TW202215921A - dry film - Google Patents

Abstract

To provide a curable resin composition suitable for use as an underlayer coating film of an adhesion-imparting coating that can perform good plating of a conductor layer even when a surface unevenness (surface roughness) is small, and has good adhesion for a plated conductor layer. There is provided a curable resin composition that is for forming an underlayer coating film provided between a base material and an adhesion-imparting coating provided in order to improve an adhesion of a plating layer to the base material, in which the curable resin composition is characterized in that: the curable resin composition comprises an epoxy resin (A) and an active ester compound (B); the adhesion-imparting coating comprises a catalyzing metal-containing silicon oligomer; and the catalyzing metal-containing silicon oligomer is obtained by subjecting a tetra-alkoxy silane and a polyvalent alcohol, in which a hydroxy group is bonded to at least n and n+1 sites or n and n+2 sites (in which n is an integer of at least 1), to a condensation reaction in the presence of a catalyzing metal.

Description

dry film

The present invention relates to the formation of a plating layer on the surface, and is suitable for use as a dry film for insulating materials.

As a method of manufacturing a multilayer printed wiring board, there is known a build-up layer in which an insulating layer and a conductor layer are alternately stacked on an inner-layer circuit board (so-called copper-clad laminate) on which a circuit is formed by pressing a prepreg and a copper foil. method of manufacturing technology. For example, it is proposed to coat an epoxy resin composition on an inner-layer circuit board on which a circuit is formed, heat and harden to form an insulating layer, and then use a roughening agent to form a roughened surface of the insulating layer on the surface of the insulating layer. A method of forming a conductor layer by treatment of electroless plating and electrolytic plating (refer to Patent Document 1 and Patent Document 2).

Furthermore, it is proposed to laminate an adhesive sheet of an epoxy resin composition on an inner-layer circuit board on which circuits are formed, heat and harden to form an insulating layer, and then use a roughening agent to form a roughened surface of the insulating layer on the surface of the insulating layer. , a method of manufacturing a multilayer printed wiring board in which a conductor layer is formed by electroless plating and electrolytic plating (refer to Patent Document 3). In such a proposed technique, the adhesion between the plating layer (conductor circuit layer) and the insulating layer is improved by roughening the surface of the insulating layer.

On the other hand, in recent high-definition conductor circuit patterns, for example, when an unnecessary electroless plating portion under a plating resist is removed by etching during conductor circuit formation, an etching solution may enter the surface of the insulating layer. In the concave portion, when the conductor circuit is peeled off due to erosion of the circuit bottom of the conductor layer, there is a problem that a fine conductor circuit cannot be formed with high precision. In addition, there is also a problem that the contact area between the conductor layer and the insulating layer is increased due to the uneven surface of the insulating layer, so the transmission loss of the electrical signal especially at high frequencies increases.

Further, in the laminate structure in the wiring board, since the surface unevenness is formed on the insulating layer, in order to electrically insulate the upper and lower conductor layers, the thickness of the necessary layer is increased by the height of the unevenness. Thinning becomes difficult. In view of such a problem, in order to obtain a thinner and higher-definition wiring board, there is a need for a technique for realizing excellent adhesion to the conductor circuit without roughening the insulating layer.

In this regard, the following invention has been proposed: by treating the surface of the substrate with a coating agent containing a metal oligomer containing a catalyst, without roughening the surface of the substrate, a plating layer is formed. (refer to Patent Document 4). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 7-304931 [Patent Document 2] Japanese Patent Application Laid-Open No. 7-304933 [Patent Document 3] Japanese Patent Application Laid-Open No. 11-87927 [Patent Document 4] International Publication No. 2016/017792

[The problem to be solved by the invention]

However, the inventors have evaluated the coating agent proposed in Patent Document 4 in order to deposit a plated layer (conductor layer) on the insulating layer without the roughening treatment step, and found that the coating agent should be used as a coating agent. Depending on the type of insulating layer of the base, the adhesion of the plating layer may not necessarily be obtained.

Therefore, an object of the present invention is to provide an insulating material which can obtain excellent adhesion to a plated layer (conductor layer) even if the surface unevenness (surface roughness) is small (for example, even if Ra is 200 nm or less). [means to solve the problem]

The present inventors, as a result of intensive studies to solve the above-mentioned problems, found that the above-mentioned problems can be solved by a dry film having a resin layer, and completed the present invention. The resin layer is a layer composed of a thermosetting resin composition composed of a specific component and a layer composed of a coating composition composed of a specific composition that imparts plating adhesion on a film substrate. The resin layer of the 2-layer structure. That is, the present invention is as follows.

The dry film of the present invention is A dry film having a resin layer with a two-layer structure on a film substrate, the two-layer structure of the resin layer is a layer of a curable resin composition containing an epoxy resin and an active ester compound, and a layer containing an acrylic resin and a contact The dry film is composed of a layer of an adhesion-imparting coating composition of a catalyst-containing metal-silicon oligomer, and the dry film is characterized in that the catalyst-containing metal-silicon oligomer is prepared by mixing tetraalkoxysilane with at least A polyol having a hydroxyl group bonded to the n, n+1 position or n, n+2 position (only n is an integer of 1 or more) undergoes a condensation reaction in the presence of a metal having catalytic properties for electroless plating The obtained catalyst-containing metal silicon oligomer.

The said dry film can harden the resin layer which consists of it, and becomes a hardened material.

It can be an electronic part having an insulating layer containing the above-mentioned cured product. [Effect of invention]

According to the present invention, even if the surface unevenness (surface roughness) is small (for example, even if Ra is 200 nm or less), it is possible to provide an insulating material that can obtain excellent adhesion to a plated layer (conductor layer).

The curable resin composition of each layer constituting the dry film of the present invention and the coating composition for imparting plating adhesion will be described in detail.

Furthermore, the curable resin composition of the present invention and the coating composition for imparting plating adhesion can be produced in accordance with known methods, for example, by blending, stirring, and uniformly dispersing each component.

In addition, in the present invention, the solid content refers to components other than the solvent (especially the organic solvent) constituting the respective raw materials in the curable resin composition and the coating composition for imparting plating adhesion, or its mass or volume.

In the present invention, when the compound name is simply expressed, all of its isomers are included.

＜＜＜Curable resin composition＞＞＞ ＜＜Ingredients＞＞ The curable resin composition forming the first layer (insulating layer) of the dry film of the present invention contains an epoxy resin and an active ester compound. The resin layer composed of the curable resin composition is a layer that serves as a base layer of a layer composed of a coating composition that imparts plating adhesion, which will be described later, and serves as an insulating layer provided on a substrate on which a circuit is formed. layer.

＜Epoxy resin＞ The epoxy resin is not particularly limited, and may be bifunctional or trifunctional or more. Moreover, a monofunctional epoxy resin may be contained as a reactive diluent.

Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin Oxygen resin, bisphenol Z type epoxy resin, etc. bisphenol type epoxy resin; bisphenol A novolac type epoxy resin, phenol novolak type epoxy resin, cresol novolac epoxy resin, etc. novolak type ring Oxygen resin; biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, aryl alkylene type epoxy resin, tetraphenol ethane type epoxy resin, naphthalene type epoxy resin, anthracene type ring Oxygen resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, trihydroxyphenylmethane type epoxy resin, hydantoin type epoxy resin, tetraphenol Ethane type epoxy resin, brominated epoxy resin, hydrogenated (bisphenol) type resin, glycidylamine type epoxy resin, alicyclic epoxy resin, diglycidyl phthalate resin, Tetraglycidyl xylyl ethane resin, glycidyl methacrylate copolymer epoxy resin, cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin, cyclohexyl Oxygen-modified polybutadiene rubber derivatives, CTBN-modified epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, 1,6-hexyl Glycol Diglycidyl Ether, Diglycidyl Ether of Ethylene Glycol or Propylene Glycol, Sorbitol Polyglycidyl Ether, Ps(2,3-epoxypropyl)isocyanurate, Epoxy resins such as triglycidyl ginseng (2-hydroxyethyl) isocyanurate, etc. These epoxy resins can be used alone or in combination of two or more.

Among them, from the viewpoint of thermal dimensional stability of the obtained cured product, biphenyl type epoxy resin or naphthalene type epoxy resin is preferably used; from the viewpoint of low dielectric properties, dicyclopentadiene type epoxy resin is preferably used Resin; From the viewpoint of heat resistance, a novolak-type epoxy resin is preferably used.

These can be used alone or in combination of two or more.

＜＜Active ester compound＞＞ The active ester compound may be any compound as long as it has an active ester group, and is preferably a compound having at least two active ester groups in the molecule.

The active ester group in the active ester compound can react with the epoxy group by heating to act as a hardener for the epoxy resin used in the present invention.

The active ester compound is preferably an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound from the viewpoint of improving the heat resistance of the cured product obtained. As the active ester compound, it is more preferable to react a carboxylic acid compound with one or two or more kinds selected from the group consisting of an aromatic compound having a phenolic hydroxyl group (a phenol compound, a naphthol compound, etc.) and a thiol compound The obtained active ester compound is particularly preferably an aromatic compound obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group, and having at least two active ester groups in the molecule.

Specific examples of the carboxylic acid compound used to form the active ester compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. acid etc. Among these, from the viewpoint of improving the heat resistance of the obtained electrical insulating layer, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are particularly preferred; Phthalic acid, isophthalic acid, terephthalic acid; more preferably isophthalic acid, terephthalic acid.

Specific examples of the thiocarboxylic acid compound used to form the active ester compound include thioacetic acid, thiobenzoic acid, and the like.

Specific examples of the hydroxy compound used to form the active ester compound include dihydroxybenzene, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylbenzene Alkylated bisphenol S, phenol, cresol, naphthol, dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, benzenetriol, dicyclopentadienyl dicyclopentadienyl Phenol, phenol novolac, etc.

Among these, from the viewpoint of improving the solubility of the active ester compound and improving the heat resistance of the resulting cured product, the hydroxy compound for forming the active ester compound is preferably dihydroxynaphthalene, dihydroxynaphthalene, and dihydroxydihydroxydihydroxynaphthalene. Benzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac; more preferably dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone Benzophenone, dicyclopentadienyl diphenol, phenol novolak; more preferably, dicyclopentadienyl diphenol, phenol novolak.

Specific examples of the thiol compound for forming the active ester compound include benzenedithiol, triazinedithiol, and the like.

The manufacturing method of an active ester compound is not specifically limited, It can manufacture by a well-known method. For example, it can be obtained by the condensation reaction of the aforementioned carboxylic acid compound and/or thiocarboxylic acid compound and a hydroxyl compound and/or a thiol compound.

In the present invention, as the active ester compound, for example, an aromatic compound having an active ester group disclosed in Japanese Patent Laid-Open No. 2002-12650 and a polyfunctional polyester disclosed in Japanese Patent Laid-Open No. 2004-277460, or commercially available Taste. Examples of commercially available products include trade names "EXB9451, EXB9460, EXB9460S, Epiclon HPC-8000-65T" (the above, manufactured by DIC Corporation, "Epiclon" is a registered trademark), trade names "DC808" (manufactured by Japan Epoxy Resin Corporation), Trade name "YLH1026" (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

These can be used alone or in combination of two or more.

＜Other ingredients＞ (Phenolic resin) It is preferable to contain a phenol resin as a component other than the said epoxy resin and an active ester compound. The hardened product of epoxy resin and active ester compound is hard and brittle, so it may be cracked and peeled due to physical impact. Manufacture of peeling failures A curable resin composition with excellent stability.

The phenol resin is not particularly limited, and may be bifunctional or trifunctional or more. Specifically, phenol novolac resins, alkylphenol novolac resins, phenol novolac resins containing a triazine structure, bisphenol A novolac resins, phenol resins containing a dicyclopentadiene structure, and Xylok-type phenol resins may be mentioned. , terpene-modified phenol resins, polyvinyl phenols, phenolic hardeners containing naphthalene structure, phenolic hardeners containing pycnogenol structure, etc.

These can be used alone or in combination of two or more.

(other resin components) Examples of other resin components of the curable resin composition include polyester-based resins, phenoxy-based resins, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylate copolymers, polybutadiene resins, Polycarbonate resin, polyimide resin, polyimide resin, acrylic resin, polyimide resin or fluororesin, etc.

These can be used alone or in combination of two or more.

(Ingredients other than resin components) As components other than the resin component of the curable resin composition, known conventional ones such as inorganic fillers, curing accelerators, organic solvents, colorants, tackifiers, antifoaming agents, leveling agents, and adhesion imparting agents may be included. the ingredients.

Inorganic fillers include barium sulfate, barium titanate, silica (amorphous silica, crystalline silica, fused silica, spherical silica, etc.), talc, clay, magnesium carbonate, carbonic acid Calcium, aluminum oxide, aluminum hydroxide, aluminum oxide, silicon nitride, boron nitride, aluminum nitride, etc. These can be used alone or in combination of two or more.

Among them, as the inorganic filler, from the viewpoint of having a small specific gravity, being able to be blended in a high proportion in the curable resin composition, and being excellent in thermal dimensional stability (low thermal expansion), silica is preferred, and the filling property is Excellent point of view, particularly preferred is spherical silica.

The average particle diameter of the inorganic filler is preferably 3 μm or less, more preferably 1 μm or less. In addition, the average particle diameter of an inorganic filler can be calculated|required by the laser diffraction particle diameter distribution measuring apparatus.

Examples of hardening accelerators include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl- Imidazole derivatives of 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.; dicyandiamine, benzyldimethylamine, 4-(dimethylimidazole) amino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc. Amine compounds; hydrazine compounds such as dihydrazine adipate, dihydrazine sebacate, etc.; phosphorus compounds such as triphenylphosphine; guanamine, acetoguanamine, benzoguanamine, melamine, 2, 4-Diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diazine Amino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc. The S-triazine derivatives and so on. These can be used alone or in combination of two or more.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, celosyl acetate, propylene glycol monomethyl ether acetate, carbitol acetic acid Acetates such as esters; serosols such as serosol and butyl carbitol; carbitols such as carbitol and butyl carbitol; aromatic hydrocarbons such as toluene and xylene, etc. Dimethylformamide, dimethylacetamide, etc. are mentioned. These can be used alone or in combination of two or more.

As a coloring agent, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. are mentioned, for example. These can be used alone or in combination of two or more.

Examples of the tackifier include asbestos, organic bentonite (Orben), and organic bentonite. These can be used alone or in combination of two or more.

As an antifoaming agent, a polysiloxane type antifoaming agent, a fluorine type antifoaming agent, a polymer type antifoaming agent, etc. are mentioned, for example. These can be used alone or in combination of two or more.

Examples of the adhesion-imparting agent include thiazole-based adhesion-imparting agents, triazole-based adhesion-imparting agents, and silane coupling agents. These can be used alone or in combination of two or more.

＜＜Content＞＞ In the curable resin composition, the blending amount of the epoxy resin and the active ester is not particularly limited. Generally speaking, the ratio (Eq2/Eq1) of the epoxy equivalent (Eq1) of the epoxy group contained in the epoxy resin to the active ester equivalent (Eq2) contained in the active ester (Eq2/Eq1) can be 0.7~1.4, more The optimum range is 0.8~1.2. When the equivalence ratio falls within such a range, the cured product of the curable resin composition has excellent adhesion to the base material or the layer composed of the coating composition for imparting adhesion to plating, and can be used as an insulating material. material properties.

In addition, when a phenol resin is further combined and used, the blending amount of the phenol resin is not particularly limited. Generally speaking, the ratio {(Eq2+Eq3)/Eq1} of the above-mentioned epoxy equivalent (Eq1) to the sum of the above-mentioned active ester equivalent (Eq2) and the hydroxyl equivalent of the phenolic hydroxyl group contained in the phenol resin (Eq3) It is 0.4~1.2, more preferably 0.5~1.0, and the ratio (Eq3/Eq2) of active ester equivalent (Eq2) to phenolic hydroxyl equivalent (Eq3) may be 0.05~10, more preferably 0.1~1.0. By being within this range, the cured product of the curable resin composition is provided with excellent flexibility (extensibility), and the stability of manufacture and reliability as electronic parts (multilayer printed wiring boards, etc.) are improved.

<<<Coating composition for imparting plating adhesion >>> ＜＜Ingredients＞＞ The coating composition for imparting plating adhesion, which forms the second layer (plating adhesion layer) of the dry film of the present invention, contains an acrylic resin and a catalyst-containing metal silicon oligomer. As such a coating composition for imparting adhesion to plating, a commercial item can be used, for example, SIPAC300 manufactured by JCU Corporation, and the like. In the present invention, the layer composed of the coating composition for imparting plating adhesion is formed on the base material via the layer composed of the aforementioned curable resin composition, and the metal plating layer is formed on the layer. .

＜Acrylic resin＞ The acrylic resin is a polymer including a structural unit derived from at least one (meth)acrylic monomer selected from the group consisting of (meth)acrylic acid and derivatives thereof. In addition, in this specification, (meth)acrylic acid means acrylic acid, methacrylic acid, or both acrylic acid and methacrylic acid. For example, homopolymers of (meth)acrylic monomers such as (meth)acrylic acid, (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, etc., or two kinds of these can be mentioned. The above copolymers, and copolymers obtained by polymerizing (meth)acrylic monomers and other monomers that can be copolymerized with the monomers, and the like. In the acrylic resin, the above-mentioned (meth)acrylic monomers and/or other monomers that can be copolymerized with these may be polymerized by a conventionally known method. Among them, alkyl (meth)acrylate copolymers, colloidal silica/acrylic acid composites, and ethylene/acrylic acid copolymer ammonium salts are particularly preferred; and alkyl (meth)acrylate copolymers are more preferred. These resins can be used 1 type or 2 or more types. In addition, these resins may be in the form of a solution or in the form of a powder.

<Catalyst-containing metal silicon oligomer> As a catalyst-containing metal silicon oligomer, a tetraalkoxysilane is used by bonding at least n, n+1 positions or n, n+2 positions (only n is an integer of 1 or more). The polyol of the hydroxyl group is obtained by performing a condensation reaction in the presence of a metal having catalytic properties (hereafter, it is described as a catalytic metal).

The tetraalkoxysilane used in the catalyst-containing metal silicon oligomer is not particularly limited, and for example, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, etc. can be used. Of these, tetraethoxysilane is particularly preferred. These tetraalkoxysilanes can be used alone or in combination.

In addition, the polyol having hydroxyl groups bonded to at least n, n+1 positions or n, n+2 positions (only n is an integer of 1 or more) used in the catalyst-containing metal-silicon oligomer is not particularly limited. For example, the dihydric to tetrahydric alcohol in which n is an integer of 1 to 3, the dihydric to trihydric alcohol in which n is an integer of 1 to 2 is preferable, and the like. Specific examples of these polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol, for example. , 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol and other dihydric alcohols; glycerin Trivalent alcohols such as erythritol, etc.; tetravalent alcohols such as erythritol. Among these polyhydric alcohols, dihydric alcohols are particularly preferred, ethylene glycol and/or 1,3-propanediol are more preferred, and ethylene glycol is particularly preferred. These polyols may be used alone or in combination.

Further, the catalyst metal used in the catalyst metal-silicon oligomer is not a metal having a catalytic function in the condensation reaction of tetraalkoxysilane and polyol, but in the precipitation reaction of the plating described later. Metals with autocatalytic properties. Therefore, it is different from the metal catalyst mentioned in WO2014/207885 or WO2014/207886.

As such a catalyst metal, iron, nickel, cobalt, copper, palladium, silver, gold, platinum, etc. are mentioned, for example. Among these catalyst metals, iron, nickel, cobalt, copper, and palladium are particularly preferred; iron, nickel, copper, and palladium are more preferred; and palladium is particularly preferred. Furthermore, the above-mentioned catalyst metal is preferably present in a state of being dissolved in the above-mentioned polyol during the condensation reaction. Metal salts containing catalyst metals such as gold(III), silver(I) chloride, platinum(IV) chloride, etc. Furthermore, when the catalyst metal is hardly dissolved in the polyol, it can be dissolved in a mineral acid such as hydrochloric acid in advance. These catalytic metals may be used alone or in combination, and in this case, at least palladium is preferably contained.

The method for condensing tetraalkoxysilane and polyol in the presence of catalyst metal is not particularly limited. For example, catalyst metal can be added to the above-mentioned polyol at a rate of 0.01~20g/kg, preferably 0.1~10g /kg and dissolved, it was heated to the reaction temperature while stirring, and tetraalkoxysilane was further added and reacted. The reaction temperature is 25 to 150° C., preferably 30 to 70° C., and the reaction time is 30 minutes to 8 hours, preferably 2 hours to 4 hours. In addition, it is important that the tetraalkoxysilane and the polyol are reacted at a molar ratio of 4:1 to 1:4, preferably 1:2 to 1:4, during the reaction. Thereby, a polyol is incorporated between the tetraalkoxysilane and the tetraalkoxysilane.

In addition, although alcohol is produced|generated in the said reaction, it is preferable not to fractionate alcohol because the polymerization reaction will be controlled by not fractionating this alcohol.

In addition, in the above reaction, the tetraalkoxysilane and the polyol are separated into two layers before the condensation reaction is performed. However, when the reaction is completed, it becomes one layer. Therefore, the reaction can be terminated when the one layer is formed.

The catalyst-containing metal-silicon oligomer obtained in this way is a silicon oligomer obtained by condensation reaction of 2-4 tetraalkoxysilanes and 1-13 polyols with a catalyst metal incorporated therein.

Furthermore, the catalyst-containing metal silicon oligomer is the alkoxy group of tetraalkoxysilane, and one or two hydroxyl groups at the n, n+1 position or n, n+2 position present in the polyol Those obtained by a condensation reaction have, for example, the following partial structures (a) to (d). In addition, it is presumed that the catalyst metal is present between oxygen atoms in a catalyst metal-silicon oligomer to form a 5-membered ring structure or a 6-membered ring structure with the catalyst metal as a vertex, and it is stabilized. Therefore, after the catalyst-containing metal silicon oligomer of the present invention is formed, the precipitation of the catalyst metal is not observed even after one year.

The catalyst-containing metal silicon oligomer can be identified by known methods such as NMR, IR, and MASS such as 1HNMR and 29SiNMR. Specifically, in the case of NMR, the alcohol generated by the condensation reaction of tetraalkoxysilane and polyol can be confirmed by 1HNMR, and the number of silicon in the catalyst-containing metal silicon oligomer can be confirmed by 29SiNMR. , to identify the catalyst-containing metal silicon oligomer of the present invention. In addition, the incorporation of the catalyst metal into the silicon oligomer can be confirmed by the fact that no precipitation of the catalyst metal is observed after a certain period of time, such as one year, after the silicon oligomer is formed.

Catalyst-containing metal-silicon oligomers can be prepared by combining two or more catalyst-containing metal-silicon oligomers with different catalyst metals, or by using them in the preparation of catalyst-containing metal-silicon oligomers. Those prepared in the presence of two or more kinds of catalytic metals are preferred because the catalytic effect of the catalytic metals is enhanced. In addition, the combination of the catalyst metal is not particularly limited, and for example, it is preferably a combination of palladium and one or more selected from iron, nickel, cobalt, and copper.

＜Other ingredients＞ (resin components other than acrylic resin) The coating composition for imparting plating adhesion may contain resin components other than acrylic resins. Such resin components are not particularly limited as long as they are soluble or dispersed in the coating composition for imparting plating adhesion, and examples thereof include urethane-based resins, phenol-based resins, and epoxy-based resins. Wait.

(Ingredients other than resin components) The coating composition for imparting the adhesion to the plating can be blended with a well-known and conventional solvent, or as long as the effect of the present invention is not impaired, a colorant, a friction coefficient modifier, a film enhancer, and other functional agents can be blended. additive. For example, as a solvent, water, isopropyl alcohol, ethyl cyloxine, etc. are mentioned.

＜＜Content＞＞ In the coating composition for imparting plating adhesion, the blending amount of the acrylic resin and the catalyst-containing metal silicon oligomer is not particularly limited. In general, in the coating composition for imparting plating adhesion, the concentration of the metal catalyst derived from the catalyst metal silicon oligomer is in the range of 50 to 200 ppm, and the concentration of the metal catalyst other than acrylic resin or acrylic resin is in the range of 50 to 200 ppm. The resin component is blended in a range of 50 mass % or less, preferably 0.1 to 50 mass %, more preferably 1 to 20 mass % of the coating composition for imparting plating adhesion.

＜＜＜Dry Film＞＞＞ The dry film of the present invention is obtained by forming, on a film substrate, a resin layer having a two-layer structure consisting of a layer of a curable resin composition and a layer of a coating composition that imparts plating adhesion.

＜＜Manufacturing method of dry film＞＞ In the dry film of the present invention, the first layer (a layer composed of a thermosetting resin composition) is first formed on the film substrate, and then a second layer (a layer composed of a thermosetting resin composition) is formed on the surface of the first layer. After forming the second layer, the first layer can be formed on the surface of the second layer, or the first layer and the second layer can be formed separately, and the The two are made to fit together.

Specifically, after the first layer is formed on the film base, when the second layer is formed on the surface of the first layer to form a dry film, the film is first formed by coating the thermosetting resin composition on the film base. , forming the first layer. The film can be formed by heating the thermosetting resin composition to reduce the viscosity and coating it on the film base, or by diluting it with a solvent and coating it on the film base in advance, and then removing the solvent by heating. conduct. Next, the surface of the first layer formed on the film base material can be coated with a coating composition for imparting plating adhesion to form a film, thereby forming a second layer to prepare a dry film. For the film formation, the same method as described above can be used.

Furthermore, as described above, after forming the second layer on the film substrate, and then forming the first layer on the surface of the second layer to prepare a dry film, the second layer may be formed on the film substrate, and then, the first layer may be formed on the film substrate. The surface of the two layers was coated with the thermosetting resin composition to form the first layer, thereby producing a dry film. In addition, when the first layer and the second layer are formed separately, and the two are laminated to produce a dry film, the coating composition for imparting adhesion constituting the second layer and the thermosetting resin constituting the first layer may be combined The composition was applied to a film substrate, respectively, to form a film, and the two were laminated to produce a dry film.

Here, as the coating method, a conventionally known method can be applied, and a flat press method, a notch wheel coater, a knife coater, a lip coater, a rod coater, a extrusion coater, a reverse coater, etc. can be used. Known means such as coater, roll coater, gravure coater, spray coater, dip coater and the like. After coating, it is dried for 1 to 30 minutes at a temperature of 25 to 130°C. This drying can be performed using a hot air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like.

Film substrates include polyolefins such as polyethylene and polyvinyl chloride; polyesters such as polyethylene terephthalate; polycarbonate, polyimide, and further release paper or other materials such as copper foil and aluminum foil. Metal foil, etc. Furthermore, on the film substrate, matting treatment, corona treatment, and mold release treatment can also be performed.

In the dry film of the present invention produced in this way, the thickness of the first layer is preferably thicker than the thickness of the conductor circuit on the substrate adjacent to the first layer as an insulating material. For example, the thickness of the conductor circuit of the printed wiring board is approximately 5 to 100 μm, so the thickness of the first layer is preferably 10 to 120 μm. In addition, the thickness of the second layer is not particularly limited, but in a practical range, it is 0.01 to 5 μm, preferably 0.5 to 1 μm.

In the dry film of the present invention, the film base material may be peeled off after forming the first layer and the second layer, but the handleability can be improved by leaving it as a support (support film) as it is. In addition, on the surface of the non-film base material of the resin layer of the two-layer structure consisting of the first layer and the second layer, another film base material can be pasted as a protective material (protective film), so that damage or damage can be suppressed. Defects such as adhesion of foreign objects. As such a protective material (protective film), the same material as the above-mentioned film base material can be used, and it can be bonded together by a roll laminator or the like.

The dry film of this invention is laminated|stacked on the base material, such as a printed wiring board, so that a 1st layer (layer which consists of a thermosetting composition) may adjoin. Here, the lamination system uses a roll lamination machine, a batch type vacuum lamination machine, a vacuum pressing device, etc., under the conditions that the first layer will flow, such as a temperature of 30 to 130°C, a pressure of 1.5 MPa or less, and a time of 180 seconds or less. to implement.

＜＜＜hardened product＞＞＞ The cured product of the present invention can be obtained by heating the resin layer laminated using the dry film of the present invention to perform a curing reaction. Here, the hardening method is not particularly limited, and may be heated by, for example, an inert gas oven, a hot plate, a vacuum oven, a vacuum press, or the like. In addition, the heating temperature and time may be appropriately changed depending on the reactivity of the thermosetting component, for example, it is performed at 100 to 200° C. for 30 to 120 minutes.

＜＜＜Electronic Parts＞＞＞ The electronic component of the present invention has the above-mentioned cured product. More specifically, it has a cured product (layer) laminated in the order of the first layer and the second layer of the dry film of the present invention on a substrate on which a circuit is formed, such as a printed wiring board, and the second layer described above. A conductor layer (plating layer) formed by a plating process on the layer. Therefore, the dry film in which the said 1st layer and the 2nd layer were respectively formed may be laminated|stacked on a base material in this order of a 1st layer, and a 2nd layer, and it may be hardened.

As the manufacturing method of the electronic component of the present invention, for example, the cured product (layer) obtained by the above-mentioned dry film lamination method and curing method can be obtained by a CO ₂ laser or a UV-YAG laser or the like. Shots or drills to form holes (holes). The hole (hole) can be any one of a through hole (through hole) for the purpose of conducting the front and back surfaces of the substrate, and a bottomed hole (through hole) for the purpose of conducting the circuit on the substrate and the circuit on the second layer. .

After the holes (holes) are formed, the residues (smears) produced by the processing are removed by desmearing liquid or plasma treatment as required. Usually, the surface of the second layer may be roughened by smear removal. Considering the adaptation to high-frequency communication (such as 5G communication, etc.), the arithmetic mean surface roughness Ra (according to JIS) is usually required. B 0601) is 200 nm or less.

Next, the surface of the cured product (layer) can be irradiated with ultraviolet rays with an irradiation intensity of at least 10 mW/cm ² or more. Thereby, the adhesiveness of the surface of a hardened|cured material (layer) and a plated layer is further improved. The dominant wavelength of the ultraviolet rays at this time is about 310 nm or less, preferably about 260 nm or less, and more preferably about 150 to 200 nm. The wavelengths of the ultra-optimal ultraviolet rays include two kinds of about 184 nm and about 254 nm.

As the light source of ultraviolet rays, low-pressure mercury lamps, excimer lasers, barrier discharge lamps, dielectric barrier discharge lamps, microwave electrodeless discharge lamps, and instantaneous discharge lamps can be used. For example, when using a low-pressure mercury lamp, the dominant wavelengths of 184.9 nm and 253.7 nm are particularly effective. When using an excimer lamp, specifically, Ar2*(126nm), Kr2*(146nm), F2*(153nm), ArBr*(165nm), Xe2*(172nm), ArCl*(175nm), ArF(193nm), KrBr*(207nm), KrCl*(222nm), KrF(248nm), Xel*(253nm), Cl2*(259nm), XeBr*(283nm), Br2*(289nm), XeCl*(308nm) ) of the wavelength of light. Especially Xe2* and KrCl* have stability, small wavelength and high energy, so the surface modification effect is large and better.

Although the irradiation time of ultraviolet rays varies according to the resin material used and the intensity of ultraviolet rays (irradiation amount), (when the intensity of ultraviolet rays is about 5~20 mW/cm ² ), it can be adjusted appropriately in the range of about 10 seconds to 30 minutes. More preferably, it is about 20 seconds to 10 minutes.

In addition, the irradiation of an ultraviolet-ray may be performed several times before performing the process of electroless plating.

Next, a plating layer is formed on the surface of the cured product (layer). Plating metals are copper, tin, solder, nickel, etc., and are not particularly limited, and a plurality of them may be used in combination.

When forming a circuit with copper plating used for general electronic parts, as a feeding layer for performing electrolytic copper plating, electroless copper plating is performed with a thickness of about 0.1 to 2.0 μm, and then electrolytic copper plating is performed to form a specific Thickness of conductor layer (copper layer). The circuit pattern of the conductor layer can be formed by a known method such as a subtractive method or a semi-additive method. Furthermore, compared with nickel plating, copper plating has a difficulty in that the adhesion to resin is low, but when copper plating is applied to the surface of the insulating layer formed in accordance with the present invention to form a conductor layer, excellent results can be obtained. adhesion strength.

The electroless plating and electrolytic plating performed on the surface of the cured product are not limited to a specific method as long as it is a known method, and the catalyst in the electroless plating treatment step preferably contains a palladium-tin mixed catalyst, and The primary particle diameter of the catalyst is 10 nm or less. Furthermore, it is preferable that the plating composition of the electroless plating treatment step contains hypophosphorous acid as a reducing agent.

For electroless plating, methods described in, for example, Japanese Patent Laid-Open No. 8-253869, Japanese Patent Laid-Open No. 2002-57456, and Japanese Patent Laid-Open No. 2000-212762 can be applied.

In addition, the formation of the insulating layer and the plating adhesion layer with the dry film of the present invention, and the formation of the conductor circuit layer can be repeated as many times as necessary, thereby producing a desired multilayer printed wiring board.

Semiconductor elements and the like can be further packaged as electronic parts. The electronic components obtained by the present invention have less transmission loss of high-frequency electrical signals, and can be suitably used for large-capacity high-speed communications represented by the fifth-generation communication system (5G) or ADAS (advanced driving system) suitable for automobiles. Millimeter wave radar, etc. [Example]

The present invention will be described in more detail below using examples. In addition, the compounding quantity in a table|surface shows the mass part as a non-volatile component.

As the raw material of the curable resin composition, the following are used.

＜＜Ingredients＞＞ ＜Resin composition＞ • Epoxy resin (A) jER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A epoxy resin) NC-3000H (made by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin) • Phenolic resin (B) LA-3018-50P (manufactured by DIC Corporation, aminotriazine-containing phenol novolac resin, methyl ethyl ketone solution, non-volatile content 50% by mass, the description in Table 1 is not counting volatile content) HF-4M (Meiwa Chemical Co., Ltd., phenol novolak resin) • Active ester (C) HPC-8000-65T (manufactured by DIC Co., Ltd., toluene solution, non-volatile content 65% by mass, the description in Table 1 is not counting the volatile content) <Ingredients other than resin> •Inorganic fillers Admafine SC2050 ((stock) Admatechs) spherical silica (average particle size 0.5μm) • Hardening accelerator Curezol 2E4MZ (Shikoku Chemical Industry Co., Ltd.) •additive KBM-403 (Shin-Etsu Chemical Industry Co., Ltd.)

＜＜Preparation of curable resin composition＞ The above-mentioned respective raw materials were blended in the blending amounts shown in Table 1, and after stirring, they were uniformly dispersed with a 3-roll mill, and the curable resin compositions of the respective Examples and respective Comparative Examples were produced.

<<Preparation of coating composition for imparting plating adhesion>> A commercially available product, SIPAC300 manufactured by JCU Corporation, was prepared.

＜＜Production of sample (substrate)＞ Next, using each curable resin composition, a sample (substrate) for evaluation was produced according to the following procedure.

＜＜Production of dry film＞＞ First, each curable resin composition was thoroughly stirred and defoamed using an autorotation/revolution mixer, and then coated on a PET film with an applicator so that the film thickness after drying was 40 μm, and dried in a drying furnace at 90° C. for 10 Within minutes, a dry film having a layer (insulating layer) composed of each curable resin composition was produced. Next, the above-mentioned dry film provided with an insulating layer on the PET film was dip-coated with a coating composition (SIPAC300) for imparting adhesion, and was dried in a drying oven at 30° C. for 3 minutes in the state of being vertically suspended to form a 0.6 μm layer. The adhesion layer is plated, thereby producing a dry film in which the PET film, the insulating layer, the plating adhesion layer, and the PET film are laminated in sequence.

Next, peel off the PET film adjacent to the insulating layer of the prepared dry film, set the insulating layer to be adjacent to the copper-clad laminate, and use a vacuum laminating machine (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) at a temperature of 100 ℃, a pressure of 0.5 MPa, and a pressurization time of 30 seconds for superimposition. Then, the PET film on the plating adhesion layer side was peeled off, heated in a drying furnace at 90° C. for 30 minutes, and further heated at 170° C. for 30 minutes to prepare each plating substrate.

The surface average roughness Ra of each board|substrate for plating is shown in Table 1. In addition, the surface average roughness Ra was measured according to the following method. (test methods) Measuring machine: White interference microscope (Bruker Contour GT-I) Measurement conditions: VSI mode, 50x lens, measurement range 174.6×130.9 μm, the average value of 5 measurement points is the measurement value.

Next, electroless plating treatment and electrolytic plating treatment were performed on each of the produced substrates for plating to form conductor layers. Specifically, as an electroless plating treatment, immersion at 50° C. for 3 minutes in a detergent treatment solution (manufactured by JCU, ES-100), and immersion at 50° C. in a catalyst-imparting treatment solution (manufactured by JCU, ES-300) A feed layer was formed by immersing in a reduction treatment solution (manufactured by JCU, ES-400) for 2 minutes at 35°C for 5 minutes, and in an electroless plating treatment solution (manufactured by JCU, PB-507F) at 35°C for 15 minutes. Immerse in a 5% sulfuric acid aqueous solution for 10 seconds at room temperature, then in a copper sulfate plating solution (manufactured by JCU, CU-BRITE21) for 45 minutes at room temperature and a current density of 3A/dm ² to form an electrolytic plating layer. A sample (substrate) in which a copper-clad laminate, an insulating layer, a plating adhesion layer, and a plating layer are laminated.

＜＜Assessment＞＞ <Peel Strength (P/S) Test: Evaluation of Plating Adhesion> An evaluation of peel strength was performed for each sample. The peel strength was implemented as follows. First, the copper plating layer of each sample was cut with a width of 10 mm and a length of 60 mm. The one end was peeled off, and the peeled part was clamped with a clamp, and a 35 mm portion of the copper plating layer was peeled off at an angle of 90 degrees and a speed of 50 mm/min with a desktop tensile tester (EZ-SX, manufactured by Shimadzu Corporation). length, and the peel strength (N/cm) was measured.

From the above results, it was confirmed that by using the dry film of the two-layer structure, the dry film of the two-layer structure had a layer composed of a curable resin composition containing an epoxy resin and an active ester compound, and a layer composed of a curable resin composition containing an epoxy resin and an active ester compound, and a dry film containing an acrylic resin. A layer composed of a resin and a composition for forming a plating layer containing a catalyst metal silicon oligomer can form an insulating layer with good adhesion to the conductor layer even if the surface roughness is small (even if Ra is 200 nm or less). layer.

Claims (3)

A dry film, which is a dry film having a resin layer with a two-layer structure on a film substrate, the two-layer structure of the resin layer is composed of a layer of a curable resin composition containing an epoxy resin and an active ester compound, and a layer containing an acrylic acid. It is composed of a layer of a resin and a coating composition containing a catalyst metal silicon oligomer that imparts plating adhesion. The dry film is characterized by The aforementioned catalyst-containing metal-silicon oligomer is obtained by making a tetraalkoxysilane bond with a hydroxyl group at least at the n, n+1 position or n, n+2 position (only n is an integer of 1 or more). The polyol is a catalyst-containing metal-silicon oligomer obtained by condensation reaction in the presence of a metal having catalytic properties for electroless plating. A cured product obtained by curing a resin layer constituting the dry film of claim 1. An electronic part having an insulating layer containing the hardened product as claimed in claim 2.