benzene can be used.

[0051] Furthermore, the modification rate of the resin represented by the general formula (2) can be defined by the ratio of n to the sum of m and n in the general formula (2), that is, the value of (n / (m+n)). The modification rate can be appropriately adjusted according to the intended use, but when a resin molded body is prepared from the resin composition, from the viewpoint of controlling the crosslinking density to be appropriate, it is, for example, 0.15 or more, preferably 0.20 or more, and, for example, 0.60 or less, preferably 0.50 or less.

[0052] Specific examples of phenols used in preparing the resin represented by general formula (2) include phenol, o-cresol, m-cresol, p-cresol, xylenol, alkylphenols, catechol, resorcinol, etc. These phenols may be used alone or in combination of two or more.

[0053] As aldehydes used in preparing the resin represented by general formula (2), for example, aldehyde compounds such as formaldehyde, paraformaldehyde, benzaldehyde, and substances serving as sources of these aldehyde compounds or solutions of these aldehyde compounds can be used. In addition, these aldehydes can be used alone or in combination of two or more.

[0054] Examples of substituted benzenes used in the preparation of the resin represented by the general formula (2) include toluene, xylene, mesitylene, and cyclohexylbenzene.

[0055] When preparing the resin represented by the general formula (2), it is preferred to use benzene or toluene or xylene among the above-mentioned substituted benzenes, and to use R as the phenol from the viewpoint of high availability. 1 A benzene-modified novolac phenolic resin, a toluene-modified novolac phenolic resin or a xylene-modified novolac phenolic resin is prepared by using a phenol whose groups are all hydrogen atoms, and the resin is used as the resin represented by the general formula (2).

[0056] When component (A) contains a novolac-type phenolic resin, from the viewpoint of achieving excellent processability of a resin molded body, the content of the novolac-type phenolic resin relative to the entire component (A) contained in the resin composition exceeds 0% by mass, preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably 20% by mass or more.

[0057] In addition, from the viewpoint of improving the mechanical strength of the resin molded body, the content of the novolac-type phenolic resin is 100% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, further preferably 30% by mass or less, and further preferably 20% by mass or less, relative to the total amount of component (A) contained in the resin composition.

[0058] (Epoxy resin)

[0059] The epoxy resin refers to any monomer, oligomer, or polymer having two or more epoxy groups in one molecule, and the molecular weight and molecular structure thereof are not limited.

[0060] Examples of the epoxy resin include bifunctional or crystalline epoxy resins such as biphenyl epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, stilbene epoxy resins, and hydroquinone epoxy resins; novolac epoxy resins such as cresol novolac epoxy resins, phenol novolac epoxy resins, and naphthol novolac epoxy resins; phenol aralkyl epoxy resins such as phenylene skeleton-containing phenol aralkyl epoxy resins, biphenylene skeleton-containing phenol aralkyl epoxy resins, and phenylene skeleton-containing naphthol aralkyl epoxy resins; trifunctional epoxy resins such as trisphenol methane epoxy resins and alkyl-modified trisphenol methane epoxy resins; modified novolac epoxy resins such as dicyclopentadiene-modified novolac epoxy resins and terpene-modified novolac epoxy resins; and epoxy resins containing heterocycles such as triazine core-containing epoxy resins.

[0061] The epoxy resin preferably includes a novolac type epoxy resin, and more preferably includes a cresol novolac type epoxy resin.

[0062] In addition, resin combination can include epoxy resin and curing agent. As curing agent, phenolic resin curing agent, amine curing agent, acid anhydride curing agent, thiol curing agent etc. can be enumerated. Among these, from the balanced viewpoint of flame retardancy, moisture resistance, electrical characteristics, curability, storage stability etc., preferably phenolic resin curing agent. And, the curing agent combination of multiple systems can be used.

[0063] Specific examples of the phenolic resin curing agent include the various phenolic resins described above.

[0064] From the viewpoint of improving the curing characteristics of the resin composition, the content of component (A) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the entire resin composition.

[0065] In addition, from the viewpoint of improving the adhesion with the plating film formed on the surface of the resin molded body, the content of component (A) in the resin composition can be, for example, 99 mass % or less, preferably 90 mass % or less, more preferably 80 mass % or less, further preferably 70 mass % or less, further preferably 60 mass % or less, and further preferably 50 mass % or less, relative to the resin composition as a whole.

[0066] (Component (B))

[0067] Component (B) is core-shell type elastomer particles.

[0068] By making the resin composition contain the component (A) and the component (B), a resin molded body excellent in adhesion to the plating film can be obtained stably.

[0069] The component (B) is preferably a component soluble in an acid.

[0070] Furthermore, the component (B) is, for example, a graft copolymer having a core-shell structure, and more specifically, is composed of a rubbery polymer constituting a core and a graft chain constituting a shell.

[0071] Examples of the material of the core of the component (B) include rubber-like polymers.

[0072] From the perspective of improving the adhesion with the plating film formed on the surface of the resin molded body, the core material preferably includes butadiene (co)polymers such as polybutadiene (butadiene rubber), styrene-butadiene copolymer (styrene-butadiene rubber: SBR), methyl methacrylate-butadiene-styrene copolymer (MBS), and acrylonitrile-butadiene copolymer (nitrile rubber).

[0073] In addition, as the material of the core, in addition to these, there can be mentioned polyisoprene (isoprene rubber), polychloroprene (chloroprene rubber), alkyl acrylate copolymer (acrylate rubber), ethylene-acrylate copolymer (ethylene-acrylate rubber), ethylene-propylene copolymer (ethylene-propylene rubber), epichlorohydrin (co)polymer (epichlorohydrin rubber), organosiloxane (co)polymer (silicone rubber), fluororubber, natural rubber and materials obtained by adding hydrogen to the unsaturated bonds thereof or partially adding hydrogen.

[0074] Furthermore, from the viewpoint of improving the adhesion between the resin molded body and the plating film, the material of the core preferably contains one or more selected from the group consisting of MBS polymers, SBR polymers, and acrylic ester polymers.

[0075] The material of the shell of component (B) preferably includes, for example, a (co)polymer having a structure derived from one or more monomers selected from aromatic vinyl monomers, (meth)acrylate monomers, and halogenated vinyl monomers.

[0076] Examples of the aromatic vinyl monomer include styrene compounds such as styrene, (o-, m- or p-)methylstyrene, ethylstyrene, isobutylstyrene, tert-butylstyrene, alkoxystyrene, halogenated styrene such as bromostyrene; and naphthalene compounds such as vinylnaphthalene.

[0077] Specific examples of the (meth)acrylate monomer include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and octyl methacrylate; and alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, and octyl acrylate.

[0078] Specific examples of the halogenated vinyl monomer include vinyl chloride.

[0079] In addition, from the viewpoint of improving the adhesion between the resin molded body and the plating film, the material of the shell preferably includes one or more selected from polycarbonate (PC), polybutylene terephthalate (PBT), polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA).

[0080] In addition, examples of commercially available products of component (B) include Kane Ace M series such as Kane Ace M711, Kane Ace M701, Kane Ace M577, and Kane Ace M210 (manufactured by Kaneka Corporation); Kane Ace B series such as Kane Ace B513 (manufactured by Kaneka Corporation); and Staphyloid series represented by Staphyloid AC series such as product name "Staphyloid AC-3832" (alkyl acrylate-alkyl methacrylate copolymer microparticles), product name "Staphyloid AC-3816N" (alkyl acrylate-alkyl methacrylate copolymer microparticles), and product name "Staphyloid AC-4030" (alkyl acrylate-alkyl methacrylate copolymer microparticles) (manufactured by AICA Kogyo Co., Ltd.).

[0081] From the viewpoint of improving the adhesion between the resin molded body and the plating film, the average particle size d of the component (B) is50 It is preferably 50 μm or more, more preferably 100 μm or more, and further preferably 150 μm or more, and is preferably 500 μm or less, more preferably 400 μm or less, and further preferably 300 μm or less.

[0082] Here, the average particle size d of component (B) is 50 The particle size distribution of the particles can be measured on a volume basis using a commercially available laser diffraction particle size distribution measuring device (e.g., SALD-7000 manufactured by Shimadzu Corporation). The median diameter (d 50 ) as the average particle size.

[0083] From the viewpoint of improving the adhesion between the resin molded body and the plating film, the content of component (B) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 1.5% by mass or more, and further preferably 2.5% by mass or more, relative to the resin composition as a whole.

[0084] In addition, from the viewpoint of improving the strength of the resin molded body, the content of component (B) in the resin composition is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and further preferably 4% by mass or less, relative to the entire resin composition.

[0085] In the present embodiment, the resin composition comprises components (A) and (B), and therefore, when the surface of a resin molded body composed of a cured product of the resin composition is subjected to a plating treatment, the adhesion between the resin molded body and the plated film can be effectively improved. Therefore, the resin composition of the present embodiment is suitable for obtaining a resin molded body capable of being subjected to a plating treatment on the surface.

[0086] In the present embodiment, the resin composition may contain components other than the components (A) and (B).

[0087] (Filling material)

[0088] The resin composition may further contain a filler other than the component (B). Examples of the shape of the filler other than the component (B) include fibrous and spherical particles.

[0089] Specific examples of fibrous fillers include glass fiber, carbon fiber, fibrous wollastonite and asbestos. The number average fiber diameter of the fibrous filler is, for example, 10 to 15 μm, and the number average fiber length is, for example, 20 to 5000 μm. By using such a fibrous filler, the operability when manufacturing the resin composition can be improved, and the mechanical strength of the resin molded body can be further improved.

[0090] Specific examples of the granular filler include spherical inorganic fillers, and more specifically, spherical glass such as glass beads and glass powder; silica such as spherical silica and crushed silica; kaolin; calcium carbonate; aluminum hydroxide; clay; and mica.

[0091] From the viewpoint of improving adhesion with a plating film formed on the surface of the resin molded body and improving the mechanical strength of the resin molded body, the resin composition preferably contains an inorganic filler, more preferably contains a fibrous inorganic filler, and even more preferably contains glass fiber.

[0092] From the viewpoint of improving the mechanical strength of the resin molded body, the content of the glass fiber in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and even more preferably 40% by mass or more, relative to the entire resin composition.

[0093] From the viewpoint of improving the curing characteristics of the resin composition, the content of the filler in the resin composition is preferably 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less, based on the entire resin composition.

[0094] Furthermore, the resin composition may further contain an elastomer other than component (B). Specific examples of the elastomer other than component (B) include one or more selected from butadiene rubber, butadiene-acrylonitrile copolymer, and modified polyvinyl alcohols such as alkyl acetalized polyvinyl alcohol.

[0095] In addition, the resin composition may contain various additives used in thermosetting resin molding materials. Specific examples of additives include mold release agents such as stearic acid, calcium stearate, magnesium stearate, carnauba wax, polyethylene, etc.; curing aids such as magnesium oxide, calcium hydroxide (slaked lime), etc.; colorants such as carbon black; adhesion enhancers or coupling agents for improving the bonding between the filler and the thermosetting resin; and solvents.

[0096] The content of each of these components in the resin composition is, for example, approximately 0.1 to 5% by mass with respect to the entire resin composition.

[0097] For example, as the coupling agent, specifically, one or more types of known coupling agents selected from various silane compounds such as epoxy silane, aminosilane, phenylaminosilane, alkylsilane, ureidosilane, vinylsilane, methacrylate silane, titanium compounds, aluminum chelates, aluminum / zirconium compounds, etc. can be cited.

[0098] Next, the physical properties of the resin composition or its cured product will be described.

[0099] From the viewpoint of improving the reliability of the temperature cycle of the molded body obtained by plating the surface of the resin molded body, for the cured product obtained by molding the resin composition at 175°C for 3 minutes and then curing it at 180°C for 8 hours, the linear expansion coefficient in the plane direction (XY direction, MD) in the range of 40°C to 150°C measured by thermomechanical analysis (TMA) at a heating rate of 5°C / min is preferably 5 ppm / °C or more, more preferably 8 ppm / °C or more, further preferably 10 ppm / °C or more, and can be, for example, 70 ppm / °C or less, preferably 30 ppm / °C or less, more preferably 25 ppm / °C or less, further preferably 20 ppm / °C or less, and further preferably 18 ppm / °C or less.

[0100] From the viewpoint of improving the reliability of the temperature cycle of the molded body obtained by plating the surface of the resin molded body, for the cured product obtained by molding the resin composition at 175°C for 3 minutes and then curing it at 180°C for 8 hours, the linear expansion coefficient in the thickness direction (Z direction, TD) in the range of 40°C to 150°C measured by thermomechanical analysis (TMA) at a heating rate of 5°C / min is preferably 5 ppm / °C or more, more preferably 10 ppm / °C or more, further preferably 15 ppm / °C or more, further preferably 20 ppm / °C or more, and for example can be 70 ppm / °C or less, preferably 35 ppm / °C or less, more preferably 30 ppm / °C or less, and further preferably 25 ppm / °C or less.

[0101] In addition, when the resin composition is molded at 175° C. for 3 minutes and then cured at 180° C. for 8 hours to obtain a cured product as a test piece and the strength when the test piece is broken by a method based on JIS K 6911 is taken as the bending strength, the bending strength of the cured product is preferably 140 MPa or more, preferably 170 MPa or more. With such a bending strength, the adhesion with the plated film can be further improved, and the mechanical strength of the resin molded body can be further improved.

[0102] In addition, when the cured product obtained by molding the resin composition at 175°C for 3 minutes and then curing it at 180°C for 8 hours is used as a test piece, and the strength when the test piece is broken by a method based on JIS K 6911 is used as the bending strength, the bending modulus of the cured product obtained from the slope in the elastic domain of the stress-strain curve is preferably 10.0 GPa or more, preferably 18.0 GPa or more. If it is such a bending modulus of elasticity, the adhesion with the plated film can be further improved, and the mechanical strength of the resin molded body can be further improved.

[0103] About the manufacture method of resin combination, for example, can be by utilizing known method by mixing above-mentioned each component, further utilize roller, kneading machine or extruder etc. to carry out melt mixing, and obtain by the method for pulverizing after cooling.In addition, according to need, can obtain granular resin combination with ingot (tablet) shape after pulverizing in the above-mentioned method.In addition, can obtain sheet-like resin combination by vacuum lamination molding or compression molding after pulverizing in the above-mentioned method, for example.In addition, can appropriately adjust the dispersity or fluidity etc. of the resin combination obtained.

[0104] Among them, when the resin composition contains a filler, from the viewpoint of making the raw material dispersible, it is preferred to mix the component (B) and the filler in advance and then mix the mixture with the component (A). More specifically, the component (B) and the filler are pre-treated and mixed using a mixer equipped with a rotary blade such as a Henschel mixer. In this case, it is more preferred to pre-treat and mix the component (B), the filler and the coupling agent.

[0105] (Resin molded body)

[0106] The resin molded body (molded article) is composed of a cured product of the above-mentioned resin composition.

[0107] Furthermore, the resin molded body can be obtained by molding the above-mentioned resin composition. The molding method is preferably transfer molding or injection molding.

[0108] The conditions at this time also depend on the thickness of the resin molded body. For example, when a molded product with a wall thickness of about 5 mm is molded by injection molding, the conditions of mold temperature of 170 to 190°C, molding pressure of 100 to 150 MPa, and curing time of 30 to 90 seconds can be adopted.

[0109] Furthermore, the obtained resin molding can be post-baked as needed, and the post-baking conditions can be appropriately selected according to the purpose. For example, the highest reaching temperature can be set to 150°C to 270°C, and the holding time can be set to 1 hour to 15 hours. More preferably, the highest reaching temperature can be set to 170°C to 240°C, and the holding time can be set to 1 hour to 10 hours. There is a trend that the higher the temperature at which the post-baking is performed, the smaller the heating dimensional change under the use environment.

[0110] Furthermore, from the viewpoint of further improving the adhesion between the resin molded body and the plating film, the resin molded body preferably has a sea-island structure, and more preferably the resin molded body has a sea-island structure, and component (B) is present in the island phase.

[0111] Among them, the sea-island structure can be confirmed by electron microscopy.

[0112] (Molding body)

[0113] The molded body comprises: a cured product of the resin composition; and a plating layer provided so as to be in contact with a surface of the cured product.

[0114] Figure 1 It is a cross-sectional view showing a structural example of a molded body in the embodiment. Figure 1 The molded body 100 shown includes: a resin molded body 101 composed of a cured product of a resin composition; and a plating layer 103 provided so as to be in contact with the surface of the resin molded body 101 .

[0115] Furthermore, the plating layer 103 may be composed of one layer or may have multiple layers, for example, Figure 1 2 shows a structure in which the plating layer 103 includes a first plating layer 105 and a second plating layer 107 from the resin molded body 101 side.

[0116] Furthermore, the plating layer 103 is preferably provided on the entire surface of the resin molded body 101 .

[0117] The plating methods of the first plating layer 105 and the second plating layer 107 may be the same or different.

[0118] Specifically, the first plating layer 105 is an electroless plating layer from the viewpoint of improving the adhesion between the resin molded body and the plating layer 103. In addition, the second plating layer 107 may be an electroless plating layer or an electrolytic plating layer.

[0119] Furthermore, the first plating layer 105 and the second plating layer 107 are specifically metal layers, and for example, these layers are independently layers containing one or more selected from Cu, Ni, Al, Fe, Au, and alloys thereof.

[0120] From the viewpoint of improving the adhesion between the resin molded body and the plating layer 103 , it is preferred that one of the first plating layer 105 and the second plating layer 107 is a Ni film and the other is a Cu film.

[0121] From the viewpoint of improving the adhesion between resin molded body 101 and plating layer 103 , resin molded body 101 preferably has a roughened layer on the bonding surface with plating layer 103 , and plating layer 103 is provided inside a recess provided in the roughened layer.

[0122] From the viewpoint of improving adhesion with the plating layer 107 and improving electromagnetic wave shielding properties, the thickness of the first plating layer 105 is preferably 0.1 μm or more, more preferably 0.3 μm or more, and preferably 5 μm or less, more preferably about 3 μm.

[0123] From the viewpoint of improving electromagnetic wave shielding properties, the thickness of the second plating layer 107 is preferably 0.5 μm or more, more preferably 1 μm or more, and is preferably 50 μm or less, more preferably 30 μm or less.

[0124] In addition, from the viewpoint of improving electromagnetic wave shielding properties, the thickness of the entire plating layer 103 is preferably 0.1 μm or more, more preferably 0.5 μm or more, and is preferably 60 μm or less, more preferably 30 μm or less.

[0125] Next, a method for producing the molded body 100 is described. The method for producing the molded body includes, for example, a step of preparing a resin molded body 101 which is a cured product of the resin composition; a step of etching the surface of the resin molded body 101 to roughen it; and a step of forming a plating layer 103 on the roughened surface.

[0126] The step of etching the surface of the resin molded body 101 to roughen it is specifically a step of etching the surface where the plated layer 103 is to be formed before the plating treatment, so as to dissolve and remove calcium carbonate present near the surface of the resin molded body 101, thereby forming a roughened layer having uneven surfaces. In addition, when the resin molded body 101 contains an elastomer dissolved in the etching solution, it is preferable to remove the elastomer present near the surface of the resin molded body 101 together with the calcium carbonate.

[0127] As an etching method, for example, acid treatment can be cited. As specific examples of the acid used in the acid treatment, chromic acid, sulfuric acid, etc. can be cited. For example, when the acid used is only chromic acid, the etching conditions can be appropriately set according to the types of components such as thermosetting resin contained in the resin molded body 101.

[0128] Furthermore, it is preferable to clean and neutralize the surface of the resin molded body 101 after the acid treatment and before forming the plating layer 103 .

[0129] In the step of forming the plating layer 103, the first plating layer 105 and the second plating layer 107 are sequentially formed using a known method according to the type of metal constituting the plating film and the plating method. For example, a seed layer is formed on the roughened surface of the resin molded body 101, and a metal film is grown with the seed layer as a base point.

[0130] In this embodiment, since the rough layer is formed on the resin molded body 101, the first plated layer 105 can be formed by filling the inside of the recessed portion provided in the rough layer with the plated film. Therefore, the plated layer 103 having excellent adhesion to the resin molded body 101 can be obtained.

[0131] Through the above process, we can obtain Figure 1 A shaped body 100 is shown.

[0132] The use of the molded article 100 obtained in this embodiment is not limited, and can be expanded to various uses, for example, it can be used for aircraft parts, automobile parts, electronic equipment parts, home appliance parts, industrial equipment parts, etc.

[0133] Among them, the molded body 100 can be suitably used for a component in which the plating layer 103 functions as a heat diffusion component or a component in which the plating layer 103 functions as an electromagnetic wave shielding layer, for example, it can be used for a component of an inverter or a component of an air conditioner.

[0134] As mentioned above, although embodiment of this invention was demonstrated, these are illustrations of this invention, and various technical schemes other than the above-mentioned can also be adopted.

[0135] [Example]

[0136] Hereinafter, the present embodiment will be described in detail with reference to Examples and Comparative Examples. In addition, the present embodiment is not limited at all by the description of these Examples.

[0137] (Example 1 to Example 6, Comparative Example 1 to Comparative Example 4)

[0138] (Preparation of resin composition)

[0139] For each embodiment and each comparative example, a sealing resin composition was prepared in the following manner. That is, a mixture obtained by mixing each component in the proportion shown in Table 1 was kneaded using heating rollers with different rotation speeds, and the material cooled in a flake form was crushed to obtain a granular molding material (thermosetting resin composition). Among them, regarding the kneading conditions of the heating rollers, the rotation speed was 20 / 14 rpm for the high speed side / low speed side, the temperature was 90 / 20°C for the high speed side / low speed side, and the kneading time was 5 to 10 minutes.

[0140] The details of each component in Table 1 are as follows. In addition, the mixing ratio of each component shown in Table 1 represents the mixing ratio (mass %) with respect to the entire resin composition.

[0141] (A) Thermosetting resin 1: Resol type phenolic resin, PR-53529 (manufactured by Sumitomo Bakelite Co., Ltd.)

[0142] (A) Thermosetting resin 2: Resol type phenolic resin, PR-51723 (manufactured by Sumitomo Bakelite Co., Ltd.)

[0143] (A) Thermosetting resin 3: Novolac type phenolic resin, A-1087 (manufactured by Sumitomo Bakelite Co., Ltd.)

[0144] (A) Thermosetting resin 4: Novolac type phenolic resin, A-1082G (manufactured by Sumitomo Bakelite Co., Ltd.)

[0145] (A) Thermosetting resin 5: o-cresol type epoxy resin, EPICLON N-670 (manufactured by DIC Corporation)

[0146] (A) Thermosetting resin 6: Novolac type phenolic resin, PR-51470 (manufactured by Sumitomo Bakelite Co., Ltd.)

[0147] Curing aid 1: slaked lime, SA074 (manufactured by Chichibu Lime Industry Co., Ltd.)

[0148] Curing aid 2: slaked lime, Ashidachi LS (manufactured by Ashidachi Lime Co., Ltd.)

[0149] Curing aid 3: 2-phenyl-4-methylimidazole, 2P4MZ (manufactured by SHIKOKU CHEMICALS CORPORATION)

[0150] Filler 1: Glass fiber, CS3E479 (manufactured by Nitto Boseki Co., Ltd.), number average fiber diameter 11 μm, number average fiber length 3 mm

[0151] Filler 2: Kaolin, ECKALITE (manufactured by IMERYS)

[0152] Filler 3: crushed silica, RD-8 (manufactured by Tatsumori Ltd.), average particle size d 50=15μm

[0153] (B) Elastomer 1: core-shell type, core: MBS polymer, Kane Ace M711 (manufactured by Kaneka Corporation), average particle size d 50 =200μm

[0154] (B) Elastomer 2: core-shell type, core: MBS polymer, Kane Ace M701 (manufactured by Kaneka Co., Ltd.), average particle size d 50 =250μm

[0155] (B) Elastomer 3: core-shell type, core: SBR polymer, shell: PVC, Kane Ace B513 (manufactured by Kaneka Co., Ltd.), average particle size d s0 =200μm

[0156] (B) Elastomer 4: core-shell type, core: acrylic ester polymer, shell: PVC, KaneAce M577 (manufactured by Kaneka Co., Ltd.), average particle size d 50 =250μm

[0157] (B) Elastomer 5: core-shell type, core: acrylic polymer, shell: PMMA, Kane Ace M210 (manufactured by Kaneka Corporation), average particle size d 50 =200μm

[0158] Elastomer 6: a mixture of butadiene-acrylonitrile copolymer and calcium carbonate, TR2250 (manufactured by JSR Corporation)

[0159] Elastomer 7: Alkyl acetalized polyvinyl alcohol, S-LEC BX-5 (manufactured by Sekisui Chemical Co., Ltd.)

[0160] Release agent 1: carnauba wax, CARNAUBA F-2 (manufactured by DAINICHI CHEMICAL INDUSTRY Co., Ltd.)

[0161] Release agent 2: montanic acid ester wax, Licolub WE-4 (manufactured by Clariant Japan)

[0162] Release agent 3: calcium stearate, CA-ST (manufactured by NITTO CHEMICAL INDUSTRY CO., LTD.)

[0163] Colorant 1: Carbon black, #750B (manufactured by Mitsubishi Chemical Corporation)

[0164] The following measurements were performed on the resin composition obtained in each example. The results are collectively shown in Table 1.

[0165] (Method for measuring physical properties of resin molded article)

[0166] (Method for measuring coefficient of linear expansion (CTE))

[0167] For the resin composition obtained in each example, a bending test piece was formed under the conditions of 175°C and 3 minutes, and then a curing treatment was performed in an oven at 180°C for 8 hours to obtain a cured test piece. TMA measurements were performed in the flow direction (plane direction or XY direction) and thickness direction (Z direction) of the obtained test piece. TMA measurements were performed at a heating rate of 5°C / min, and the average linear expansion coefficient of 40 to 150°C was taken as CTE.

[0168] (Evaluation method)

[0169] (Peel strength measurement method)

[0170] The resin composition obtained in each example was molded into a 125 mm square × 1.5 mm thick molded article at 175°C for 90 seconds to obtain a resin molded body. Thereafter, the plated film-forming surface of the resin molded body obtained by curing at 180°C for 8 hours in an oven was subjected to chromic acid etching at 65°C for 20 minutes to roughen the plated film-forming surface. The etching solution was an aqueous solution containing chromic anhydride and sulfuric acid at the following concentrations, respectively.

[0171] (Etching liquid)

[0172]

[0173] After that, a 0.1 to 3 μm Ni film is formed on the etched surface of the resin molded body by electroless Ni plating, and then a 10 to 50 μm Cu film is formed by electrolytic Cu plating. The plating width is 10 mm. The composition of the plating solution (aqueous solution) used in each plating step is shown below.

[0174] (Plating solution for electroless Ni plating)

[0175]

[0176] (Plating solution for electrolytic Cu plating)

[0177]

[0178] The strength when the plating layer is vertically peeled off from the molded body obtained by the above steps, that is, the maximum peel strength in a 90° peel test is taken as the peel strength. The strength is measured as follows.

[0179] Measurement method: After peeling one end of the copper foil to an appropriate length, install it on a support bracket, clamp the front end of the peeled copper foil with a clamp, and continuously peel about 50 mm at a speed of about 50 mm per minute in the direction perpendicular to the copper foil surface. The lowest value of the load during this period is the peel strength [N / cm].

[0180] (Measurement method of flexural strength and flexural elastic modulus)

[0181] For the resin composition obtained in each example, a bending test piece was formed under the curing conditions of 175° C. and 3 minutes based on JIS K 6911, and then cured at 180° C. for 8 hours to obtain a test piece. The strength when the test piece was broken by the method based on JIS K 6911 was taken as the bending strength. In addition, the bending modulus was calculated from the slope in the elastic domain of the stress-strain curve.

[0182]

[0183] As can be seen from Table 1, in the molded body obtained by using the resin composition in each example, the peel strength of the plated film from the resin molded body is higher than that of the molded body in the comparative example. Therefore, by using the resin composition in each example, the adhesion between the plated film and the resin molded body when the plated film is formed on the surface of the resin molded body can be improved.

[0184] Furthermore, the resin composition obtained in each example also has preferable characteristics in terms of the flexural strength, flexural modulus and linear expansion coefficient of the cured product.

[0185] This application claims priority based on Japanese patent application No. 2019-146703 filed on August 8, 2019, and all the disclosed contents are incorporated herein by reference.

[0186] Description of Reference Numerals

[0187] 100 molded body, 101 resin molded body, 103 plating layer, 105 first plating layer, 107 second plating layer.

Claims

1. A thermosetting resin composition for a resin molded body whose surface can be plated, wherein the thermosetting resin composition is in a granular form and comprises the following components (A) and (B), (A) Thermosetting resin, (B) Core-shell elastomer particles, The component (A) comprises a resol type phenolic resin and a novolac type phenolic resin, The content of the resol-type phenolic resin is 50% to 95% by mass, and the content of the novolac-type phenolic resin is 5% to 50% by mass, based on the entire component (A) contained in the thermosetting resin composition.

2. The thermosetting resin composition according to claim 1, characterized in that: The core of the component (B) comprises polybutadiene or a butadiene copolymer.

3. The thermosetting resin composition according to claim 1 or 2, characterized in that: The content of the component (B) in the thermosetting resin composition is 0.1% by mass or more and 10% by mass or less based on the entire thermosetting resin composition.

4. The thermosetting resin composition according to claim 1 or 2, characterized in that: Also contains fiberglass.

5. The thermosetting resin composition according to claim 4, characterized in that: The content of the glass fiber in the thermosetting resin composition is 10% by mass or more and 70% by mass or less based on the entire thermosetting resin composition.

6. The thermosetting resin composition according to claim 1 or 2, characterized in that: The resin molded article has a sea-island structure, and the component (B) is present in the island phase.

7. The thermosetting resin composition according to claim 1 or 2, characterized in that: For the cured product obtained by molding the thermosetting resin composition at 175°C for 3 minutes and then curing it at 180°C for 8 hours, the linear expansion coefficient in the plane direction within the range of 40°C to 150°C measured by thermomechanical analysis at a heating rate of 5°C / min is 5 ppm / °C to 25 ppm / °C.

8. The thermosetting resin composition according to claim 1 or 2, characterized in that: The thermosetting resin composition was molded at 175° C. for 3 minutes and then cured at 180° C. for 8 hours. The flexural strength of the cured product was 140 MPa or more.

9. The thermosetting resin composition according to claim 1 or 2, characterized in that: The flexural modulus of a cured product obtained by molding the thermosetting resin composition at 175° C. for 3 minutes and then curing it at 180° C. for 8 hours was 10.0 GPa or more.

10. A molded body, characterized in that: have: A cured product of the thermosetting resin composition according to any one of claims 1 to 9; and A plating layer is provided so as to be in contact with the surface of the cured product.

11. The molded body according to claim 10, characterized in that: The solidified product has a roughened layer on the bonding surface with the plated layer, The plating layer is provided inside the recessed portion provided in the roughened layer.

12. The molded body according to claim 10 or 11, characterized in that: The plating layer is a layer containing one or more selected from Cu, Ni, Al, Fe, Au and alloys thereof.

13. The molded body according to claim 10 or 11, characterized in that: The thickness of the plating layer is greater than or equal to 0.1 μm and less than or equal to 60 μm.

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