Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
  • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/387—Block-copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2421/00—Presence of unspecified rubber
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2451/00—Presence of graft polymer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2463/00—Presence of epoxy resin

Definitions

• the present disclosure relates to a curable resin composition, a curable film, and a laminated film.
• Patent Document 1 proposes an adhesive composition containing a styrene elastomer.
• the cured product formed from the adhesive composition described in Patent Document 1 does not have sufficient low dielectric properties in a high frequency region, and there is room for further improvement.
• the present disclosure has been made in view of the above circumstances, and provides a curable resin composition capable of forming a cured product having excellent low dielectric properties in a high frequency region while having adhesive properties to adherends, and a curable resin composition using the same.
• the purpose is to provide a curable film and a laminated film.
• the present disclosure provides the following curable resin composition, curable film, and laminated film.
• a curable resin composition containing (A) a rubber component, (B) a crosslinking component having an epoxy group, (C) an ester curing agent, and (D) a curing accelerator.
• a curable resin composition according to [1] above which is used to form a protective layer for covering an electric circuit.
• the curable resin composition according to [1] or [2] above, wherein the crosslinking component (B) having an epoxy group has a weight average molecular weight of 200 to 1,000.
• the content of the above (D) curing accelerator is based on 100 parts by mass of the above (A) rubber component, the above (B) crosslinking component having an epoxy group, and the above (C) ester curing agent.
• a curable film comprising the curable resin composition according to any one of [1] to [4] above.
• a laminated film comprising a base film and the curable film according to [5] above, provided on the base film.
• a curable resin composition capable of forming a cured product having excellent low dielectric properties in a high frequency region while having adhesiveness to an adherend, a curable film using the same, and a laminated film can be provided.
• a numerical range indicated using "-" indicates a range that includes the numerical values written before and after "-" as the minimum and maximum values, respectively.
• the upper limit or lower limit of the numerical range of one step may be replaced with the upper limit or lower limit of the numerical range of another step.
• the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples.
• Solid content refers to nonvolatile content excluding volatile substances (water, solvent, etc.) in the resin composition. That is, the “solid content” refers to components other than the solvent that remain without being volatilized during drying of the resin composition described below, and also includes components that are liquid, starch syrup-like, or wax-like at room temperature (25° C.).
• (meth)acrylic acid means “acrylic acid” and “methacrylic acid” corresponding thereto, and the same applies to other similar words.
• the curable resin composition according to the present embodiment contains (A) a rubber component, (B) a crosslinking component having an epoxy group, (C) an ester curing agent, and (D) a curing accelerator. .
• the curable resin composition may contain (E) filler as necessary.
• the curable resin composition according to this embodiment can be used for forming a protective layer (coverlay) covering an electric circuit in a printed wiring board, as an interlayer adhesive in a multilayer printed wiring board, and the like. According to the curable resin composition according to the present embodiment, it has adhesive properties with materials constituting the printed wiring board such as the metal part of the printed wiring board, the base material, etc., and can be used in a high frequency region.
• the curable resin composition according to the present embodiment contains the (A) rubber component, the cured product thereof can have elasticity. Therefore, the curable resin composition according to this embodiment can be suitably used, for example, for forming a protective layer of a flexible printed wiring board and as an interlayer adhesive.
• Each component that can be included in the curable resin composition will be explained below.
• the rubber component is, for example, acrylic rubber, isoprene rubber, butyl rubber, styrene butadiene rubber, butadiene rubber, styrene butylene styrene rubber, styrene ethylene propylene styrene rubber, styrene ethylene butylene styrene rubber, acrylonitrile butadiene rubber, silicone rubber, urethane rubber. , chloroprene rubber, ethylene propylene rubber, fluororubber, sulfurized rubber, epichlorohydrin rubber, and chlorinated butyl rubber.
• a rubber component with low gas permeability may be used from the viewpoint of reducing the influence of moisture absorption on insulation reliability, connection reliability, and damage to wiring.
• the rubber component (A) may include at least one selected from styrene-butadiene rubber, butadiene rubber, styrene-ethylene-butylene-styrene rubber, and butyl rubber.
• the rubber component may include styrene ethylene butylene styrene rubber.
• acrylic rubbers examples include Nipol AR series by Nippon Zeon Co., Ltd. and Clarity series by Kuraray Co., Ltd.
• Examples of commercially available isoprene rubber include Nipol IR series manufactured by Nippon Zeon Co., Ltd.
• butadiene rubber Commercial products of butadiene rubber include, for example, Nipol BR series manufactured by Nippon Zeon Co., Ltd.
• Examples of commercial products of acrylonitrile butadiene rubber include ENEOS Materials Co., Ltd.'s "NBR Series” (formerly JSR Corporation's “JSR NBR Series”).
• silicone rubber examples include Shin-Etsu Silicone Co., Ltd.'s "KMP Series.”
• Examples of commercially available ethylene propylene rubber include ENEOS Materials Co., Ltd.'s "EP Series” (formerly JSR Corporation's “JSR EP Series”).
• fluororubber products examples include Daikin Corporation's "Daiel Series” and the like.
• epichlorohydrin rubber examples include Nippon Zeon Co., Ltd.'s "Hydrin Series.”
• the rubber component can also be produced by synthesis.
• acrylic rubber can be obtained by reacting (meth)acrylic acid, (meth)acrylic acid ester, aromatic vinyl compound, vinyl cyanide compound, etc.
• the rubber component may include rubber having a crosslinking group.
• the crosslinking group may be any reactive group that can proceed with the reaction of crosslinking the molecular chains of the rubber component (A). Examples include reactive groups, acid anhydride groups, amino groups, hydroxyl groups, epoxy groups, and carboxy groups possessed by the crosslinking component (B) described below.
• the rubber component (A) may include a rubber having at least one crosslinking group selected from acid anhydride groups and carboxy groups.
• Examples of rubbers having acid anhydride groups include rubbers partially modified with maleic anhydride. Rubbers partially modified with maleic anhydride are polymers containing structural units derived from maleic anhydride.
• the rubber component may include rubber partially modified with maleic anhydride.
• a commercially available rubber partially modified with maleic anhydride includes, for example, the styrene elastomer "Tuffrene 912" manufactured by Asahi Kasei Corporation.
• the rubber partially modified with maleic anhydride may be a hydrogenated styrenic elastomer partially modified with maleic anhydride.
• Hydrogenated styrene elastomers can also be expected to improve connection reliability, insulation reliability, and weather resistance.
• a hydrogenated styrenic elastomer is an elastomer obtained by adding hydrogen to the unsaturated double bonds of a styrenic elastomer having a soft segment containing an unsaturated double bond.
• Examples of commercially available hydrogenated styrenic elastomers partially modified with maleic anhydride include “FG1901” and “FG1924GT” manufactured by Clayton Polymer Japan Co., Ltd., and “Tuftec M1911” and “Tuftec M1913” manufactured by Asahi Kasei Corporation. ” and “Tuftec M1943.”
• the hydrogenated styrenic elastomer partially modified with maleic anhydride may be a hydrogenated styrene ethylene butylene styrene elastomer partially modified with maleic anhydride.
• the weight average molecular weight of the rubber component (A) may be 20,000 to 200,000, 30,000 to 150,000, or 50,000 to 125,000 from the viewpoint of coating properties and circuit embedding properties.
• the weight average molecular weight (Mw) here means a standard polystyrene equivalent value determined by gel permeation chromatography (GPC).
• the content of (A) rubber component is 60 to 95% by mass based on the total amount of (A) rubber component, (B) crosslinking component, and (C) ester curing agent. It is preferably 65 to 90% by mass, and even more preferably 70 to 85% by mass.
• (A) When the content of the rubber component is 60% by mass or more, the rubber component and the crosslinking component tend to mix well. When the content of the rubber component (A) is 95% by mass or less, the resulting cured product tends to have particularly excellent properties in terms of adhesiveness, connection reliability, insulation reliability, and heat resistance.
• the content of the rubber component (A) in the cured product may be within the above range based on the mass of the cured product.
• the crosslinking component having an epoxy group is a component that crosslinks during the curing reaction to form a crosslinked polymer.
• the crosslinking component having an epoxy group is a component that does not correspond to the (A) rubber component.
• the crosslinking component having an epoxy group is not particularly limited as long as it has an epoxy group in the molecule, and may be, for example, a common epoxy resin.
• the epoxy resin may be monofunctional, bifunctional, or polyfunctional (trifunctional or more), and is not particularly limited, but from the viewpoint of obtaining more sufficient curability, bifunctional or polyfunctional epoxy resins may be used. Good too.
• epoxy resin examples include bisphenol A type, bisphenol F type, phenol novolac type, naphthalene type, dicyclopentadiene type, and cresol novolak type epoxy resins. From the viewpoint of low tackiness, dielectric properties, and heat resistance, a naphthalene type or dicyclopentadiene type epoxy resin may be selected as the crosslinking component having an epoxy group (B), and a dicyclopentadiene type epoxy resin may be selected. You may choose. These epoxy resins can be used alone or in combination of two or more.
• the combination of a rubber having a maleic anhydride group or a carboxyl group and a compound having an epoxy group tends to produce particularly excellent effects in terms of heat resistance, low moisture permeability, and adhesion of the cured product. There is.
• the heat resistance of the cured product improves, it is possible to suppress deterioration of the cured product during a heating process such as nitrogen reflow, for example.
• the weight average molecular weight of the crosslinking component having an epoxy group may be, for example, 200 to 2,000, but from the viewpoint of the fluidity of the resin composition and the dielectric properties of the cured product, it is preferably 200 to 1,000. , more preferably from 250 to 800, even more preferably from 300 to 550, particularly preferably from 350 to 450.
• the number average molecular weight of the crosslinking component having an epoxy group may be, for example, from 100 to 1,000, but from the viewpoint of the fluidity of the resin composition and the dielectric properties of the cured product, it is preferably from 150 to 500. , more preferably from 200 to 400, even more preferably from 250 to 350, particularly preferably from 250 to 300.
• weight average molecular weight (Mw) and number average molecular weight (Mn) mean standard polystyrene equivalent values determined by gel permeation chromatography (GPC).
• the epoxy equivalent of the crosslinking component having an epoxy group may be, for example, 200 to 330 g/eq. It may be ⁇ 290g/eq, 220-270g/eq, or 230-260g/eq.
• the curable resin composition may contain other crosslinking components other than (B) the crosslinking component having an epoxy group, as long as the effects of the present disclosure are not significantly impaired.
• the content of the other crosslinking components is preferably less than 10 parts by mass based on 100 parts by mass of the crosslinking component (B) having an epoxy group, from the viewpoint of more sufficiently reducing the dielectric loss tangent of the cured product.
• ester curing agent itself is a compound that participates in the curing reaction, and can reduce the dielectric loss tangent while improving the heat resistance of the cured product.
• Ester-based curing agents are not particularly limited, but from the viewpoint of more fully achieving the effect of improving heat resistance and reducing the dielectric loss tangent, phenol esters, esters containing a dicyclopentadiene structure, and esters containing a naphthalene structure are used.
• Compounds having one or more ester groups with high reaction activity in one molecule such as esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used.
• the ester curing agent a compound containing a naphthalene structure may be used.
• ester curing agent for example, "EPICLON HPC8000-65T”, “EPICLON HPC8000-L-65MT”, “EPICLON HPC8150-60T”, “EPICLON HPC8150-62T”, “EPICLON H PC8150-65T” ( All are trade names manufactured by DIC Corporation). These can be used alone or in combination of two or more.
• ester curing agent reacts with the crosslinking component (B) as shown in the following formula (I) during the curing reaction. No hydroxyl groups are generated in the reaction between the ester curing agent (C) and the crosslinking component (B), and even if a side reaction occurs, hydroxyl groups are difficult to generate, resulting in a low dielectric loss tangent. It is considered possible.
• R 1 , R 2 and R 3 each independently represent a monovalent organic group, but since the effects of the present disclosure can be more fully obtained, R 1 , R 2 and R 3 each independently represent a monovalent organic group having an aromatic ring. Good too.
• the curable resin composition may contain other curing agents other than the ester curing agent (C) as long as the effects of the present disclosure are not significantly impaired.
• the content of the other curing agent is preferably less than 10 parts by mass based on 100 parts by mass of the ester curing agent (C) from the viewpoint of more sufficiently reducing the dielectric loss tangent of the cured product.
• the total content of (B) crosslinking component and (C) ester curing agent is based on the total amount of (A) rubber component, (B) crosslinking component, and (C) ester curing agent.
• the amount is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, and even more preferably 15 to 30% by weight.
• the total content of (B) the crosslinking component and (C) the ester curing agent is 5% by mass or more, sufficient curing is easily obtained, and the cured product has good adhesive properties, connection reliability, and insulation reliability. , and tend to have particularly excellent properties in terms of heat resistance.
• the total content of (B) the crosslinking component and (C) the ester curing agent is 40% by mass or less, the rubber component and the crosslinking component tend to mix well, and the cured product has better dielectric properties. They tend to have superior properties.
• the content ratio of the crosslinking component (B) and the ester curing agent (C) is the ratio between the epoxy group in the (B) epoxy resin and the ester bond in the (C) ester curing agent.
• the equivalent ratio is preferably in the range of 4:5 to 5:4, more preferably in the range of 4.5:5 to 5:4.5.
• the content ratio is within the above range, it is easier to obtain sufficient curing, and the cured product tends to have particularly excellent properties in terms of dielectric properties, adhesiveness, insulation reliability, and heat resistance. .
• a curing accelerator is a compound that functions as a catalyst for a curing reaction.
• the curing accelerator may be selected from tertiary amines, imidazole, organic acid metal salts, phosphorus compounds, Lewis acids, amine complex salts, and phosphines.
• imidazole may be used from the viewpoint of storage stability of the varnish of the curable resin composition, curability, and dielectric properties of the cured product.
• an imidazole that is compatible with this may be selected.
• the imidazole may be 1-benzyl-2-methylimidazole.
• the content of the curing accelerator (D) is 0.1 parts by mass based on 100 parts by mass of the total amount of the (A) rubber component, (B) crosslinking component, and (C) ester curing agent. It may be up to 10 parts by mass.
• the content of the curing accelerator is 0.1 parts by mass or more, sufficient curing tends to be easily obtained.
• the curable resin composition has particularly excellent storage stability of varnishes, films, etc., heat resistance of the cured product, and dielectric properties of the cured product. It tends to be effective.
• the content of the curing accelerator (D) is 0.3 to 7 parts by mass, 0.3 to 5 parts by mass, 0.3 to 2 parts by mass, 0.3 to 1 part by mass, 0.5 parts by mass. It may be 5 parts by weight, 0.5 to 2 parts by weight, or 0.5 to 1 part by weight.
• the filler (E) may be a filler having at least one group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, and a phenylamino group.
• a filler having at least one group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, and a phenylamino group By having these groups, in terms of compatibility with the resin component at the filler interface, filler dispersibility, storage stability of the curable resin composition, linear expansion coefficient of the cured product, and adhesiveness of the cured product, They tend to have particularly good properties. Therefore, the curable resin composition can be more suitably used as an interlayer adhesive for multilayer printed wiring boards.
• the filler includes a filler having at least one group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, and a phenylamino group from the viewpoint of linear expansion coefficient and adhesiveness. is preferable, it is more preferable that a filler having at least one group selected from the group consisting of a vinyl group, an epoxy group, and a phenylamino group is included, and it is even more preferable that a filler having an epoxy group is included.
• fillers having a vinyl group or epoxy group are more preferable from the viewpoint of linear expansion coefficient and adhesion to a low polarity resin base material, and from the same point of view, fillers having an epoxy group are particularly preferable. preferable.
• the low polarity resin base material include liquid crystal polymers.
• the filler may be a filler that has been subjected to surface treatment.
• the surface-treated filler can be obtained by treating the surface of the filler with a surface treatment agent such as an organic silane compound.
• a surface treatment agent such as an organic silane compound.
• the surface treatment filler may include a filler having at least one group selected from the group consisting of (meth)acryloyl group, vinyl group, epoxy group, and phenylamino group from the viewpoint of linear expansion coefficient and adhesiveness.
• a filler having at least one group selected from the group consisting of a vinyl group, an epoxy group, and a phenylamino group and even more preferably a filler having an epoxy group.
• fillers having a vinyl group or epoxy group are more preferable from the viewpoint of linear expansion coefficient and adhesion to a low polarity resin base material, and from the same point of view, fillers having an epoxy group are particularly preferable.
• the low polarity resin base material include liquid crystal polymers.
• the cured product of the curable resin composition tends to have better adhesion to the materials constituting the printed wiring board. Adhesion to a base material having a surface tends to be further improved.
• conventional curable resin compositions it has been difficult to improve adhesion to, for example, non-roughened liquid crystal polymer films, but the cured product of the curable resin composition containing the above-mentioned surface treatment filler has a low polarity. It tends to be possible to obtain good adhesion to resin base materials such as non-roughened liquid crystal polymer films.
• the content of the filler (E) is 30 to 75% by mass based on the total solid content of the curable resin composition. , 30 to 70% by mass, 40 to 70% by mass, or 50 to 70% by mass. (E) When the content of the filler is within the above range, both the fluidity of the curable resin composition and the reduction in the coefficient of linear expansion of the cured product can be achieved.
• the average particle size of the filler may be 0.01 ⁇ m or more, 0.1 ⁇ m or more, or 0.2 ⁇ m or more from the viewpoint of excellent dielectric properties, adhesive properties, and film appearance of the cured product, and 5 It may be .0 ⁇ m or less, 4.0 ⁇ m or less, 3.0 ⁇ m or less, 1.0 ⁇ m or less, or 0.8 ⁇ m or less. That is, the average particle size of the filler (E) is 0.01-5.0 ⁇ m, 0.1-4.0 ⁇ m, 0.2-3.0 ⁇ m, 0.2-1.0 ⁇ m, or 0.2-5.0 ⁇ m. It may be 0.8 ⁇ m.
• the average particle size of the filler means the particle size at a cumulative frequency of 50% in the particle size distribution determined by laser diffraction/scattering method.
• an inorganic filler may be used from the viewpoint of further reducing the coefficient of linear expansion and improving the modulus of elasticity.
• examples of inorganic fillers include silica, alumina, titania, tantalum oxide, zirconia, silicon nitride, gallium oxide, boron nitride, barium titanate, barium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate, and titanium.
• Examples include fillers containing at least one inorganic substance selected from the group consisting of: One type of inorganic filler may be used alone or two or more types may be used in combination.
• the inorganic filler may be an inorganic filler containing any one of silica, alumina, titania, or boron nitride from the viewpoint of dispersibility and heat resistance of the cured product.
• the inorganic filler may be an inorganic filler containing silica from the viewpoint of dielectric properties.
• an organic filler may be used.
• Organic fillers are generally particulate and do not dissolve in organic solvents but are dispersed in them. Further, the organic filler does not correspond to the rubber component (A).
• examples of the organic filler include fillers made of liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), and the like. One type of organic filler may be used alone or two or more types may be used in combination.
• the filler (E) may be a combination of one or more inorganic fillers and one or more organic fillers.
• the filler may be an inorganic filler whose surface is treated with silica, alumina, titania, or boron nitride; It's good to be there.
• the filler may be a surface-treated silica filler obtained by surface-treating silica from the viewpoint of linear expansion coefficient and adhesiveness.
• organic silane compounds such as epoxysilane compounds, aminosilane compounds, (meth)acrylic silane compounds, and vinylsilane compounds may be used from the viewpoint of linear expansion coefficient and adhesiveness.
• organic silane compound examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropylmethyldimethoxy.
• Silane 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N-(1,3-dimethylbutylidene)-3-a
• the curable resin composition also contains an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, a filler, and a flame retardant, as necessary.
• an antioxidant an anti-yellowing agent, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, a filler, and a flame retardant, as necessary.
• a leveling agent, etc. may be further included within a range that does not significantly impair the effects of the present disclosure.
• the curable resin composition may contain at least one deterioration inhibitor selected from the group consisting of antioxidants, heat stabilizers, light stabilizers, and hydrolysis inhibitors.
• Antioxidants suppress deterioration due to oxidation.
• the antioxidant provides the cured product with sufficient heat resistance at high temperatures.
• the heat stabilizer provides the cured product with stability at high temperatures.
• light stabilizers include ultraviolet absorbers that prevent deterioration due to ultraviolet rays, light blocking agents that block light, and quenchers that have a quenching function that stabilizes organic materials by accepting light energy absorbed by organic materials. Can be mentioned.
• Hydrolysis inhibitors suppress deterioration due to moisture.
• the deterioration inhibitor may be at least one selected from the group consisting of antioxidants, heat stabilizers, and ultraviolet absorbers.
• the deterioration inhibitor only one type of the components listed above may be used, or two or more types may be used in combination. In order to obtain better effects, two or more types of deterioration inhibitors may be used in combination.
• the curable resin composition may be prepared as a resin varnish in which each of the above-mentioned components is dissolved or dispersed in an organic solvent.
• the organic solvent is not particularly limited, but includes, for example, aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; acetone, methyl ethyl ketone (MEK), Ketones such as methyl isobutyl ketone (MIBK), cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, ⁇ -butyrolactone; ethylene carbonate, propylene Examples include carbonic acid esters such as carbonate; amides such as N,N-dimethylform
• toluene or N,N-dimethylacetamide may be used.
• These organic solvents can be used alone or in combination of two or more.
• the solid content (components other than the organic solvent) concentration in the resin varnish may be 20 to 80% by mass.
• the mixing and kneading of the above resin varnish can be carried out using an appropriate combination of conventional dispersing machines such as a stirrer, a sieve, a three-roll mill, and a ball mill.
• the curable film according to this embodiment is made of the above-mentioned curable resin composition.
• a curable film can be easily produced, for example, by applying a resin varnish containing a curable resin composition to a base film and removing the solvent from the coating film. According to this method, a laminated film including a base film and a curable film provided on the base film can be obtained.
• the solvent is removed from the coating film on the base film by drying at a temperature that does not cure the curable resin composition and under conditions that sufficiently volatilize the solvent. Specifically, the coating film is dried by heating usually at 60 to 180°C for 0.1 to 90 minutes.
• the residual volatile content of the obtained curable film is preferably 10% by mass or less. When the residual volatile content is 10% by mass or less, it is easy to suppress voids from remaining inside the cured product due to foaming due to solvent volatilization during assembly heating. Further, contamination of surrounding materials or members due to volatile components generated during heating can be easily suppressed.
• the material of the base film is not particularly limited, and examples include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; polycarbonate, polyamide, polyimide, polyamideimide, and polyether.
• polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate
• polyolefins such as polyethylene and polypropylene
• polycarbonate polyamide, polyimide, polyamideimide, and polyether.
• Examples include imide, polyether sulfide, polyether sulfone, polyether ketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, and liquid crystal polymer.
• polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyarylate, and polysulfone are preferred.
• the thickness of the base film may be changed as appropriate depending on the desired flexibility, and may be from 3 to 250 ⁇ m. Generally, when the thickness is 3 ⁇ m or more, the film strength is sufficient, and when the thickness is 250 ⁇ m or less, sufficient flexibility is obtained. From the above viewpoint, the thickness may be 5 to 200 ⁇ m or 7 to 150 ⁇ m. From the viewpoint of improving the releasability from the curable film, a base film that has been subjected to a release treatment with a silicone compound, a fluorine-containing compound, etc. may be used as necessary.
• a protective film may be pasted on the curable film to form a laminate film with a three-layer structure consisting of a base film, a curable film, and a protective film.
• the material of the protective film is not particularly limited, and examples include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene. Among these, from the viewpoint of flexibility and toughness, polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene are preferred. From the viewpoint of improving the releasability from the curable film, a protective film that has been subjected to a release treatment using a silicone compound, a fluorine-containing compound, or the like may be used as necessary.
• the thickness of the protective film may be changed as appropriate depending on the desired flexibility, and may be from 10 to 250 ⁇ m. Generally, when the thickness is 10 ⁇ m or more, the film strength is sufficient, and when the thickness is 250 ⁇ m or less, sufficient flexibility is obtained. From the above viewpoint, the thickness may be 15 to 200 ⁇ m or 20 to 150 ⁇ m.
• the thickness of the curable film after drying is not particularly limited, but may usually be 5 to 1000 ⁇ m. When the thickness is 5 ⁇ m or more, the curable film or its cured product tends to have sufficient strength. When the thickness is 1000 ⁇ m or less, sufficient drying can be performed, so that the amount of residual solvent in the curable film tends to be easily reduced.
• the laminated film can be easily stored, for example, by winding it up into a roll.
• a sheet-like laminated film cut into a suitable size from a roll-like film can also be stored.
• the curable resin composition, curable film, and laminated film according to the present embodiment are suitable for forming a protective layer (coverlay) that covers an electric circuit in a printed wiring board, and as an interlayer adhesive in a multilayer printed wiring board. It is particularly suitable for forming a protective layer (coverlay).
• the printed wiring board in this embodiment includes as a component a laminate formed from a metal portion forming an electric circuit (conductor circuit) and a resin base material.
• the printed wiring board can be manufactured, for example, using a metal-clad laminate by a conventionally known method such as a subtractive method.
• the printed wiring board in this embodiment is a so-called flexible circuit board (FPC) in which a conductive circuit formed by a metal part is partially or entirely covered with a coverlay film or screen printing ink, etc. ), flat cables, circuit boards for tape automated bonding (TAB), etc.
• FPC flexible circuit board
• the printed wiring board of this embodiment can have any laminated structure that can be adopted as a printed wiring board.
• it can be a printed wiring board having a base material layer, an adhesive layer, a metal part, and a protective layer.
• a multilayer printed wiring board can be constructed by laminating two or three or more of the above printed wiring boards using an interlayer adhesive.
• any base material conventionally used as a base material for printed wiring boards can be used as the base material layer.
• any resin conventionally used as a base material for printed wiring boards can be used as the base material layer.
• the resin for the base layer include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, epoxy resin, maleimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, polytetrafluoroethylene (PTFE), etc. Examples include fluororesins (PTFE, etc.).
• the curable resin composition of this embodiment can be used for each adhesive layer, protective layer, and interlayer adhesive of a printed wiring board.
• the curable resin composition has high adhesion to the materials constituting the printed wiring board such as the base layer and metal parts, and the curable resin composition
• the layer itself formed using this material has excellent low dielectric properties.
• the cured product of the curable resin composition of this embodiment has excellent adhesion particularly to low polarity substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resins, and PTFE.
• the curable resin composition according to this embodiment contains the (A) rubber component, the cured product thereof can have flexibility. Therefore, the curable resin composition according to this embodiment can be suitably used for forming a protective layer of a flexible printed wiring board and as an interlayer adhesive.
• the metal portion is not particularly limited, but may be copper from the viewpoint of wiring formability.
• the material forming the copper there are no particular restrictions on the material forming the copper, and for example, electrolytic copper foil and rolled copper foil used for copper-clad laminates, printed wiring boards, etc. can be used.
• electrolytic copper foils include, for example, F0-WS-18 (manufactured by Furukawa Electric Co., Ltd., trade name), NC-WS-20 (manufactured by Furukawa Electric Co., Ltd., trade name), and YGP-12 (manufactured by Nippon Denki Co., Ltd.).
• rolled copper foil examples include TPC foil (manufactured by JX Nippon Mining & Metals Co., Ltd., trade name), HA foil (manufactured by JX Nippon Mining & Metals Co., Ltd., trade name), HA-V2 foil (manufactured by JX Nippon Mining & Metals Co., Ltd., trade name), and C1100R.
• a roughened copper foil may be used.
• rolled copper foil may be used.
• the metal portion may have a roughened surface formed by roughening treatment.
• Examples of finely roughened copper foil include FV (FHG)-WS (FV-WS/FHG-WS, copper foil product, manufactured by Furukawa Electric Co., Ltd., trade name), FZ-WS (copper foil product, manufactured by Furukawa Electric Co., Ltd.), (manufactured by Denki Kogyo Co., Ltd., product name).
• the above-mentioned curable resin composition can be used for the following purposes in addition to being used as a composition for forming a protective layer (coverlay) or as an interlayer adhesive. That is, the curable resin composition can be used for applications such as a primer layer of a difficult-to-adhesive material, an adhesive layer of a low dielectric material with an adhesive layer, and the like.
• the method for applying the curable resin composition is not particularly limited, and for example, a comma coater, a bar coater, a die coater, dipping, spin coating, or the like can be used.
• the above-mentioned curable film can be used for applications such as a build-up film, a resin layer of resin-coated copper foil, and a low dielectric expansion/contraction base material.
• Rubber component FG1924 Maleic anhydride modified styrene ethylene butylene styrene elastomer (Kraton Polymer Japan Co., Ltd., product name "FG1924GT”)
• Ester curing agent HPC8150-62T Ester curing agent (manufactured by DIC Corporation, product name "EPICLON HPC8150-62T", active ester compound containing a naphthalene structure, toluene solution with solid content of 62% by mass)
• Curing accelerator 1B2MZ 1-benzyl-2-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name "1B2MZ")
• a release-treated polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., trade name "Purex A3100", thickness 25 ⁇ m) was prepared as a base film.
• the above-mentioned curable resin composition was applied onto the release-treated surface of this PET film using a knife coater (manufactured by Yasui Seiki Co., Ltd., trade name "SNC-350”).
• the coating film was dried by heating at 80° C. for 15 minutes in a dryer (manufactured by Futaba Kagaku Co., Ltd., trade name “MSO-80TPS”) to form a curable film with a thickness of 30 ⁇ m.
• the same release-treated PET film as the base film was attached as a protective film to the formed curable film with the release-treated side facing the curable film to obtain a laminated film.
• VLP-Cu foil an electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd., (trade name “F2-WS-18", thickness 18 ⁇ m) (hereinafter also referred to as "VLP-Cu foil”) were stacked with the roughened surface facing the curable film side.
• VLP-Cu foil was placed under the conditions of a pressure of 0.5 MPa, a temperature of 100°C, and a pressing time of 60 seconds. Laminated to curable film.
• VLP-Cu foil was placed on the exposed curable film with the roughened surface facing the curable film, and the VLP-Cu foil was laminated on the curable film under the above conditions. Thereafter, by heating at 180°C for 60 minutes in a dryer (manufactured by Futaba Kagaku Co., Ltd., trade name "MSO-80TPS"), the VLP-Cu foil and the cured film, which is a cured product of the curable film, were separated from the VLP-Cu foil. - A laminate having Cu foil was obtained.
• Vector network analyzers E8364B manufactured by Keysight Technologies
• CP531 manufactured by Kanto Denshi Applied Development Co., Ltd.
• CPMA-V2 program

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• 2023
  • 2023-07-10 JP JP2024533705A patent/JPWO2024014432A1/ja active Pending
  • 2023-07-10 WO PCT/JP2023/025467 patent/WO2024014432A1/ja not_active Ceased
  • 2023-07-10 CN CN202380034332.9A patent/CN119138110A/zh active Pending
  • 2023-07-10 US US18/860,281 patent/US20250297143A1/en active Pending
  • 2023-07-10 KR KR1020247040300A patent/KR20250038205A/ko active Pending
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