JP2008255140A - Epoxy resin-molded article, method for modifying surface of epoxy resin-molded article, and method for forming electroconductive film by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin-molded article of which surface is modified by a simple method without roughening the surface of the epoxy resin-molded article, a method for modifying the surface of the same, and a method for forming an electroconductive film, capable of easily forming the electroconductive film on the epoxy resin-molded material of which surface is modified by the above modifying method. <P>SOLUTION: This epoxy resin-molded material formed by curing a mixture of the epoxy resin and an acrylic resin is characterized by having ≥80 strength of the acrylic resin component within 30% thickness region from its surface based on the whole thickness of the epoxy resin-molded article, in the case of setting the strength by the mass analysis of the acrylic resin component in the surface of the epoxy resin-molded material as 100. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for modifying the surface of a molded body mainly composed of an epoxy resin and a method for forming a conductive film using the same, and more particularly to a method for forming a conductive film useful for a printed wiring board.

Conventionally, an epoxy resin substrate mainly composed of an epoxy resin is most commonly used as an insulating substrate for a printed wiring board, and a circuit is formed by forming a conductor with a predetermined pattern on the surface of the epoxy resin substrate. It is formed.
As a method of forming a conductor (conductive film) on an epoxy resin substrate, a method of chemically treating the surface of the epoxy resin substrate with a desmear liquid (desmear treatment) to form irregularities (roughening), an epoxy resin A method of performing electroless plating by adsorbing a plating catalyst after making the surface of a substrate hydrophilic is known. As a hydrophilization method, UV ozone treatment, corona treatment, plasma treatment, treatment with a photocatalyst, etc. are known (for example, Non-Patent Document 1).

  However, the desmear treatment has a problem that the substrate surface becomes rough and the high-frequency characteristics deteriorate. In addition, the UV ozone treatment, corona treatment, and plasma treatment are not as high as desmear treatment, but the substrate surface is damaged and slightly roughened, and each device requires a special surface treatment, resulting in high costs. There is a problem of becoming. Furthermore, the treatment with the photocatalyst is specifically a method of immersing the substrate in an aqueous dispersion of titanium dioxide and then irradiating with UV light for a long time to make hydrophilic using the oxidizing power of the photocatalyst. For example, it is difficult to say that this is a practical method for manufacturing a printed wiring board.

  On the other hand, a method has been proposed in which a polymer having a polymerizable group is applied to the surface of an epoxy resin substrate, and then an ultraviolet ray is irradiated to generate a graft polymer on the substrate surface, and a conductive material is imparted to the surface graft polymer. (For example, patent document 1). However, it cannot be said that the adhesion between the epoxy resin substrate and the graft polymer is sufficient, and since the application of the polymer and the ultraviolet irradiation are necessary, the cost may increase.

Abstracts of the 44th Annual Meeting of the Adhesion Society of Japan p181-184 JP 2006-57059 A

  Various methods for modifying the surface of the epoxy resin substrate have been proposed as described above, but the surface of the epoxy resin substrate can be modified by a simple method without roughening the surface of the epoxy resin substrate. The method is desirable.

  The present invention has been made in consideration of the above-mentioned conventional technical problems, and the epoxy resin surface is modified by a simple method without roughening the surface of the epoxy resin molded body. It is an object of the present invention to provide a body and a surface modification method thereof. Another object of the present invention is to form a conductive film capable of easily forming a conductive film on an epoxy resin molded body whose surface is modified by the surface modification method of the epoxy resin molded body of the present invention. It is to provide a method.

  In order to achieve the above object, the present invention provides the following method.

<1> An epoxy resin molded body in which a mixture of an epoxy resin and an acrylic resin is cured, and in a region having a thickness within 30% from the surface with respect to the total thickness of the epoxy resin molded body,
An epoxy resin molded body, wherein the strength of the acrylic resin composition in the region is 80 or more when the strength by mass spectrometry of the acrylic resin composition on the surface of the epoxy resin molded body is 100.

<2> The epoxy resin molded body according to <1>, wherein the thickness from the surface is within 20% of the total thickness of the epoxy resin molded body.

<3> The epoxy resin molded body according to <1> or <2>, wherein the thickness from the surface is within 10% of the total thickness of the epoxy resin molded body.

<4> The epoxy resin molded article according to any one of <1> to <3>, wherein the mass spectrometry is SIMS (secondary ion mass spectrometry).

<5> The epoxy resin molded body according to any one of <1> to <4>, wherein the acrylic resin has an SP value in a range of 20 to 29.

<6> The epoxy resin molded body according to any one of <1> to <5>, wherein the acrylic resin has an SP value in a range of 23 to 28.

<7> The epoxy resin molded article according to any one of <1> to <6>, wherein the content of the acrylic resin is 1 to 10% by mass as a concentration in the total solid content. .

<8> The epoxy resin molded article according to any one of <1> to <7>, wherein the acrylic resin has a functional group capable of adsorbing a plating catalyst in a molecule.

<9> The epoxy resin molded article according to <8>, wherein the functional group capable of adsorbing the plating catalyst is a cyano group, an amino group, or a nitrogen-containing heterocyclic group.

<10> The epoxy resin molded body according to any one of <1> to <9>, wherein the mixture of the epoxy resin and the acrylic resin further contains a curing agent.

<11> The epoxy resin molded article according to <10>, wherein the curing agent contains at least one of an amino group and a hydroxyl group in the molecule.

<12> The epoxy resin molded body according to any one of <1> to <11>, wherein the mixture of the epoxy resin and the acrylic resin further contains a phenoxy resin.

<13> The epoxy resin molded body according to any one of <1> to <12>, wherein the mixture of the epoxy resin and the acrylic resin further includes a curing accelerator.

<14> Epoxy resin, a curing agent that reacts with the epoxy resin, a solvent, and an SP value in the range of 20 to 29, and a mixture containing 1 to 10% by mass of acrylic resin as a concentration in the total solid content A method for modifying the surface of an epoxy resin molded product, comprising the steps of:

<15> The method for modifying a surface of an epoxy resin molded article according to <14>, wherein the acrylic resin has an SP value in the range of 23 to 28.

<16> The method for modifying a surface of an epoxy resin molded article according to <14>, wherein the solvent contains a ketone solvent.

<17> The method for modifying a surface of an epoxy resin molded article according to <16>, wherein at least one of methyl ethyl ketone and cyclohexanone is used as the ketone solvent.

<18> A step of applying an electroless plating catalyst or a precursor thereof to the surface of the epoxy resin molded body according to any one of <1> to <13>, and the electroless plating catalyst or the precursor thereof. A process for forming a conductive film by performing electroless plating on the applied epoxy resin mixture.

<19> The method for forming a conductive film according to <18>, wherein the electroless plating catalyst is palladium.

  According to the present invention, an epoxy resin mixture in which an acrylic resin is added to a mixture containing an epoxy resin as a main component is molded and cured by heating to form an epoxy resin molded body, whereby the surface of the epoxy resin molded body is acrylic. It is possible to provide an epoxy resin molded body that has been efficiently modified with a resin. According to such a method, the surface modification of the epoxy resin molded body can be performed by a simple method without roughening the surface of the epoxy resin molded body. Further, by selecting an acrylic resin, it is possible to easily form a conductive film on the surface-modified epoxy resin molded body.

The method for modifying the surface of an epoxy resin molded body according to the present invention includes molding an epoxy resin mixture containing an epoxy resin, a curing agent that reacts with the epoxy resin, an acrylic resin, and a solvent, and curing the epoxy resin. It includes a step of forming an epoxy resin molded body segregated on the surface.
As a result of intensive studies, the present inventors have determined that the epoxy resin substrate formed by heat curing is chemically or chemically treated by desmear treatment, UV ozone treatment, corona treatment, plasma treatment, photocatalytic treatment, etc. Rather than physical treatment, when forming an epoxy resin substrate, the epoxy resin mixture to which a small amount of acrylic resin is added is molded into a molded product that is heat-cured, so that almost the original physical properties of the epoxy resin are obtained. It has been found that the surface can be efficiently modified with acrylic resin without damage. In particular, by using an acrylic resin having a functional group capable of adsorbing a plating catalyst, it is possible to form a surface with good plating catalyst adsorption, and after applying the plating catalyst, electroless plating is performed to form a conductive film. It has been found that it can be reliably formed.

<Epoxy resin>
The epoxy resin used in the present invention is an epoxy compound having two or more epoxy groups in one molecule, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule. It is. The epoxy group may be a structure having an oxirane ring structure, and examples thereof include a glycidyl group, an oxyethylene group, and an epoxycyclohexyl group. Such polyvalent epoxy compounds are widely disclosed in, for example, published by Masaki Shinbo “Epoxy Resin Handbook” published by Nikkan Kogyo Shimbun (1987), and these can be used.

  Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin. These may be used alone or in combination of two or more. Use of a polyfunctional epoxy, an epoxy with a low epoxy equivalent, a naphthalene type epoxy, a dicyclopentadiene type epoxy or the like provides an epoxy resin excellent in heat resistance.

  The concentration of the epoxy resin in the total solid content is preferably 20% by mass or more, more preferably 30 to 80% by mass, and more preferably 40 to 60% by mass in the total solid content contained in the resin mixture. % Is particularly preferred.

<Mass spectrometry>
In the epoxy resin molded body of the present invention, the acrylic resin distribution is non-uniform in the epoxy resin molded body and is concentrated on the surface layer (outer periphery) portion. This is called “segregation” in the present invention. The segregation state of the acrylic resin in the epoxy resin molded body can be analyzed using various analysis methods. In the present invention, when the epoxy resin molded body is formed on various substrates, the surface and the surface layer portion refer to the interface with the air on the opposite side of the substrate, and when not formed on the substrate, the epoxy It refers to the interface with the air at the outer periphery of the resin molded body.
As a method for analyzing the segregation state of the epoxy resin molded body in the present invention, secondary ion mass spectrometry can be suitably used. As a method that can be preferably used by analyzing the segregation state of the epoxy resin molding of the present invention, TOF-SIMS (time-of-flight secondary ion mass spectrometry) can be mentioned. When TOF-SIMS irradiates a sample surface (solid) with an ion beam with energy of several hundreds to tens of thousands of eV, some of the atoms in the sample that received the energy jump out as particles. Most of the ejected particles are electrically neutral, but some are charged (charged) into ions (called secondary ions) and separated according to the mass / charge ratio. be able to. This is a method of analyzing the chemical composition and isotope composition of a sample by counting the ions thus separated.

  The segregation state of the epoxy resin molded article of the present invention can be obtained from the vertical axis (detection intensity) of the spectrum obtained by the mass spectrometry. For example, when the epoxy resin molding of the present invention is obliquely cut and the distribution is measured using TOF-SIMS (PHI-TRIFT II), the spectrum curve is shown in the region where the acrylic resin is segregated according to the acrylic resin content. Obtainable. It can be seen from the curve that the acrylic resin is segregated near the surface of the epoxy resin molded body. In the present invention, when the strength of the outermost surface of the epoxy resin molded body in which the acrylic resin is segregated is 100, the relative value of the portion having the acrylic resin content of 80 or more is the total thickness of the epoxy resin molded body. On the other hand, the thickness is within 30% from the surface, and the thickness from the surface is preferably 20% or less, more preferably 10% or less.

The method for analyzing the segregation state of the epoxy resin molding of the present invention is not limited to the above method as long as the segregation state can be analyzed. For example, an electron probe microanalyzer (EPMA) or an X-ray photoelectron spectrometer ( XPS), ultra-low accelerating voltage scanning electron microscope, Auger electron spectroscopy, glow discharge emission spectroscopy, Raman scattering spectroscopy, etc. can be used.
In the present invention, for example, the measurement conditions of TOF-SIMS include primary ion Au +, acceleration voltage: 22 kV, primary ion current: 2 nA, neutralization gun on, spectrum measurement (positive / negative), bunching, measurement area: The segregation state can be analyzed by 80 μm □ and the measurement time of 3 min. However, the segregation state is not limited to this condition, and the measurement can be performed under desired conditions as long as the segregation state can be confirmed.
Furthermore, in the present invention, in a single measurement, it is sufficient that there is a portion having an acrylic resin content (relative value) of 80 or more even with respect to the surface region, preferably the acrylic resin content. It is preferable that the part whose amount (relative value) is 80 or more occupies more than half of the surface area.

<Curing agent>
As the curing agent that reacts with the epoxy resin, a compound having a functional group that reacts with two or more epoxy groups in one molecule (referred to as a curing agent in the present invention) is used. Examples of the functional group in such a curing agent include a functional group such as a carboxyl group, a hydroxyl group, an amino group, and a thiol group.
Specific examples of curing agents include polyfunctional carboxylic acid compounds such as terephthalic acid, bifunctional phenol compounds such as bisphenol A, bisphenol F, bisphenol S, resorcinol derivatives, and catechol derivatives, phenol resins such as phenol novolac resins and cresol novolac resins. And polyfunctional amino compounds such as amino resin, 1,3,5-triaminotriazine, and 4,4′-diaminodiphenylsulfone. Among these, a compound having at least one of a hydroxyl group and an amino group as a functional group that reacts with an epoxy group is preferably used as a curing agent.

  As the addition amount of the curing agent, the ratio of the functional group of the curing agent to the epoxy group in the epoxy resin (solid content of the curing agent (g) / curing agent equivalent) / (solid content of the epoxy resin (g) / Epoxy equivalent) is preferably 0.1 to 5.0, more preferably 0.3 to 2.0. In the above definition formula, the equivalent means the number of functional groups per molecule, the number of functional groups that react with an epoxy group as a curing agent, and the number of epoxy groups as an epoxy resin.

<Acrylic resin>
Acrylic resin is added to reform the surface properties by imparting a function to the surface of the epoxy resin molded body (surface modification), and the function of the functional group contained in the acrylic resin is epoxy resin molding. It will be reflected in the surface characteristics of the body. Various functional groups such as a hydrophilic group, a hydrophobic group, and a photosensitive group can be used as the functional group contained in the acrylic resin. In addition, by using an acrylic resin having a plating catalyst-adsorptive group, it is possible to conduct plating by forming a plating on the surface of the epoxy resin molded body. The functional group capable of adsorbing the plating catalyst preferably has at least one of a cyano group, an amino group, and a nitrogen-containing heterocyclic group.

The functional group and functional group other than the functional group contained in the acrylic resin are preferably groups that do not react with the epoxy resin. If the acrylic resin has a functional group that reacts with the epoxy resin, it will react with the epoxy resin during heat curing, and the acrylic resin will be present in the epoxy resin in a nearly uniform distribution, making surface modification efficient. There is a risk that it will not be performed.
As the functional group other than the functional group contained in the acrylic resin, various functional groups can be selected from the viewpoint of imparting solubility to an organic solvent as long as the functional group does not react with the epoxy resin. In addition, it is preferable that photosensitive groups, such as an acryloyl group and a methacryloyl group, are included from the point of fixing an acrylic resin on the surface of an epoxy resin molding after surface segregation.

  Moreover, it becomes easy to control the degree of surface segregation by controlling the SP (Solubility Parameter) value as a physical property value of the acrylic resin. The SP value is a value represented by the cohesive energy density, that is, the square root of the evaporation energy per unit volume of one molecule. As SP value (Okitsu method) of the acrylic resin used by this invention, 20-29 are preferable and 23-28 are especially preferable. The Okitsu method is one of the methods for calculating the SP value. 29, no. 6 (1993) pages 249 to 259. In the case of an acrylic resin, a weighted average value was adopted according to the molar ratio of copolymerization components.

  Moreover, although the addition amount of an acrylic resin changes also with the SP value, surface modification | reformation is possible with a small amount of acrylic resin, As a density | concentration in a total solid, 0.01-30 mass% is preferable, and 1 10 mass% is especially preferable.

  Examples of the acrylic resin that can be used in the present invention include adsorption of photosensitive groups and plating catalysts described in Japanese Patent Application No. 2006-53430, paragraph numbers [0095] to [0097], Japanese Patent Application No. 2006-287930, and the like. An acrylic resin containing a functional group can be given. Specifically, the following compounds can be mentioned.

In the present invention, the acrylic resin may or may not have a photosensitive group, but when it has a photosensitive group, on the surface of the epoxy resin molded body produced in the present invention, Furthermore, a polymer etc. can be couple | bonded by polymerization reaction.
Examples of the acrylic resin containing a photosensitive group and a plating catalyst adsorbing group include copolymer polymers represented by the following general formula (1) and general formula (2).

In general formulas (1) and (2), R ^{1 to} R ⁵ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and Y independently represents a single bond or a substituted In addition, it represents an unsubstituted divalent organic group, an ester group, an amide group, or an ether group, and L ¹ and L ² each independently represent a substituted or unsubstituted divalent organic group.

When R ^{1 to} R ⁵ are substituted or unsubstituted alkyl groups, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the substituted alkyl group include methoxy And a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a group, a hydroxy group, chlorine, bromine, fluorine and the like.
R ¹ is preferably a hydrogen atom, a methyl group, a hydroxyl group, or a methyl group substituted with bromine.
R ² is preferably a hydrogen atom, a methyl group, a hydroxyl group, or a methyl group substituted with bromine.
R ³ is preferably a hydrogen atom.
R ⁴ is preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom or a methyl group.

When Y is a substituted or unsubstituted divalent organic group, examples of the organic group of the divalent organic group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
As the aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, a butylene group, or a group in which these groups are substituted with a methoxy group, a hydroxy group, chlorine, bromine, fluorine or the like is preferable.
As the aromatic hydrocarbon group, an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, a hydroxy group, chlorine, bromine, fluorine or the like is preferable.
Among _{them, - (CH 2) n- (} n is an integer of 1 to 3) are preferred, more preferably, -CH ₂ - is.

L ¹ is preferably a divalent organic group having a urethane bond or a urea bond, and among them, those having a total carbon number of 1 to 9 are preferable. Incidentally, the total number of carbon atoms of L ^1, means the total number of carbon atoms contained in L ^1.
More specifically, the structure of L ¹ is preferably a structure represented by the following formula (1-1).

In the general formula (1-1), R ^a and R ^b each independently represent a substituted or unsubstituted methylene group, ethylene group, propylene group, or butylene group.

L ² is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group in which these are combined with a single bond, an ether group, an ester group, an amide group, a urethane group, or a urea group. . Among them, ^{L 2} is preferably a total carbon number of 1 to 15. Incidentally, the total number of carbon atoms of L ^2, means the total number of carbon atoms contained in L ^2.
Specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, or a group in which these groups are substituted with a methoxy group, a hydroxy group, chlorine, bromine, fluorine, or the like, or a combination thereof. Groups.

  As the acrylic resin of the present invention, the unit represented by the formula (1) is preferably a unit represented by the following formula (3).

In the above formula (3), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and Z represents a single bond or a substituted or unsubstituted divalent organic group. Represents a group, an ester group, an amide group, or an ether group, W represents a nitrogen atom or an oxygen atom, and L ¹ represents a substituted or unsubstituted divalent organic group.

^{R 1} and ^{R 2} in Formula (3), the formula (1) has the same meaning as ^{R 1} or ^{R 2} in, are the preferable examples.

Z in formula (3) has the same meaning as Z in formula (1), and the preferred examples are also the same.
Further, ^{L 1} in the formula (3) also has the same meaning as ^{L 1} in Formula (1), and preferred examples are also the same.

As the acrylic resin of the present invention, the unit represented by the formula (3) is preferably a unit represented by the following formula (4).

In formula (4), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and V and W each independently represent a nitrogen atom or an oxygen atom. , L ¹ represents a substituted or unsubstituted divalent organic group.

^{R 1} and ^{R 2} in the formula (4), the formula (1) have the same meanings as ^{R 1} and ^{R 2} in, and so are the preferable examples.

L ¹ in Formula (4) has the same meaning as L ¹ in Formula (1), and the preferred examples are also the same.

In the formulas (3) and (4), W is preferably an oxygen atom.
In the formulas (3) and (4), L ¹ is preferably an unsubstituted alkylene, a divalent organic group having a urethane bond or a urea bond, and particularly one having a total carbon number of 1 to 9. preferable.

  Moreover, as an acrylic resin of this invention, it is preferable that the unit represented by the said Formula (2) is a unit represented by following formula (5).

In the above formula (5), R ² represents a hydrogen atom or a substituted or unsubstituted alkyl group, U represents a nitrogen atom or an oxygen atom, and L ² represents a substituted or unsubstituted divalent organic group. Represents a group.

R ² in Formula (5) has the same meaning as R ¹ and R ² in Formula (1), and is preferably a hydrogen atom.

L ² in Formula (5) has the same meaning as L ² in Formula (1), and is a linear, branched, or cyclic alkylene group, aromatic group, or a single bond, ether group, ester group thereof. , An amide group, a urethane group, and a urea group are preferable.
In particular, in formula (5), L ² is preferably a divalent organic group having a linear, branched, or cyclic alkylene group at the site of connection with the nitrile group. The organic group preferably has 1 to 10 carbon atoms.
As another preferred embodiment, L ² in formula (5) is preferably a divalent organic group having an aromatic group at the site of connection with the nitrile group, and among these, the divalent organic group However, it is preferable that it is C6-C15.

The acrylic resin of the present invention comprises a unit represented by the above formulas (1) to (5), and is a polymer having a photosensitive group and a nitrile group in the side chain.
This acrylic resin can be synthesized, for example, as follows.

  As synthesis methods, i) a method in which a monomer having a nitrile group and a monomer having a photosensitive group are copolymerized, ii) a monomer having a nitrile group and a monomer having a double bond precursor are copolymerized, Examples thereof include a method of introducing a double bond by treatment with a base or the like, and iii) a method of introducing a double bond (introducing a photosensitive group) by reacting a polymer having a nitrile group with a monomer having a photosensitive group. From the viewpoint of synthesis suitability, ii) a method in which a monomer having a nitrile group and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like, iii) nitrile In this method, a polymer having a group and a monomer having a photosensitive group are reacted to introduce a photosensitive group.

  Examples of the monomer having a photosensitive group used in the synthesis method i) include allyl (meth) acrylate and the following compounds.

  Examples of the monomer having a double bond precursor used in the synthesis method ii) include compounds represented by the following formula (a).

In the above formula (a), A is an organic group having a photosensitive group, R ^{1 to} R ³ are each independently a hydrogen atom or a monovalent organic group, and B and C are removed by elimination reaction. This is a leaving group, and the elimination reaction referred to here is one in which C is extracted by the action of a base and B is eliminated. B is preferably eliminated as an anion and C as a cation.
Specific examples of the compound represented by the formula (a) include the following compounds.

  Further, in the synthesis method of ii), in order to convert the double bond precursor into a double bond, as shown below, a method for removing the leaving groups represented by B and C by elimination reaction, That is, a reaction in which C is extracted by the action of a base and B is eliminated is used.

  Preferred examples of the base used in the elimination reaction include alkali metal hydrides, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds. Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, Examples include potassium hydrogen carbonate and sodium hydrogen carbonate. Preferable examples of the organic amine compound include trimethylamine, triethylamine, diethylmethylamine, tributylamine, triisobutylamine, trihexylamine, trioctylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N- Methyldicyclohexylamine, N-ethyldicyclohexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, 1,4-dimethyl Piperazine, quinuclidine, 1,4-diazabicyclo [2,2,2] -octane, hexamethylenetetramine, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, Cytidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), N, N'-dicyclohexylcarbodiimide (DCC), diisopropylethylamine, Schiff base, and the like. Preferable examples of the metal alkoxide compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These bases may be used alone or in combination of two or more.

  Examples of the solvent used for adding (adding) the base in the elimination reaction include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate , Ethyl lactate, water and the like. These solvents may be used alone or in combination of two or more.

  The amount of the base used may be equal to or less than the equivalent to the amount of the specific functional group (the leaving group represented by B or C) in the compound, or may be equal to or more than the equivalent. Moreover, when an excess base is used, it is also a preferred form to add an acid or the like for the purpose of removing the excess base after the elimination reaction.

In the synthesis method of iii), the monomer having a photosensitive group to be reacted with the polymer having a nitrile group varies depending on the kind of the reactive group in the polymer having a nitrile group, but the monomer having the following combination of functional groups: Can be used.
That is, (reactive group of polymer, functional group of reactive compound) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, benzyl halide), (Hydroxyl group, carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, halogenated benzyl) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group) and the like.
Specifically, the following monomers can be used.

As for the acrylic resin of this invention synthesize | combined as mentioned above, it is preferable that the ratio of a photosensitive group containing unit and a nitrile group containing unit is the following ranges with respect to the whole copolymerization component.
That is, the photosensitive group-containing unit is preferably contained in an amount of 5 to 50 mol%, more preferably 5 to 40 mol%, based on the entire copolymer component. If it is 5 mol% or less, the reactivity (curability and polymerizability) is lowered, and if it is 50 mol% or more, it is easily gelled during synthesis and is difficult to synthesize.
Moreover, it is preferable that a cyano group containing unit is contained by 1-95 mol% with respect to the whole copolymerization component, More preferably, it is 10-95 mol%.

In addition, the acrylic resin of this invention may contain other units other than a cyano group containing unit and a photosensitive group containing unit. As the monomer used for forming the other unit, any monomer can be used as long as it does not impair the effects of the present invention.
However, when the photosensitive group is introduced after reacting with the polymer as described above, it is difficult to introduce 100%, and a small amount of reactive portion remains, which may be the third unit. There is also.
Specifically, when the polymer main chain is formed by radical polymerization, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl Unsubstituted (meth) acrylates such as (meth) acrylate and stearyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, Halogen-substituted (meth) acrylic esters such as 2-chloroethyl (meth) acrylate, ammonium group-substituted (meth) acrylic esters such as 2- (meth) acryloyloxyethyltrimethylammonium chloride, butyl (meth) acrylamide, Iso (Meth) acrylamides such as propyl (meth) acrylamide, octyl (meth) acrylamide, dimethyl (meth) acrylamide, styrenes such as styrene, vinylbenzoic acid, p-vinylbenzylammonium chloride, N-vinylcarbazole, vinyl acetate, Vinyl compounds such as N-vinylacetamide and N-vinylcaprolactam, and dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-ethylthio-ethyl (meth) acrylate, (meth) acrylic acid, 2 -Hydroxyethyl (meth) acrylate etc. can be used.
Moreover, the macromonomer obtained using the monomer of the said description can also be used.

  When the polymer main chain is formed by cationic polymerization, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol vinyl ether, di (ethylene glycol) vinyl ether, 1,4-butanediol vinyl ether, 2-chloroethyl vinyl ether, 2 -Vinyl ethers such as ethylhexyl vinyl ether, vinyl acetate, 2-vinyloxytetrahydropyran, vinyl benzoate, vinyl butyrate, styrenes such as styrene, p-chlorostyrene, p-methoxystyrene, allyl alcohol, 4-hydroxy-1- Terminal ethylenes such as butene can be used.

  The molecular weight (Mw) of the acrylic resin of the present invention is preferably 3000 to 200,000, more preferably 4000 to 100,000.

Specific examples of the acrylic resin used in the present invention are shown below. However, the copolymer which can be used in the present invention is not limited to these.
In addition, as for the weight average molecular weight of these specific examples, all are the range of 3000-100000.

  For example, when preparing compound 2-2-11, acrylic acid and 2-cyanoethyl acrylate are dissolved in N-methylpyrrolidone, for example, and radical polymerization is performed using, for example, azoisobutyronitrile (AIBN) as a polymerization initiator. Thereafter, glycidyl methacrylate can be synthesized by addition reaction using a catalyst such as benzyltriethylammonium chloride and a polymerization inhibitor such as tertiary butylhydroquinone. For example, when compound 2-2-19 is prepared, the following monomers and p-cyanobenzyl acrylate are dissolved in a solvent such as N, N-dimethylacrylamide, and dimethyl azoisobutyrate is used as a polymerization initiator. It can be synthesized by performing radical polymerization using a suitable polymerization initiator and then dehydrochlorinating using a base such as triethylamine.

  The epoxy resin mixture (polymer alloy) used in the present invention is required to contain the above epoxy resin, curing agent, and acrylic resin as the resin component, but other components depending on the purpose and the like. Can also be added.

<Curing accelerator>
For example, a curing accelerator for further promoting thermal curing may be added. As the curing accelerator, imidazole compounds such as 2-ethyl-4-methylimidazole, pyridine compounds such as 4-dimethylaminopyridine, organic phosphine compounds such as triphenylphosphine, and the like can be used. When blending such a curing accelerator, the blending amount is within the range of 0.5 to 2% by weight, for example, when the blending amount of the curing agent such as the phenol-based curing agent is 100% by weight. It is preferable.

<Thermoplastic resin>
Furthermore, a thermoplastic resin can be blended.
In recent years, high melting point solder that does not use lead is becoming mainstream as a solder used in the field of semiconductor encapsulating materials and printed wiring boards due to environmental regulations. For this reason, for example, the reflow temperature at the time of mounting the semiconductor chip rises from the conventional temperature, and cracks tend to occur inside the insulating layer due to the high temperature at the time of reflow. For this reason, high heat resistance and reduction of stress generation are desired for the epoxy resin molded body constituting the printed wiring board.

Therefore, as a method for imparting crack resistance, a thermoplastic resin can be mixed in order to relieve the generated stress. Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenylene ether, polyether imide, and the like. Examples of other thermoplastic resins include the following thermoplastic resins (1) to (3).
(1) 1,2-bis (vinylphenyl) ethane resin (1,2-Bis (vinylphenyl) ethane resin) or a modified resin of this and a polyphenylene ether resin (Satoru Ama et al., Journal of Applied Polymer Science Vol. 92, 1252-1258 (2004))
(2) Liquid crystalline polymers (Kuraray "Bexstar" etc.)
(3) Fluororesin (PTFE etc.)
In addition, as a thermosetting resin used by this invention, a phenoxy resin is preferable from the grade of stress relaxation among the above.

  The thermoplastic resins may be used alone or in combination of two or more. As content of a thermoplastic resin, in order to fully exhibit the stress relaxation effect, 10 mass%-80 mass% in total solid content are preferable, and 30 mass%-60 mass% are more preferable.

  In addition, the addition amount of components other than the epoxy resin as described above is preferably in the range of 30 to 300% by mass, more preferably in the range of 50 to 200% by mass with respect to the epoxy resin. If the blending amount of the other additive component is 30% by mass or more with respect to the epoxy resin, the effect of the additive component can be sufficiently obtained. It can prevent effectively that characteristics, such as intensity, fall.

<Solvent>
Examples of the solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, aromatic hydrocarbons such as toluene and xylene, methoxypropanol, dimethylformamide, Examples thereof include dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and the like. Of these, ketone solvents are preferable, and methyl ethyl ketone and cyclohexanone are particularly preferable. Any kind of solvent may be used alone, or two or more kinds of mixed solvents may be used.
The content of the solvent is preferably 20% by mass to 90% by mass and more preferably 30% by mass to 60% by mass in the total mixture from the viewpoint of easy application of the resin mixture.

-Molding (heat curing) process-
After preparing an epoxy resin mixture containing the epoxy resin as described above, a curing agent that reacts with the epoxy resin, an acrylic resin, and a solvent, and further containing a curing accelerator, a thermoplastic resin, etc., if necessary, this epoxy resin The mixture is molded and heat-cured to form an epoxy resin molded body in which the acrylic resin is segregated on the surface. In addition, the shape, thickness, etc. are not specifically limited with the epoxy resin molding as used in the field of this invention, For example, it is good also as a layer form of thickness of micrometer order, and can also be set as the board | substrate form of mm order. Moreover, a molded object is not restricted to flat form, For example, it is good also as a shape which has a curved shape and an unevenness | corrugation, and thickness does not necessarily need to be uniform.

The method for forming the epoxy resin molded body is not particularly limited as long as the acrylic resin segregates on the surface layer after the epoxy resin mixture is molded and heat-cured. Usually, the liquid epoxy resin mixture (varnish) is applied onto a support, and is cured by heating in a state of being formed into a predetermined shape and thickness. The method for applying the epoxy resin mixture onto the support is not particularly limited, and may be selected according to the purpose or the like. For example, knife coating, roll coating, curtain coating, spin coating, dip coating, bar coating, etc. can be employed. The thickness of the epoxy resin mixture applied on the support is not particularly limited, and may be determined according to the ratio of the solvent and the purpose of the epoxy resin molded body obtained after heat curing, but is preferably 0.5 μm or more, and 3 μm. By setting it as the above, the effect of this invention can be acquired more highly.
The material of the support may be selected according to the purpose and the like, and may be a plastic material such as polyimide, or a non-plastic material such as metal or paper. Further, the shape of the support is not particularly limited, and a desired shape can be adopted in addition to the plate shape. The support may be integrated with the heat-cured epoxy resin molding, or may be separated from the support after the heat-curing. In this case, for example, a release agent may be provided on the support in advance.

  After the epoxy resin mixture is applied on the support and molded, heat curing is performed. In addition, when an epoxy resin mixture is provided on a support and then heat-cured immediately, the acrylic resin may be cured without being sufficiently segregated on the surface. Although it depends on the component ratio of each resin component and solvent, the film thickness, etc., usually, after applying a liquid epoxy resin mixture (varnish) on the support, it is at least 5 minutes, preferably 10 minutes to 30 minutes at room temperature. put.

The heat curing conditions depend on the component ratio of the resin mixture, the film thickness, and the like, but generally the heating temperature is preferably 20 to 200 ° C, more preferably 80 to 180 ° C. The heating time is preferably 1 second to 50 hours, more preferably 10 seconds to 10 hours. By adopting such heating conditions, the acrylic resin can be more reliably deposited on the surface.
As described above, the epoxy resin mixture according to the present invention is applied and molded on the support, and further heat-cured, whereby the acrylic resin is segregated on the surface in the process of heat-curing. Thereby, the epoxy resin molded object in which the acrylic resin surface-segregated can be formed.

According to the method as described above, the surface of the epoxy resin can be efficiently modified by adding a small amount of an acrylic resin to the epoxy resin without substantially impairing the original physical properties of the epoxy resin. In addition, since it is a one-step method that performs surface modification at the same time as heat curing, it is simpler and less expensive than, for example, a method of forming an epoxy resin substrate and then applying an acrylic resin to the surface. It is extremely practical. In addition, unlike the method of applying an acrylic resin, since there is no clear interface between the epoxy resin and the surface segregated acrylic resin, the adhesion is excellent. Furthermore, by selecting an acrylic resin having various types of functional groups according to the purpose, the surface of the epoxy resin molded body can be modified to a surface having a desired function by a simple method.
The method for confirming that the acrylic resin is segregated on the surface (surface layer) of the epoxy resin molded body obtained as described above is not particularly limited. For example, the molded body is cut obliquely. The cut surface can be analyzed and examined by a time-of-flight secondary ion mass spectrometer, an optical microscope, an electron microscope, or the like.

  The use of the epoxy resin molded body whose surface has been modified as described above is not particularly limited. For example, when an acrylic resin having a functional group capable of adsorbing a plating catalyst in the molecule is used, A conductive film can be easily formed on the surface of an epoxy resin molded body whose surface has been modified by surface precipitation of an acrylic resin. Hereinafter, a method for forming such a conductive film will be specifically described.

-Plating catalyst application process-
In this step, an electroless plating catalyst or a precursor thereof is applied to the surface of the surface-modified epoxy resin molded body.

<Electroless plating catalyst>
Electroless plating catalysts that can be used in this step are mainly zero-valent metals, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, and Co. In the present invention, Pd and Ag are particularly preferable from the viewpoint of good handleability and high catalytic ability. As a method for fixing the zero-valent metal on the surface of the epoxy resin molded body, for example, the functional group of the acrylic resin segregated on the surface of the epoxy resin molded body (functional group capable of adsorbing the plating catalyst) is as described above. A technique of applying a metal colloid whose charge is adjusted so as to interact with an electroless plating catalyst or a precursor thereof can be used.
In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be controlled by the surfactant or the protective agent used here, and the plating catalyst adsorption of the acrylic resin segregated on the surface of the epoxy resin molded body with the charge-adjusted metal colloid. By interacting with the functional group, the metal colloid (electroless plating catalyst) can be selectively adsorbed on the surface of the epoxy resin molded body.

<Electroless plating catalyst precursor>
On the other hand, any electroless plating catalyst precursor can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst can be used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The electroless plating catalyst metal ion is applied to the surface of the surface-modified epoxy resin molded body, and before immersion in the electroless plating bath, it is changed to a zero-valent metal by a separate reduction reaction. The catalyst may be used, or the electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

For example, the metal ion which is the electroless plating precursor as described above is applied to the surface of the epoxy resin molded body in the form of a metal salt, and interacts with the functional group of the acrylic resin deposited on the surface. Such a metal salt is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, Pd ions and the like, and Ag ions and Pd ions are preferable in terms of catalytic ability.

  As a method for applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor to the surface of an epoxy resin molded body, for example, a metal colloid is dispersed in an appropriate dispersion medium, or a metal Prepare a solution containing the dissociated metal ions by dissolving the salt with an appropriate solvent, and apply the solution to the surface of the epoxy resin molded body segregated from the acrylic resin, or put the epoxy resin molded body in the solution. May be immersed. By bringing the solution containing metal ions into contact with the surface of the epoxy resin molded body by such a method, the interactive group (plating catalyst adsorbing group) possessed by the acrylic resin segregated on the surface of the epoxy resin molded body, Metal ions can be adsorbed or impregnated using ion-ion interactions or bipolar-ion interactions. From the viewpoint of sufficiently adsorbing or impregnating such metal ions, the metal ion concentration or metal salt concentration of the solution brought into contact with the epoxy resin molded body is preferably in the range of 1 to 50% by mass, and 10 to 30%. More preferably, it is in the range of mass%. Further, the contact time is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 1 hour, from the viewpoint of productivity and the like, although it depends on the metal ion concentration and the like.

-Electroless plating process-
Next, electroless plating is performed on the epoxy resin composition shaped body to which the electroless plating catalyst or its precursor is applied. Thereby, a high-density metal film, that is, a conductive film is formed on the surface of the epoxy resin molded body. The conductive film thus formed has excellent conductivity and adhesion.

Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
In the electroless plating in this step, for example, the epoxy resin molded body having the electroless plating catalyst applied to the surface is washed with water to remove excess electroless plating catalyst (metal such as Pd, Ag), and then electroless. Immerse in a plating bath. As the electroless plating bath, a known electroless plating bath can be used.

  In addition, when the electroless plating catalyst precursor is immersed or impregnated in the epoxy resin molded body, the surface of the epoxy resin molded body is washed with water to remove excess electroless plating catalyst precursor ( After removing the metal salt, etc., it is immersed in an electroless plating bath. In this case, the reduction of the precursor and subsequent electroless plating are performed in an electroless plating bath. A known electroless plating bath can also be used as the electroless plating bath in this embodiment.

The composition of a general electroless plating bath mainly includes (1) metal ions for plating, (2) reducing agents, and (3) additives (stabilizers) that improve the stability of metal ions. Use. The plating bath may further contain a known additive such as a plating bath stabilizer.
Copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in the electroless plating bath, and copper and gold are particularly preferable from the viewpoint of conductivity.

In addition, it is preferable to select an optimal reducing agent and additive according to the metal formed on the surface of the epoxy resin molded body by electroless plating. For example, the electroless plating bath of copper preferably contains Cu (SO ₄ ) ₂ as a copper salt, HCOH as a reducing agent, and a chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer as an additive. The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate, sodium succinate, etc. as a complexing agent. Is preferably included. Further, the electroless plating bath of palladium preferably contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ or H ₂ NNH ₂ as a reducing agent, and EDTA as a stabilizer. These plating baths may contain components other than the above components.

  The film thickness of the metal film formed on the surface of the epoxy resin molded body by electroless plating as described above depends on the type of metal salt in the plating bath, metal ion concentration, immersion time in the plating bath, temperature of the plating bath, etc. From the viewpoint of conductivity, the thickness is preferably 0.1 μm or more, and more preferably 1 μm or more. From the viewpoint of productivity and the like, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

As described above, after applying a plating catalyst or its precursor to the surface of an epoxy resin molded body whose surface has been modified by surface precipitation of an acrylic resin, an electroless plating is performed to form a highly adhesive conductive film. Can be formed.
In addition, after forming a conductive film on the surface of the epoxy resin molded body by electroless plating as described above, electrolytic plating can be further performed.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not restrict | limited to these.

<Example 1>
The following thermosetting epoxy resin mixture containing an acrylic resin was applied on a polyimide film (Toray Dupont Co., Ltd., Kapton 500H, thickness 128 μm) using a coating bar. Then, the epoxy resin layer with a thickness of 8 μm was formed by heating and curing for 30 minutes under a temperature condition of 170 ° C.

-Thermosetting epoxy resin mixture-
(A) Epoxy resin 16.7g
(Japan epoxy resin, Epicoat 806, Epoxy equivalent 167)
(B) Aminotriazine novolac resin 6.6 g
(Dainippon Ink & Chemicals, Phenolite LA7052, nonvolatile content 62% by mass, nonvolatile phenolic hydroxyl group equivalent 120)
(C) Phenoxy resin 30.5g
(Non-volatile content 35% by mass, Tohto Kasei Co., Ltd., YP-50EK35)
(D) 2-ethyl-4-methylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g
(E) Methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.) 23g
(F) Acrylic resin A (SP value: 23.35, according to the Okitsu method) 3.5 g

The substrate obtained as described above is obliquely cut at an oblique cutting angle of 5 ° (cutting device: Leica ultramicrotome, glass knife), and then using TOF-SIMS (PHI-TRIFTII) under the following measurement conditions, The distribution of acrylic resin A was measured from directly above the substrate surface.
Primary ion Au +, acceleration voltage: 22 kV, primary ion current: 2 nA, neutralizing gun on
Spectrum measurement (positive / negative), with bunching, measurement area: 80μm □, measurement time 3min
Imaging measurement (positive / negative), no bunching, measurement area: 150, 100 μm □, measurement time 10 min, room temperature

  FIG. 1 shows an image of a cut surface measured as described above, the space between the ab lines represents the epoxy resin molded body layer, and the strength by mass spectrometry of the portion above the a line (surface side) is shown. When it is set to 100, the intensity | strength of an acrylic resin composition part between ac lines is 80 or more, and represents the segregated acrylic resin component. From this figure, it can be seen that the acrylic resin A is distributed (segregated) near the surface of the epoxy resin layer. Further, the segregated acrylic resin region was 0.56 μm (about 7%) with respect to the total thickness of 8 μm.

<Example 2>
In place of the acrylic resin A used in Example 1, the following acrylic resin B (SP value: 24.56, according to the Okitsu method) was used, and the thermosetting epoxy resin layer was placed on the polyimide film in the same manner as in Example 1. Formed.

  After forming the epoxy resin layer, the distribution of the acrylic resin in the epoxy resin was measured using TOF-SIMS in the same manner as in Example 1. FIG. 2 shows an image of the cut surface. Like FIG. 1, the ab line represents the epoxy resin molded body layer, and the intensity by mass analysis of the part above the a line (surface side) is 100. In the case, the strength between the acrylic resin composition is 80 or more between the a-c lines, and represents the segregated acrylic resin component. From this, it can be seen that the acrylic resin B is distributed (segregated) near the surface of the epoxy resin layer. The segregated acrylic resin region was 1.44 μm (about 18%) with respect to the total thickness of 8 μm.

<Example 3>
A thermosetting epoxy resin layer was formed on the polyimide film in the same manner as in Example 1 except that the following acrylic resin C was used instead of the acrylic resin used in Example 1.

  Next, the substrate on which the epoxy resin layer was formed as described above was immersed in an acetone solution of 1% by mass of palladium nitrate (manufactured by Wako Pure Chemical Industries) for 30 minutes, and then washed with distilled water. Thereafter, electroless plating was performed for 20 minutes in an electroless plating bath having the following composition.

<Composition of electroless plating bath>
・ OPC Kappa-H T1 (Okuno Pharmaceutical Co., Ltd.) 6mL
・ OPC Kappa-H T2 (Okuno Pharmaceutical Co., Ltd.) 1.2mL
・ OPC Kappa-H T3 (Okuno Pharmaceutical Co., Ltd.) 10mL
・ Water 83mL

Next, electroplating was carried out for 20 minutes at a current density of 3 A / dm ^{2 in} an electrolytic plating bath having the following composition to form an electrolytic copper plating layer having a thickness of 8 μm. Thereafter, after-baking was performed at 100 ° C. for 60 minutes.

<Composition of electrolytic plating bath>
・ Copper sulfate 38g
・ 95 g of sulfuric acid
・ Hydrochloric acid 1mL
・ Kappa-Gream PCM (Meltex Co., Ltd.) 3mL
・ Water 500mL

The peel strength and surface resistance value of the electrolytic copper plating film thus prepared were measured.
Peel strength is measured with Tensilon (model number RTM-100, manufactured by Orientec Co., Ltd.) according to JIS C 6481, and the peel strength (Max value, Min value, Ave value) of the conductor (copper plating film) is measured. The average value of the value and the minimum value was taken as the peel strength of the conductor. As a result, the peel strength of the electrolytic copper plating film produced in Example 3 was 0.7 kN / m.

The surface resistance value was measured by a four-probe method using a surface resistance meter (Loresta-EP, model number MCP-T360, manufactured by Mitsubishi Chemical Corporation) in accordance with JISK7194. As a result, the surface resistance value of the electrolytic copper-plated film produced in Example 3 was 2.0 × 10 ⁻³ Ω / □.
From these results, it was found that the conductive film produced by the method of the present invention has high peel strength and excellent conductivity.

2 is a diagram showing an image of a cut surface of a substrate manufactured in Example 1. FIG. 6 is a diagram showing an image of a cut surface of a substrate manufactured in Example 2. FIG.

Claims (19)

An epoxy resin molded body in which a mixture of an epoxy resin and an acrylic resin is cured, and in a region having a thickness within 30% from the surface with respect to the total thickness of the epoxy resin molded body,
An epoxy resin molded body, wherein the strength of the acrylic resin composition in the region is 80 or more when the strength by mass spectrometry of the acrylic resin composition on the surface of the epoxy resin molded body is 100.   2. The epoxy resin molded body according to claim 1, wherein the thickness from the surface is within 20% of the total thickness of the epoxy resin molded body.   3. The epoxy resin molded body according to claim 1, wherein a thickness from the surface is within 10% with respect to a total thickness of the epoxy resin molded body.   The epoxy resin molded body according to any one of claims 1 to 3, wherein the mass spectrometry is SIMS (secondary ion mass spectrometry).   5. The epoxy resin molded body according to claim 1, wherein the acrylic resin has an SP value in a range of 20 to 29. 6.   The epoxy value according to any one of claims 1 to 5, wherein the acrylic resin has an SP value in a range of 23 to 28.   Content of the said acrylic resin is 1-10 mass% as a density | concentration in a total solid, The epoxy resin molded object as described in any one of Claims 1-6 characterized by the above-mentioned.   The said acrylic resin has a functional group which can adsorb | suck a plating catalyst in a molecule | numerator, The epoxy resin molded object as described in any one of Claims 1-7 characterized by the above-mentioned.   The epoxy resin molded article according to claim 8, wherein the functional group capable of adsorbing the plating catalyst is a cyano group, an amino group, or a nitrogen-containing heterocyclic group.   The epoxy resin molded body according to any one of claims 1 to 9, wherein the mixture of the epoxy resin and the acrylic resin further contains a curing agent.   The epoxy resin molded article according to claim 10, wherein the curing agent contains at least one of an amino group and a hydroxyl group in the molecule.   The epoxy resin molded body according to any one of claims 1 to 11, wherein the mixture of the epoxy resin and the acrylic resin further contains a phenoxy resin.   The epoxy resin molded body according to any one of claims 1 to 12, wherein the mixture of the epoxy resin and the acrylic resin further adds a curing accelerator.   An epoxy resin, a curing agent that reacts with the epoxy resin, a solvent, and a SP value in the range of 20 to 29, and a mixture containing 1 to 10% by mass of an acrylic resin as a concentration in the total solid content are molded. A method for modifying the surface of an epoxy resin molded product, comprising a step of heat curing.   The method for modifying a surface of an epoxy resin molded article according to claim 14, wherein the acrylic resin has an SP value in the range of 23 to 28.   The method for modifying the surface of an epoxy resin molded article according to claim 14, wherein the solvent contains a ketone solvent.   The method for modifying the surface of an epoxy resin molded article according to claim 16, wherein at least one of methyl ethyl ketone and cyclohexanone is used as the ketone solvent.   The process of providing the electroless-plating catalyst or its precursor to the surface of the epoxy resin molding as described in any one of Claims 1-13, and the epoxy which provided the said electroless-plating catalyst or its precursor Forming a conductive film by performing electroless plating on a resin mixture.   The method for forming a conductive film according to claim 18, wherein the electroless plating catalyst is palladium.