JP6574327B2 - Insulating film modifying composition and insulating film curable resin composition - Google Patents

Description

  The present invention is a dispersion medium in which the core-shell polymer with reduced impurities is dispersed in the form of primary particles, insulating properties, crack suppression during thermal cycling, vias formed by photolithography or laser processing, etc. The present invention relates to a composition for modifying an insulating film excellent in the balance of the formability of the finely shaped product, and a curable resin composition for an insulating film excellent in these various characteristics.

  In the printed wiring board, various insulating film forming materials such as a resist material, a build-up material, a prepreg material, and an FPC adhesive are used. All of these materials are required to be insulating films having desired electrical insulation properties. It is required that gaps between a plurality of copper wirings in the same layer in the printed wiring board are filled with these materials to insulate the copper wirings and insulate copper circuits in different layers. On the other hand, this insulating film does not generate cracks during thermal cycling to ensure high reliability (improvement of toughness), and vias such as photolithographic methods and laser processing methods to ensure high reliability. It is preferable that the finely shaped object has a good shape, and improvement of the fine shape forming property is also required.

  Patent Document 1 discloses a technique in which a crosslinked rubber particle having a powdery core-shell structure is blended with a resist material, and attempts to improve the thermal cycle characteristics using this core-shell powder.

  Patent Document 2 discloses that organic fine particles having a powdery core-shell multilayer structure are mixed with a thermosetting resin in order to improve the insulation deterioration due to impurities derived from inorganic fillers and re-aggregates, thereby improving the insulation characteristics. Are trying.

  Patent Document 3 discloses a photosensitive resin composition in which various physical properties are improved by setting a predetermined amount of elastomer, and a powdery core-shell type silicone rubber is exemplified as a silicone elastomer.

All of these documents use powdery core-shell polymer particles, which are commercially available in the form of powder having a particle diameter of several tens to several hundreds of microns as an aggregate (aggregate) of primary particles. For this reason, when mixing with a dispersion medium, these powdery core-shell polymers may be pulverized to a particle diameter of less than 10 μm in advance prior to mixing, or may be mixed by applying high temperature and high shearing force during mixing. Necessary. In addition, even when mixed in a dispersion medium through such complicated operations, the core-shell polymer once dispersed can be easily precipitated or floated and separated, or the aggregates are not completely dispersed in the state of primary particles. Problems such as dispersion often occur.
As described above, it is difficult to disperse all of the aggregated particles up to the primary particles, and if the aggregated particles remain, the stress generated during the thermal cycle cannot be dispersed well and cracks are generated. If moisture or the like enters, causing a decrease in insulation reliability, or if the size of the agglomerates is not sufficiently small compared to the gaps between multiple copper wirings in the same layer, the agglomerates are insulating between the copper wirings. When the aggregate is large and protrudes like a protrusion, the aggregate falls off due to a physical external force such as contact, which causes the insulation to decrease. Further, the agglomerates are insufficient in forming fine shapes such as vias by a photolithographic method or a laser processing method.
In addition, the gap between the copper wiring, the thickness of the insulating film, and the size of the via tend to decrease year by year, and the aggregates are becoming increasingly unacceptable.

  Furthermore, in addition to the above, it is usually difficult to efficiently remove electrolytes and impurities such as emulsifiers added during the polymerization of the core-shell polymer from the powdered polymer. For this reason, these electrolytes or contaminants often cause cracking or deterioration of electrical insulation characteristics.

International Publication No. 2013/172435 Pamphlet International Publication No. 2007/125806 Pamphlet JP 2010-169809 A

  Therefore, the present invention provides an insulating film modifying composition and insulating film with improved insulation, crack suppression during thermal cycling, and improved formation of fine shapes such as vias formed by photolithography and laser processing. An object is to provide a curable resin composition.

That is, the present invention that has solved the above problems includes a dispersion medium (A) and a core-shell polymer (B) having a rubber-like elastic core layer, and at least 70% (number basis) of the core-shell polymer (B). The present invention relates to a composition for modifying an insulating film, wherein the composition is dispersed in a state of primary particles in a dispersion medium (A).

A preferred embodiment is an insulating film modifying composition in which 80% (number basis) or more of the core-shell polymer (B) is dispersed in the form of primary particles.

  A preferred embodiment is a composition for modifying an insulating film, wherein the core-shell polymer (B) has a volume average particle diameter of 10 nm to 2000 nm.

  In a preferred embodiment, an aqueous latex containing a core-shell polymer (B) having a rubber-like elastic core layer is brought into contact with an organic solvent (I) and water, and aggregated in an aqueous phase while containing the organic solvent (I). An insulating film modifying composition obtained by forming an aggregate (G) of the core-shell polymer (B) to be separated, separating the aggregate (G) from the liquid phase, and mixing with the dispersion medium (A). .

  In a preferred embodiment, the composition for insulating film modification is the method of adding the organic solvent (I) to the aggregate (G) after the separation of the aggregate (G) and before mixing the dispersion medium (A). It is.

  A preferred embodiment is an insulating film modifying composition having an alkali metal ion content of 200 ppm (mass basis) or less.

  A preferred embodiment is an insulating film modifying composition having an anionic emulsifier content of 2000 ppm (mass basis) or less.

  A preferred embodiment is an insulating film modifying composition in which the dispersion medium is at least one selected from the group consisting of a thermosetting resin, a polymerizable monomer, a polymerizable oligomer, and an organic solvent.

In a preferred embodiment, the thermosetting resin is at least one selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a phenol resin, a silicone resin, a cyanate ester resin, and a polyurethane resin,
The polymerizable monomer is at least one selected from the group consisting of monofunctional acrylates, polyfunctional acrylates, epoxy compounds, oxetane compounds, and vinyl ether compounds;
The polymerizable oligomer is composed of epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, copolymer acrylate, polybutadiene acrylate, alicyclic epoxy compound, glycidyl ether type epoxy compound, polyfunctional oxetane compound, and vinyl ether compound. The insulating film modifying composition is one or more oligomers selected from the group.

In the present invention, a curable resin composition for an insulating film containing a composition for modifying an insulating film and a component that can be matrixed, a core-shell polymer (B) having a rubber-like elastic core layer, and a component that can be matrixed And a curable resin composition for insulating films, wherein at least 70% (based on the number ) of the core-shell polymer (B) is dispersed in the form of primary particles in a component capable of forming a matrix. Is done.

  A preferred embodiment is a curable resin composition for an insulating film having an alkali metal ion content of 30 ppm (mass basis) or less.

  A preferred embodiment is a curable resin composition for an insulating film having an anionic emulsifier content of 100 ppm (mass basis) or less.

  In a preferred embodiment, the component capable of forming a matrix is selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a phenol resin, a silicone resin, a cyanate ester resin, a polyurethane resin, a polymerizable monomer, and a polymerizable oligomer. It is the curable resin composition for insulating films which is a seed or more.

  In a preferred embodiment, the polymerizable monomer is at least one selected from the group consisting of monofunctional acrylates, polyfunctional acrylates, epoxy compounds, oxetane compounds, and vinyl ether compounds. It is.

  In a preferred embodiment, the polymerizable oligomer is an epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, copolymer acrylate, polybutadiene acrylate, alicyclic epoxy compound, glycidyl ether type epoxy compound, polyfunctional oxetane compound, And a curable resin composition for an insulating film, which is one or more oligomers selected from the group consisting of vinyl ether compounds.

  A preferred embodiment is a curable resin composition for an insulating film, wherein the polymerizable oligomer includes a photopolymerizable prepolymer having a carboxy group or a hydroxyl group and an ethylenically unsaturated group.

  A preferred embodiment is a curable resin composition for an insulating film, in which a polymer of the polymerizable monomer and the polymerizable oligomer contains an alkali-soluble resin.

  A preferred embodiment is a curable resin composition for an insulating film, in which a polymer of the polymerizable monomer and the polymerizable oligomer contains an alkali-insoluble resin.

  A preferred embodiment is a curable resin composition for an insulating film used for a solder resist material, a build-up material, a prepreg material, or an adhesive for a flexible printed circuit board.

  The composition for modifying an insulating film of the present invention is a curable resin composition in which the core-shell polymer is stably dispersed in the state of primary particles in advance, and preferably contains a significantly reduced amount of impurities. Suppression, high insulation, and formability of fine shapes such as vias formed by a photolithographic method or a laser processing method can be achieved.

1. Composition for insulating film modification The composition for insulating film modification of the present invention comprises a dispersion medium (A) and a core-shell polymer (B) having a rubber-like elastic core layer, and at least the core-shell polymer (B). 70% (based on the number) is dispersed in the state of primary particles in the dispersion medium (A). Since such a modifying composition contains the core-shell polymer (B) excellent in elasticity, the toughness of the cured product of the resin composition can be obtained by blending with the curable resin composition for the insulating film. Can be improved. In the modifying composition of the present invention, since the core-shell polymer (B) is dispersed in the form of primary particles, the occurrence of cracks is reduced even when the modified insulating film is subjected to a thermal cycle. it can. Furthermore, even when the resin composition is used as a photosensitive material, homology (mask error factor, etc.) with the mask shape can be increased, and a via hole having a good shape can be formed.

In the present specification, primary particles refer to particles in which individual particles are independently dispersed throughout the dispersion medium (or composition, cured product thereof). The primary particles cure the composition containing the core-shell polymer, and a section of the obtained cured product can be observed with an electron microscope.
For example, the dispersion ratio of primary particles is calculated by calculating the number of primary particles per predetermined area and the number of aggregated particles other than primary particles, {number of primary particles / (number of primary particles + number of aggregated particles other than primary particles). Number)} × 100.

In particular, 80% (number basis) or more of the core-shell polymer (B) is preferably dispersed in the form of primary particles, and more preferably 85% (number basis) or more of the core-shell polymer is primary. More preferably, 90% (number basis) or more of the core-shell polymer is dispersed in a primary dispersion state. The upper limit of the core-shell polymer is not particularly limited as long as 70% (number basis) or more is dispersed in the state of primary particles in the insulating film modifying composition. If it is less than 70% (number basis) , the proportion of aggregated particles increases, and physical properties may not be improved.

  The core-shell polymer (B) is a core-shell polymer having at least one rubber-like elastic layer, and a rubber particle core (B-1) made of a polymer mainly composed of a polymer having rubber elasticity, and graft polymerization thereon. It is preferable that it is a polymer comprised from the shell layer (B-2) which consists of the polymer component made.

  The polymer constituting the rubber particle core (B-1) is cross-linked and can swell in a good solvent of the polymer but does not substantially dissolve and is a dispersion medium (for example, a curable resin such as an epoxy resin). It is preferable that it is insoluble. The gel content of the core part is preferably 60% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. Since the polymer constituting the core portion preferably has rubber properties, the glass transition temperature (Tg) is preferably 0 ° C. or lower, and more preferably −10 ° C. or lower.

The polymer constituting the rubber particle core (B-1) is preferably a diene rubber, an acrylic rubber, a polysiloxane rubber, or a combination thereof.
The diene rubber and / or the acrylic rubber is at least one monomer selected from the group consisting of a diene monomer (conjugated diene monomer) and a (meth) acrylic acid ester monomer ( X) It is preferably a rubber elastic body composed of 50% by mass or more and 100% by mass or less and other copolymerizable vinyl monomer (Y) by 0% by mass or more and 50% by mass or less. When the monomer (X) is less than 50% by mass, the toughness tends to decrease.
The monomer (X) is more preferably 60% by mass or more, further preferably 65% by mass or more, further preferably 70% by mass or more, and more preferably 95% by mass or less or 90% by mass or less.
The monomer (Y) is more preferably 5% by mass or more, further preferably 10% by mass or more, still more preferably 15% by mass or more, more preferably 45% by mass or less, and further preferably 40% by mass or less. It is.
In the present invention, (meth) acryl means acryl and / or methacryl.

  Examples of the conjugated diene monomer constituting the rubber elastic body include butadiene, isoprene, chloroprene and the like, and butadiene is particularly preferable. Examples of the (meth) acrylic acid ester monomer include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and the like, but butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. These can be used alone or in combination.

  Further, the rubber elastic body may be a copolymer of a conjugated diene monomer or a (meth) acrylic acid ester monomer and a vinyl monomer copolymerizable therewith. The vinyl monomer copolymerizable with the conjugated diene monomer or the (meth) acrylate monomer is selected from the group consisting of aromatic vinyl monomers and vinyl cyanide monomers. A vinyl monomer can be illustrated. As the aromatic vinyl monomer, for example, styrene, α-methylstyrene, vinyl naphthalene and the like can be used. As the vinyl cyanide monomer, for example, (meth) acrylonitrile or substituted (meth) acrylonitrile is used. It can be used. These can be used alone or in combination.

  Further, as a component constituting the rubber elastic body, a polyfunctional monomer may be included in order to adjust the degree of crosslinking. Examples of the polyfunctional monomer include divinylbenzene, butanediol di (meth) acrylate, triallyl (iso) cyanurate, allyl (meth) acrylate, diallyl itaconate, diallyl phthalate and the like. These usage-amounts are 10 mass% or less with respect to the total mass of a core part (B-1), for example, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less. When the usage-amount of a polyfunctional monomer exceeds 10 mass%, there exists a tendency for the toughness by a rubber particle core (B-1) to fall.

  A chain transfer agent may be used to adjust the molecular weight and the degree of crosslinking of the polymer constituting the rubber elastic body. Specific examples include alkyl mercaptans having 5 to 20 carbon atoms. These usage-amounts are 5 mass% or less preferably with respect to the total mass of a core part (B-1), More preferably, it is 3 mass% or less. When the amount of the chain transfer agent used exceeds 5% by mass, the amount of the uncrosslinked component of the rubber particle core (B-1) increases, and when the dispersion medium is a curable resin, the heat resistance, viscosity, etc. are adversely affected. There is a case.

  Furthermore, it is also possible to use a polysiloxane rubber as the rubber particle core (B-1) instead of the rubber elastic body or in combination with them. When polysiloxane rubber is used as the rubber particle core (B-1), for example, polysiloxane rubber composed of alkyl or aryl disubstituted silyloxy units such as dimethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, etc. It can be used. When such a polysiloxane rubber is used, if necessary, (i) a method in which a polyfunctional alkoxysilane compound is partially used at the time of polymerization, or (ii) a vinyl reactive group or a mercapto group. A method in which a reactive group such as a vinyl group is introduced and then a vinyl polymerizable monomer or an organic peroxide is added to cause a radical reaction, or (iii) a polyfunctional vinyl compound or a mercapto group after polymerization of a polysiloxane rubber It is preferable to introduce a cross-linked structure by a method of polymerizing by adding a cross-linkable monomer such as a containing compound.

  The polymer constituting the shell layer (B-2) is graft-polymerized to the polymer constituting the rubber particle core (B-1) from the viewpoint of the affinity between the curable resin such as an epoxy resin and the core-shell polymer. It is preferably bonded to the polymer constituting the rubber particle core (B-1) substantially. Of the polymers constituting the shell layer (B-2), preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more are bonded to the rubber particle core (B-1). It is desirable.

  The shell layer (B-2) may have an affinity for the dispersion medium (A) because the core-shell polymer (B) is stably dispersed in the state of primary particles in the insulating film modifying composition. The layer (B-2) preferably has swelling, compatibility or affinity for the organic solvent (I) and the dispersion medium (A) described later.

  Moreover, it is preferable that the shell layer (B-2) has reactivity with a dispersion medium (A) such as an epoxy resin or a curing agent blended at the time of use, if necessary, thereby dispersing the epoxy resin or the like. Under the condition that the medium (A) reacts with the curing agent and cures, it has the function of chemically reacting with these to form a bond, so that the core-shell polymers are reaggregated under the curing condition and the dispersion state is deteriorated. It can be effectively suppressed.

  The polymer constituting the shell layer (B-2) is a (meth) acrylic acid ester monomer, an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated acid derivative, or a (meth) acrylamide derivative. And (co) polymers obtained by copolymerizing at least one component selected from maleimide derivatives. Furthermore, in particular, when the chemical reactivity of the shell layer (B-2) when curing a dispersion medium such as an epoxy resin is required, a (meth) acrylic acid ester monomer, an aromatic vinyl monomer, cyanide is used. Monomers containing functional groups selected from epoxy groups, carboxyl groups, hydroxyl groups, and carbon-carbon double bonds in addition to vinyl monomers, unsaturated acid derivatives, (meth) acrylamide derivatives, or maleimide derivatives It is more preferable to use a copolymer obtained by copolymerizing at least one kind. These functional groups may have reactivity with a dispersion medium (A) such as an epoxy resin, which will be described later, or a curing agent or curing catalyst thereof.

  Examples of the (meth) acrylic acid ester monomer include (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Examples thereof include alkyl acrylates. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, alkyl-substituted styrene, and halogen-substituted styrenes such as bromostyrene and chlorostyrene. Examples of the vinyl cyanide monomer include (meth) acrylonitrile and substituted (meth) acrylonitrile. Moreover, as a monomer containing the functional group which has reactivity, (meth) acrylic acid ester which has a reactive side chain, for example, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2- Aminoethyl, glycidyl (meth) acrylate and the like; Examples of the vinyl ether containing a reactive group include glycidyl vinyl ether and allyl vinyl ether. Examples of the unsaturated carboxylic acid derivative include (meth) acrylic acid, itaconic acid, crotonic acid, maleic anhydride and the like. Examples of the (meth) acrylamide derivative include (meth) acrylamide (including N-substituted product). Examples of maleimide derivatives include maleic imide (including N-substituents).

  In the present invention, for example, aromatic vinyl monomer (especially styrene) 0 to 50% by mass (preferably 5 to 40% by mass), vinyl cyanide monomer (especially acrylonitrile) 0 to 50% by mass (preferably 1-30% by mass, more preferably 10-25% by mass), (meth) acrylic acid ester monomers (particularly methyl methacrylate) 0-50% by mass (preferably 5-45% by mass), reactivity Monomers for forming a shell layer in which 0 to 50% by mass (preferably 5 to 30% by mass, more preferably 10 to 25% by mass) of monomers (particularly glycidyl methacrylate) containing functional groups containing It is preferable that the shell layer be a polymer (mass%).

  The rubber particle core (B-1) / shell (B-2) ratio (mass ratio) of the core-shell polymer (B) is, for example, in the range of 40/60 to 95/5, preferably 60/40 to 90/10. It is. When the ratio (B-1) / (B-2) deviates from 40/60 and the ratio of the core (B-1) decreases, the stress reduction effect tends to decrease. When the ratio falls outside 95/5 and the ratio of the shell (B-2) decreases, aggregation tends to occur at the time of handling in the present invention, which may cause problems in operability and may not provide desired physical properties.

  The production of the core-shell polymer (B) is not particularly limited, and can be produced by a known method such as emulsion polymerization, suspension polymerization, microsuspension polymerization and the like. Among these, the production method by multistage emulsion polymerization is particularly preferable. Specific examples of the emulsifying (dispersing) agent in the aqueous medium include alkyl or aryl sulfonic acids such as dioctyl sulfosuccinic acid and dodecyl benzene sulfonic acid, alkyl or aryl ether sulfonic acids, and dodecyl sulfuric acid. Alkyl or aryl sulfuric acid, alkyl or aryl ether sulfuric acid, alkyl or aryl ether-substituted phosphoric acid, alkyl or aryl ether-substituted phosphoric acid, N-alkyl or aryl sarcosine acid represented by dodecyl sarcosine acid, oleic acid or Alkali metal salts or ammonium salts of various acids, such as alkyl or aryl carboxylic acids, alkyl or aryl ether carboxylic acids such as stearic acid, etc. Emissions emulsifiers or dispersing agents, polyvinyl alcohol, alkyl substituted cellulose, polyvinyl pyrrolidone, dispersants such as polyacrylic acid derivatives. These can be used alone or in appropriate combination.

  The emulsifier is preferably an anionic emulsifier from the viewpoint of polymerization stability, more preferably an anionic emulsifier of an alkali metal salt, and still more preferably an anionic emulsifier of a sodium salt and / or a potassium salt.

  These emulsifying (dispersing) agents are used in as little amount as possible within the range that does not hinder the dispersion stability in the preparation process of the aqueous latex containing the core-shell polymer (B), in the sense of the preferred embodiment of the present invention. May be. Alternatively, in the process of producing the insulating film modifying composition of the present invention, the remaining amount may be extracted and removed so as not to affect the physical properties of the produced dispersion medium. For this reason, it is more preferable that the emulsifier (dispersant) has water solubility.

  The core-shell polymer (B) that can be used in the present invention is usually 1 to 70% by mass, preferably 2 to 60% by mass, more preferably 5 to 5%, based on the total of the dispersion medium (A) and the core-shell polymer (B). It can be mix | blended in 50 mass%, and becomes a composition for insulation film modification | reformation.

  The volume average particle diameter of the core-shell polymer (B) can be used without any problem as long as the core-shell polymer (B) can be stably obtained in the state of an aqueous latex. Is preferably 10 nm to 2000 nm, more preferably 30 nm to 1000 nm, and still more preferably 50 nm to 500 nm. If it is less than 10 nm or more than 2000 nm, the production becomes difficult, and there is a possibility that it cannot be stably obtained in the state of an aqueous latex. Moreover, when it is over 2000 nm, there is a possibility that the insulating property may be lowered when it enters between the fine copper wiring and the copper wiring. The volume average particle diameter can be measured using, for example, Microtrac UPA (manufactured by Nikkiso Co., Ltd.).

The dispersibility of the primary particles of the core-shell polymer (B) is preferably achieved by employing the following means.
That is, in the composition for insulating film modification of the present invention, the aqueous latex containing the core-shell polymer (B) having a rubber-like elastic core layer is referred to as an organic solvent (I) (hereinafter referred to as an aggregate-forming organic solvent). And an aggregate (G) of the core-shell polymer (B) that contains the organic solvent (I) and aggregates in the aqueous phase while containing the organic solvent (I). It is preferably obtained by separating and mixing with the dispersion medium (A). The core-shell polymer (B) can be aggregated by bringing the aqueous latex into contact with an organic solvent. In addition, by coexisting water at this time, water-soluble impurities in the aqueous latex can be removed to the aqueous phase side. The aggregate (G) can be separated and acquired by collecting the organic solvent phase. The water-soluble contaminant refers to an emulsifier or dispersant used in the preparation of the aqueous latex, an electrolyte or a water-soluble substance such as a water-soluble polymerization initiator or a reducing agent, and particularly an anionic emulsifier or Alkali metal ions are typical.

  Here, the specific organic solvent (I) mixed with the aqueous latex containing the core-shell polymer (B) includes, for example, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, diethyl ketone, Ketones such as methyl isobutyl ketone, alcohols such as ethanol, (iso) propanol and butanol, ethers such as tetrahydrofuran, tetrahydropyran, dioxane and diethyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride Examples thereof include one or more organic solvents selected from halogenated hydrocarbons such as chloroform or a mixture thereof, and those having a solubility in water at 20 ° C. of 5% by mass to 40% by mass are particularly preferable. obtain. When the solubility of the organic solvent (I) in water is less than 5% by mass, mixing with the aqueous latex containing the core-shell polymer (B) tends to be somewhat difficult, and conversely when it exceeds 40% by mass. However, after adding a water-soluble electrolyte or an aqueous latex and an immiscible organic solvent, it tends to become increasingly difficult to efficiently separate and remove the aqueous phase. The second organic solvent (II) added to the aggregate (G) when preparing the dispersion (E) is not necessarily limited to the specific organic solvent (I) (which is mixed with the aqueous latex of the core-shell polymer (B) ( It is not necessary to use the same kind of organic solvent for forming aggregates).

In the present invention, it is preferable to add the second organic solvent (II) to the aggregate (G) after the separation of the aggregate (G) and before mixing of the dispersion medium (A). This dispersion method is advantageous in that the core-shell polymer is primarily dispersed in various dispersion media. As the organic solvent (II), the same organic solvent (I) for forming aggregates as described above can be used.
Further, the core-shell polymer (B) may be washed with water after the addition of the second organic solvent (II). The number of times of washing with water may be one, preferably two or more.

  The alkali metal ion content is preferably 200 ppm (mass basis) or less, more preferably 100 ppm (mass basis) or less, and further preferably 50 ppm (mass basis) or less in the composition for insulating film modification. If the amount of alkali metal ions is more than 200 ppm, the insulating property may be lowered. The lower limit of the alkali metal ion content is preferably closer to 0 ppm.

  The anionic emulsifier content is preferably 2000 ppm (mass basis) or less, more preferably 1000 ppm (mass basis) or less, and still more preferably 500 ppm (mass basis) or less. If the content of the anionic emulsifier exceeds 2000 ppm, impurities such as alkali metal ions remain, and there is a possibility that the insulating property is lowered.

As the dispersion medium, various liquids capable of dispersing the core-shell polymer (B) can be used. The dispersion medium is not limited to a non-reactive dispersion medium such as a solvent (particularly an organic solvent (III)), and may be a reactive dispersion medium that can also be used as a matrix forming material for an insulating film described later. Such reactive dispersion media include thermosetting resins, polymerizable monomers, polymerizable oligomers, and the like. These thermosetting resins, polymerizable monomers, polymerizable oligomers, and organic solvents (III) may be used singly or in appropriate combination of two or more. The reactive dispersion medium may be selected according to the use or matrix component of the insulating film curable resin composition to be blended such as thermosetting and photopolymerization, and the matrix component and the dispersion medium are the same. There may be.
When the dispersion medium is a reactive dispersion medium (thermosetting resin, polymerizable monomer, polymerizable oligomer, etc.), the aggregate-forming organic solvent (I) or added organic solvent (II) and the core-shell polymer (B) The reactive dispersion medium may be mixed, and then the organic solvent (I) or (II) may be distilled off.
In the insulating film modifying composition obtained as described above, the content of the dispersion medium is, for example, 30 to 99% by mass with respect to 100% by mass of the insulating film modifying composition (not including the organic solvent). Preferably it is 40-98 mass%, More preferably, it is 50-95 mass%.

  The organic solvent (III) used as the dispersion medium can be appropriately selected and used from the same range as the above-mentioned aggregate-forming organic solvent (I).

  The thermosetting resin is preferably at least one selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a phenol resin, a silicone resin, a cyanate ester resin, and a polyurethane resin.

The epoxy resin is a resin obtained by polymerizing a compound (polyvalent epoxy compound) having two or more epoxy groups (oxirane rings) in one molecule. For example, phenols, biphenols or naphthols are condensed with aldehydes. Phenol novolac epoxy resin or cresol novolac epoxy resin obtained by glycidyl etherification of the novolak resin obtained in this manner; biphenyl epoxy resin such as 2,2 ′, 6,6′-tetramethylbiphenol diglycidyl ether; biphenol, aromatic nucleus Substituted biphenols, polyphenols such as bisphenol A, F, S, trimethylolpropane or polyglycidyl ethers of polyhydric alcohols or condensates thereof; or alicyclic compounds containing a cycloolefin oxide structure skeleton in one molecule Epoxy resin etc. Widely available.
Among these, the epoxy resin is selected from a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a biphenyl type epoxy resin, a bisphenol type epoxy resin, and an alicyclic epoxy resin containing a cycloolefin oxide structure skeleton in one molecule. It is preferable to contain 50% by mass or more of the one or more epoxy resins to be added to the total amount of the epoxy resin as the dispersion medium (A).

  In addition to the above, the epoxy resin is DGBEA type, bisphenol A novolak type, halogenated bisphenol A type, halogenated novolak type epoxy resin, glycidylamine type (derived from aminophenol, xylylenediamine, diaminodiphenylmethane, etc.) In addition to other functional epoxy such as triglycidyl isocyanurate (TGIC), brominated bisphenol A type epoxy can be used.

  The epoxy resin may contain a monoepoxide as a reactive diluent, for example, an aliphatic glycidyl ether such as butyl glycidyl ether, phenyl glycidyl ether, or cresyl glycidyl ether. As is generally known, monoepoxides affect the stoichiometry of polyepoxide blends, which are epoxy resins, but this adjustment is made by the amount of curing agent or other well-known methods.

  The unsaturated polyester resin is, for example, a resin obtained by polycondensation of a polyhydric alcohol and an unsaturated polyvalent carboxylic acid or anhydride thereof to obtain an unsaturated polyester, and further copolymerization with a vinyl monomer having an unsaturated bond. It is.

  Examples of the polyhydric alcohol include carbon such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, di-1,2 propylene glycol, 1,4-butanediol, and neopentyl glycol. Examples thereof include dihydric alcohols having 2 to 12 atoms. These dihydric alcohols may be used alone or in combination of two or more.

  Examples of the unsaturated polyvalent carboxylic acid include divalent carboxylic acids having 3 to 12 carbon atoms. Specific examples include fumaric acid and maleic acid. These divalent carboxylic acids may be used alone or in combination of two or more.

  The vinyl monomer is, for example, an aromatic vinyl monomer, and is preferably styrene, α-methylstyrene, or vinylnaphthalene.

  The phenol resin is a resin obtained by (co) condensation of one or more selected from phenols and naphthols and formaldehyde which is a compound having an aldehyde group such as formaldehyde, a novolac type phenol resin, Examples include resol-type phenol resins.

  Examples of the phenols include phenol, cresol, bisphenol A, bisphenol F, catechol, and resorcinol. Examples of the naphthols include α-naphthol and β-naphthol.

  Examples of the formaldehydes include formaldehyde, paraformaldehyde, trioxymethylene, hexamethylenetetramine, and trioxane.

  The silicone resin may be a resin having a siloxane (—SiOSi—) unit in the resin skeleton, and silanes such as dichlorodimethylsilane, trichloromethylsilane, and tetrachlorosilane are hydrolyzed, and the generated silanol is dehydrated and condensed. It may also be one obtained by hydrolyzing silanes such as dialkoxydimethylsilane, trialkoxysilane, tetraalkoxysilane and the like, and the resulting silanol being dehydrated and condensed. For example, those composed only of siloxane units, siloxane-organic block polymers having an organic skeleton composed of C, H, N, O, S and halogen as constituent elements, and siloxane-organic graft polymers are included.

  The cyanate ester resin is a compound having two or more cyanate groups —OCN (cyanate ester) in the molecule, and examples thereof include 2,2-bis (4-cyanatophenyl) propane and bis (4-cyanate). Anatophenyl) ethane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3- Examples thereof include hexafluoropropane and a cyanate ester compound having a dicyclopentadiene skeleton. A cyanate ester compound may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The polyurethane resin is a resin produced by condensation of a polyisocyanate containing an isocyanate group and a polyol containing a hydroxyl group.

  Examples of the polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butanediol, 2,2′-dimethyl- 1,3-propanediol, diethylene glycol, triethylene glycol, 1,5-pentamethylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4 -Diols such as diol, cyclohexane-1,4-dimethanol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, triols such as trimethylolpropane, pentaerythritol, etc. Tetraol, the Hexa all of pentaerythritol, and the like. These can be used alone or in combination of two or more.

  As polyisocyanate, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′- Aromatic diisocyanate compounds such as diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethylhyphenyl-4,4′-diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate, etc. Aliphatic diisocyanate compound; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or 2,6) diisocyanate Sulfonates, 1,3 alicyclic diisocyanate compounds such as (isocyanatomethyl) cyclohexane. These diisocyanates can be used alone or in combination of two or more. You may use a chain extender etc. as needed.

  The polymerizable monomer is preferably at least one selected from the group consisting of monofunctional acrylates, polyfunctional acrylates, epoxy compounds, oxetane compounds, and vinyl ether compounds.

The monofunctional acrylate is a compound having one (meth) acryloyloxy group, and may have a low viscosity and excellent solubility of the polymerizable oligomer, and can function as a dilution monomer.
The monofunctional acrylate is, for example, a (meth) acrylate monomer having one (meth) acryloyloxy group in the molecule, and has a chain shape such as butyl (meth) acrylate, propyl (meth) acrylate, and hexyl (meth) acrylate. Alkyl (meth) acrylate; Cyclohexyl (meth) acrylate, cycloaliphatic alkyl (meth) acrylate such as isobornyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethoxyethoxy Alkoxyalkyl (meth) acrylates such as ethyl (meth) acrylate and 2-phenoxyethyl (meth) acrylate; 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Hydroxyl group-containing (meth) acrylates such as acrylate; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; (meth) acrylates having an ethylenically unsaturated double bond such as allyl (meth) acrylate, etc. The

  The polyfunctional acrylate is, for example, a (meth) acrylate monomer having two (meth) acryloyloxy groups in the molecule, and includes ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) ) Acrylate, alkylene glycol di (meth) acrylate such as cyclohexanedimethanol di (meth) acrylate; triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Examples include polyalkylene glycol di (meth) acrylate such as (600) di (meth) acrylate.

  The polyfunctional acrylate may be, for example, a (meth) acrylate monomer having three (meth) acryloyloxy groups in the molecule, such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate. Tri (meth) acrylate having a branched alkyl group; Tri (meth) acrylate having a branched alkylene ether group such as glycerol propoxy tri (meth) acrylate and trimethylolpropane triethoxytri (meth) acrylate; Tris (2-hydroxy Examples include tri (meth) acrylates containing a heterocyclic ring such as ethyl) isocyanurate tri (meth) acrylate.

  The polyfunctional acrylate may be, for example, a (meth) acrylate monomer having four or more (meth) acryloyloxy groups in the molecule, such as di (trimethylolpropane) tetra (meth) acrylate, dipentaerythritol hexa ( Examples include poly (meth) acrylates having a plurality of branched alkyl groups such as (meth) acrylate; poly (meth) acrylates having a plurality of branched alkyl groups such as dipentaerythritol penta (meth) acrylate and hydroxyl groups, and the like. . These (meth) acrylic acid ester monomers may be used alone or in combination of two or more.

  The epoxy compound may be, for example, a compound having one epoxy group such as phenyl glycidyl ether, butyl glycidyl ether, hexanediol glycidyl ether, tetraethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A A compound having two or more epoxy groups such as diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and novolak type epoxy compound may be used.

  The oxetane compound may be a compound having an oxetane ring, such as 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether. 1,4-bis {[3-ethyl- (3-oxetanyl) methoxy] methyl} benzene, 3,3′-dimethyl-2- (p-methoxyphenyl) -oxetane, and the like.

  The said vinyl ether compound should just have 1 or more vinyl ether structures in a molecule | numerator, and has 2 or less vinyl groups in a molecule | numerator. Vinyl ether compounds are 1,4-butanediol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, cyclohexane dimethanol divinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol mono Examples include vinyl ether, diethylene glycol monovinyl ether, 1,4-butanediol monovinyl ether, neopentyl glycol monovinyl ether, 2-chloroethyl vinyl ether, vinyl acetate and the like.

  The polymerizable oligomer is composed of epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, copolymer acrylate, polybutadiene acrylate, alicyclic epoxy compound, glycidyl ether type epoxy compound, polyfunctional oxetane compound, and vinyl ether compound. One or more oligomers selected from the group are preferred. The polymerizable oligomer may be a low polymer having, for example, about 2 to 20 repeating structural units, and the resin has a larger number of repeating structural units than the polymerizable oligomer. Also good.

The epoxy acrylate may be obtained, for example, by an addition reaction between a glycidyl ether compound and acrylic acid.
Examples of the glycidyl ether compound include 1,6-hexane diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol A type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin.
Examples of acrylic acids include acrylic acid, methacrylic acid; lower alkyl esters such as acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, and methacrylic acid propyl ester. Furthermore, it is good also as a compound which has an ester bond obtained by making a polybasic acid compound react with the hydroxyl group of an epoxy acrylate.
Examples of polybasic acid compounds include maleic anhydride, succinic anhydride, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride And methylcyclohexene dicarboxylic acid anhydride.

The urethane acrylate may be obtained by an addition reaction between a reaction product of a polyol and a polyisocyanate and an acrylate containing a hydroxyl group.
Examples of the polyol include 1,6-hexanediol diglycidyl ether, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate diol, and polyester diol.
As the polyisocyanate, known ones can be used. For example, an isocyanurate type comprising a diisocyanate compound such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or lysine diisocyanate. Polyisocyanate; Adduct type polyisocyanate of the diisocyanate compound and trimethylolpropane; Burette type polyisocyanate comprising the diisocyanate compound is preferable.
Examples of the acrylate containing a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. Furthermore, other copolymerizable monomers may be used, and methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, styrene, α-methyl styrene, and the like may be used.

The polyester acrylate may be obtained by esterification of a polyester polyol composed of a polyol and a polybasic acid and acrylic acid.
Examples of the polyol used for the synthesis of the polyester acrylate include 1,3-butanediol, 1,4-butanediol, trimethylolethane, trimethylolpropane, ditrimethylolethane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, Tripentaerythritol, diglycerol, glycerin, other polysiloxane polyols, poly (oxyalkylene) polyols, polyester polyols, polyether polyols, polyether polyester polyols, polyolefin polyols, poly (alkyl acrylate) polyols, polycarbonate polyols, etc. Can be mentioned.
Examples of the polybasic acid used for the synthesis of the polyester acrylate include saturated polybasic acids such as adipic acid, succinic acid, and sebacic acid; unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; Aromatic polybasic acids such as acid, isophthalic acid, terephthalic acid and trimellitic acid can be mentioned.

  The polyether acrylate may be a reaction product from a polyether polyol such as polyethylene glycol or polypropylene glycol and an unsaturated carboxylic acid.

  The copolymer acrylate may be an acrylic compound in which a (meth) acryloyl group is added to the side chain of the acrylate copolymer. Examples of the copolymer acrylate include a compound obtained by copolymerizing glycidyl methacrylate and adding acrylic acid, a compound obtained by copolymerizing acrylic acid and methacrylic acid and adding glycidyl methacrylate, 2-HEMA (2 -Hydroxyethyl methacrylate) and 2-HEA (2-hydroxyethyl acrylate) are copolymerized, and the compound obtained by adding an isocyanate containing acrylate is mentioned.

The polybutadiene acrylate may be an acrylic compound having a polybutadiene or hydrogenated polybutadiene skeleton.
The polybutadiene acrylate can be obtained, for example, by a method of acrylate-forming a hydroxyl group-containing polybutadiene or a method of adding a hydroxyl group-containing acrylate to a hydroxyl group-containing polybutadiene via a diisocyanate.

The alicyclic epoxy compound, the glycidyl ether type epoxy compound, the polyfunctional oxetane compound, and the vinyl ether compound may be any compound that is suitable for a cationic polymerizable reaction, and the curing reaction proceeds even when light irradiation is interrupted. , It can impart properties that cannot be imparted by radical polymerization. These compounds may be those obtained by oligomerizing those exemplified as the polymerizable monomer, as long as the molecular weight is higher than that of the polymerizable monomer.
Examples of the alicyclic epoxy compound include oligomers such as 1,2-epoxy-4-vinylcyclohexane, 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, and 3,4-epoxycyclohexylmethyl methacrylate. Is mentioned.
Examples of the glycidyl ether type epoxy compound include oligomers such as phenyl glycidyl ether, butyl glycidyl ether, and hexanediol glycidyl ether.
Examples of the polyfunctional oxetane compound include oligomers such as (3-ethyloxetane-3-yl) methyl methacrylate and 3-ethyl-3-hydroxymethyloxetane.
The vinyl ether compound is ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane. Any oligomer such as di- or trivinyl ether compounds such as trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, and 2-ethylhexyl vinyl ether may be used.

  Among the above dispersion media, preferred dispersion media are epoxy resins, more preferably orthocresol novolac type epoxy resins, phenol novolac type epoxy resins, and DGEBA type epoxy resins.

2. Curable resin composition for insulating film The present invention contains a core-shell polymer (B) having a rubber-like elastic core layer and a component that can be matrixed, and at least 70% of the core-shell polymer (B) (number basis) Is dispersed in the form of primary particles in a component that can be formed into a matrix, and includes a curable resin composition for an insulating film. Since such a curable resin composition for an insulating film contains the core-shell polymer (B), the toughness of the insulating film can be improved. In addition, since the core-shell polymer (B) is dispersed in the state of primary particles, the occurrence of cracks can be reduced even when the insulating film is subjected to a thermal cycle, and insulation is also exhibited. It becomes possible to form a via having a good shape even when finely processed by a laser processing method. Furthermore, even when the resin composition is used as a photosensitive material, homology (mask error factor, etc.) with the mask shape can be increased, and a via hole having a good shape can be formed.

The component capable of forming a matrix is preferably 50 to 95% by mass, more preferably 60 to 90% by mass in the curable resin composition for an insulating film.
A core-shell polymer (B) is 1-50 mass% normally in the curable resin composition for insulating films, Preferably it is 2-30 mass%, More preferably, it is 5-25 mass%. When the amount of the core-shell polymer (B) is less than 1% by mass, the obtained insulating film may not have a crack suppressing effect. Moreover, when the compounding quantity of a core shell polymer (B) exceeds 50 mass%, sufficient insulation may not be acquired in the obtained insulating film.

In the curable resin composition for an insulating film, it is preferable that 70% (number basis) or more of the core-shell polymer (B) is dispersed in a primary particle state, more preferably 80% ( number basis) or more, are dispersed in the state of primary particles, more preferably the 90% of the core-shell polymer (number basis) or more, are dispersed in the state of primary dispersion. The upper limit of the core-shell polymer is not particularly limited as long as 70% (number basis) or more is dispersed in the state of primary particles in the curable resin composition for an insulating film. If it is less than 70% (based on the number) , the ratio of the aggregated particles increases, and there is a possibility that improvement in physical properties such as insulation, crack suppression during thermal cycling, and fine shape formability may not be expected.

In the curable resin composition for an insulating film, the alkali metal ion content is preferably 30 ppm (mass basis) or less, more preferably 15 ppm (mass basis) or less, particularly preferably 10 ppm (mass basis) or less. . When the alkali metal ion content exceeds 30 ppm, the insulating property is lowered.
The content of alkali metal ions can be determined, for example, by high frequency induction plasma emission spectroscopy after pressure acid decomposition of the epoxy resin composition (C).

  In the curable resin composition for insulating films, the anionic emulsifier content is preferably 100 ppm (mass basis) or less, more preferably 60 ppm (mass basis) or less, particularly preferably 30 ppm (mass basis) or less. . The method for analyzing the residual emulsifier is, for example, colorimetric determination at a wavelength of 650 nm using methylene blue using a sample obtained by drying the dispersion (E) before mixing with the epoxy resin (A) and then extracting the emulsifier with ethanol. It can be determined by law.

  Such a curable resin composition for an insulating film can be prepared, for example, by mixing the composition for modifying an insulating film and a component capable of forming a matrix. In the insulating film modifying composition, since the core-shell polymer (B) is dispersed in the form of primary particles, the resulting curable resin composition for insulating film can be obtained by mixing this with a component that can be matrixed. The core-shell polymer (B) is dispersed in the form of primary particles. Moreover, since the composition for modifying an insulating film is usually suppressed in the content of an alkali metal ion or an anionic emulsifier, the content of an alkali metal ion or an anionic emulsifier in a curable resin composition for an insulating film The content can be suppressed. Insulating properties can be improved by suppressing these amounts.

The component capable of forming a matrix is at least one selected from the group consisting of epoxy resins, unsaturated polyester resins, phenol resins, silicone resins, cyanate ester resins, polyurethane resins, polymerizable monomers, and polymerizable oligomers. Is preferred.
These can be appropriately selected from the same ranges as those exemplified as the dispersion medium (A). The dispersion medium (A) and the component that can be matrixed may be the same or different.

  The component that can be formed into a matrix can be appropriately selected according to the use of the curable resin composition for an insulating film. Then, the content of the component which can be made into the specific matrix which comprises the curable resin composition for insulating films, and another structural component are demonstrated according to the use. Note that the curable resin composition for the insulating film includes, for example, thermosetting applications such as a thermosetting solder resist, a thermosetting buildup material, a thermosetting prepreg, and an adhesive for FPC; UV such as a UV curable solder resist. Curing use: Can be used for photosensitive / developing applications such as photosensitive solder resists and photosensitive build-up materials.

2-1. Thermosetting application When the insulating resin curable resin composition is used for the thermosetting application, a thermosetting resin is used as a component that can be formed into a matrix. As the thermosetting resin, the aforementioned epoxy resin, unsaturated polyester resin, phenol resin, silicone resin, cyanate ester resin, polyurethane resin and the like can be used alone or in appropriate combination.
When a thermosetting resin is used, the curable resin composition comprises a curing agent (K) or a curing catalyst, an inorganic filler (L) as necessary, and a curing accelerator (M) or a flame retardant as necessary. , A coupling agent, a mold release agent, an additive such as a pigment, and a compounding agent can be appropriately blended. As these additives and blends, those generally used in this field can be used without any problem.

  Examples of the curing agent (K) include phenolic resins such as phenol novolac resin, cresol novolac resin, naphthalene type phenol resin, amino resin, urea resin, melamine, dicyandiamide, and the like alone or in combination of two or more. Can be used in combination. Among these, it is particularly preferable to use a phenol resin from the viewpoint that the heat resistance of the resulting cured product is increased. These are normally used at a ratio of 1 to 300 parts by mass with respect to the curable resin composition for an insulating film (epoxy resin composition).

  Curing catalysts include amines, amine salts such as chlorides of the amines and quaternary ammonium salts, cyclic aliphatic acid anhydrides, aliphatic acid anhydrides, acid anhydrides such as aromatic acid anhydrides, polyamides, etc. , Imidazoles, nitrogen-containing heterocyclic compounds such as triazine compounds, organometallic compounds, and the like can be used. Preferably the usage-amount of a curing catalyst is 0.5-20 mass parts with respect to 100 mass parts of thermosetting resins (epoxy resin composition), More preferably, it is 1-10 mass parts.

  Examples of the curing accelerator (M) include phosphine compounds such as imidazole compounds, tertiary amine compounds, and triphenylphosphine. Alternatively, when photocuring is applied, for example, an aromatic sulfonium salt, an aromatic diazonium salt, an aromatic iodonium salt, or the like can be used as a curing catalyst, and a known sensitizer such as an anthracene derivative is appropriately combined. Can be used. These are normally used in a ratio of 0.01 to 50 parts by mass with respect to 100 parts by mass of the curable resin composition for an insulating film (epoxy resin composition).

  As the inorganic filler (L), for example, fused silica, crystalline silica, alumina, calcium carbonate, boron nitride, silicon carbide and the like can be used. These are usually used at a ratio of 0 to 2000 parts by mass with respect to 100 parts by mass of the insulating film modifying composition (epoxy resin composition).

  Examples of the flame retardant include brominated bisphenol A type epoxy resin, other brominated flame retardants, phosphorus flame retardants typified by condensed phosphate esters, metal hydroxide flame retardants such as magnesium hydroxide and aluminum hydroxide Silicone resin flame retardants such as polysiloxane derivatives can be used. These can be used alone or in appropriate combination at a ratio of usually about 0 to 100 parts by mass with respect to 100 parts by mass of the insulating film modifying composition (epoxy resin composition).

  As coupling agents, for example, epoxy silane, amino silane, alkyl silane, vinyl silane, organic titanate, etc., as mold release materials, for example, natural wax, synthetic wax and esters, as colorants, for example, carbon black, etc. are widely used. Can be used. Although these differ depending on the form of semiconductor encapsulation used, they can be suitably used in the range of usually about 0 to 50 parts by mass with respect to 100 parts by mass of the insulating film modifying composition (epoxy resin composition).

2-2. UV curable application, photosensitive / development application The UV curable application is an application that does not involve development and is sufficient to cure the curable resin composition for insulating film with UV. For UV curable applications, a photocurable resin is used as the component that can be matrixed. In the photosensitive / development application, as a component capable of forming a matrix, an alkali-soluble resin or an alkali-insoluble resin is used in addition to the above-described photo-curable resin used in the UV curable application. The alkali-soluble resin is used as a negative photoresist material, and the alkali-insoluble resin is used as a positive photoresist material.

  When the component which can be matrixed is a photocurable resin, the curable resin composition for insulating films contains at least one of a polymerizable monomer and a polymerizable oligomer, preferably both. By including both, the photocurability becomes better.

  The polymerizable monomer may be one or more selected from the group consisting of monofunctional acrylates, polyfunctional acrylates, epoxy compounds, oxetane compounds, and vinyl ether compounds, and these are compositions for insulating film modification It may be the same as that exemplified in.

  The polymerizable oligomer is composed of epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, copolymer acrylate, polybutadiene acrylate, alicyclic epoxy compound, glycidyl ether type epoxy compound, polyfunctional oxetane compound, and vinyl ether compound. One or more kinds of oligomers selected from the group may be used, and these may be the same as those exemplified in the composition for insulating film modification.

  The polymerizable oligomer may contain a photopolymerizable prepolymer having a carboxy group or a hydroxyl group and an ethylenically unsaturated group, and a (meth) acrylic acid ester having 4 to 20 carbon atoms and one per molecule. It may be a carboxyl group- or hydroxyl group-containing (meth) acrylic copolymer resin obtained by copolymerizing a single ethylenically unsaturated group and a compound having at least one carboxyl group or hydroxyl group.

  (Meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, etc. Glycol modification (meta) such as acid alkyl esters, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate ) Acrylates and the like.

  Examples of the compound having one ethylenically unsaturated group and at least one carboxy group in one molecule include acrylic acid and methacrylic acid. Examples of the compound having one ethylenically unsaturated group and at least one hydroxyl group in one molecule include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2 -Hydroxyl group-containing (meth) acrylic acid esters such as hydroxyethyl (meth) acrylate.

  It is preferable to contain 5 to 70 mass% of polymerizable monomers with respect to 100 mass% of all compositions, More preferably, it contains 10 to 60 mass%. It is preferable to contain 20-90 mass% of polymerizable oligomers with respect to 100 mass% of all compositions, More preferably, it is 30-80 mass%.

The alkali-soluble resin may be one obtained by polymerizing a photopolymerizable prepolymer having a carboxy group or a hydroxyl group and an ethylenically unsaturated group, or one obtained by copolymerizing a polymerizable monomer copolymerizable therewith.
The alkali-insoluble resin may have a protective group that is insoluble in alkali.

  The alkali-soluble resin or alkali-insoluble resin may be dissolved in a solvent. Examples of the solvent include glycol ether esters such as propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate and butyl acetate. And esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone;

  The alkali-insoluble resin may be washed with, for example, an alkaline aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline). On the other hand, alkali-soluble resins include: ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; It may be washed with an amide solvent such as N-dimethylacetamide; an organic solvent such as an aromatic hydrocarbon solvent such as anisole.

  When using the curable resin composition for insulating films for UV curable applications and photosensitive / development applications, the resin composition preferably also contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy- Acetophenones such as 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- ( 4-morpholinyl) phenyl] -1-butanone Aminoalkylphenones; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone Thioxanthones such as 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4 Phosphine oxide such as 6-trimethyl benzoyl phenyl phosphinothricin Nate; various peroxides; and titanocene initiators. The blending amount of the photopolymerization initiator is preferably 0.1 part by mass to 20 parts by mass, and more preferably 0.2 part by mass to 10 parts by mass with respect to a total of 100 parts by mass of the polymerizable monomer and the polymerizable oligomer.

When using the said curable resin composition for insulating films for a photosensitivity / image development use, this resin composition may contain the acid generator. By generating an acid by light irradiation, the alkali-insoluble resin can be made alkali-soluble, and the alkali-soluble resin can be made insoluble in alkali.
The acid generator may be a sulfonium salt-based, iodonium salt-based, or nonionic acid generator that absorbs light at the cation portion, generates an acid at the anion portion, and protects the alkali-insoluble resin at the light-irradiated portion. The group may be removed and solubilized with alkali. The content of the acid generator is preferably 1 part by mass or more and more preferably 3 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer and the polymerizable oligomer. Moreover, Preferably it is 30 mass parts or less, More preferably, it is 25 mass parts or less.

  When using an acid generator, you may use a crosslinking agent with an acid generator. Hexamethoxymethylmelamine, tetramethoxyglycoluril (TMGU), etc. are used as the cross-linking agent. Light is irradiated at the cation part of the acid generator at the light irradiation site, acid is generated at the anion part, and light is irradiated by the cross-linking agent The polymer at the site may be crosslinked to make it insoluble in alkali.

  In addition to the photopolymerization initiator, the photocurable resin may contain a polymerization inhibitor, an antifoaming agent, a silane coupling agent, a plasticizer, a filler, a leveling material, a pigment, and a dye as necessary.

  The composition for modifying an insulating film and the curable resin composition for an insulating film of the present invention may be used for a solder resist material, a build-up material, a prepreg material, or an adhesive for a flexible printed circuit board.

Thermosetting applications such as thermosetting solder resist materials, thermosetting build-up materials, thermosetting prepregs, adhesives for FPC, etc. When the composition is a thermosetting application, the outermost layer of the printed wiring board (solder) Resist), inner layers of multilayer printed wiring boards (build-up materials, prepreg materials), and FPC adhesives. (FPC: Flexible wiring board)
When using the said curable resin composition for insulating films as a thermosetting soldering resist material, it can be used for a printed wiring board (single-sided, double-sided, or multilayer) or COF, TAB.
When using the said curable resin composition for insulating films as a thermosetting buildup material, it can be used for a buildup multilayer wiring board.
When using the said curable resin composition for insulating films as a prepreg material, a buildup multilayer wiring board, a printed wiring board (single side, both sides, or multilayer), or multilayer FPC can be used.
When the curable resin composition for an insulating film is used as an adhesive for FPC, it can be used as an adhesive for three-layer FCCL (Flexible Copper Clad Laminate) and an adhesive for coverlay, and can be used for FPC (single side, double side or multilayer). Can be used.

UV curable application such as UV curable solder resist When the composition is used for UV curable, it can be used as an outermost layer (solder resist) of a printed wiring board.
When the curable resin composition for an insulating film is used as a UV curable solder resist material, it can be used for COF and TAB.

Photosensitivity / development applications such as photosensitive solder resist and photosensitive buildup materials When the composition is used for photosensitivity / development, the outermost layer of the printed wiring board (solder resist), the inner layer of the multilayer printed wiring board (buildup material) ) Can be used.
When the curable resin composition for an insulating film is used as a photosensitive solder resist, it can be used for a build-up multilayer wiring board, a printed wiring board (single side, double side or multilayer), or FPC (single side, double side or multilayer).
When using the said curable resin composition for insulating films as a photosensitive buildup material, it can be used for a buildup multilayer wiring board.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

  In the following, the residual amount of impurities was analyzed using the amount of emulsifier (anionic surfactant) and total ions as indicators. The dispersion state of the core-shell polymer in the epoxy resin component was determined by observing with a transmission electron microscope (TEM) after preparing an ultrathin section from a cured product prepared from the obtained epoxy resin composition.

  Prior to the examples, the analytical measurement method used in the present invention will be described below.

[1] Residual emulsifier amount The residual emulsifier amount was determined by measuring the amount of emulsifier remaining in the dispersion (E) before mixing with the epoxy resin of the dispersion medium (A) by the following analytical method. ) Was quantified as a ratio (mass%) when the total amount of the emulsifier used in the polymerization of 100) was 100 mass%, and a mass ratio (ppm) contained in the system after the preparation of the epoxy resin composition.

[1-1] Sample pretreatment 5 ml of the dispersion (E) in which the core-shell polymer (B) before mixing with the epoxy resin of the dispersion medium (A) in the method described in the following examples is dispersed, and dried. After solidification, 50 ml of ethanol was put into a beaker and stirred for 10 minutes, and then the supernatant was used as an analysis sample by the methylene blue method.

[1-2] Measurement by methylene blue method 30 ml of water, 10 ml of an alkaline sodium borate solution, and 5 ml of a methylene blue solution (0.025 mass% aqueous solution) were put into a separating funnel. 20 ml of chloroform was added and shaken for 3 to 5 minutes to separate and remove the chloroform layer. The operation of adding and removing chloroform was repeated until the chloroform layer disappeared. Next, 3 ml of dilute sulfuric acid (2.9 mass% aqueous solution), 20 ml of chloroform and 2 ml of the sample prepared in [1-1] were added, and after shaking for 3 to 5 minutes, the chloroform layer was spectrophotometer (Shimadzu Corporation). The amount of the remaining emulsifier in the dispersion (E) before mixing the epoxy resin of the dispersion medium (A) was measured in absorption at a wavelength of 650 nm using a spectrophotometer UV-2200 manufactured by Seisakusho. The alkaline sodium borate solution was prepared by mixing 500 ml of a 0.4 mass% sodium hydroxide solution with 500 ml of a 1.9 mass% aqueous solution of sodium tetraborate decahydrate.

[2] Analysis of alkali metal ion content [2-1] Pretreatment Sulfuric acid and nitric acid are added to the epoxy resin composition, and pressure acid decomposition is performed using a microwave decomposition apparatus (MLS-1200MEGA manufactured by Milestone General). did.

[2-2] Analysis of electrolytic mass by ICP mass spectrometry (ICP-MS determination)
The HP-4500 type manufactured by Yokogawa Analytical Systems was used, and the amount of Na ions and the amount of K ions were analyzed by high-frequency induction plasma emission analysis by an absolute calibration curve method using Co as an internal standard under cool plasma conditions. The total numerical value of the obtained analytical values was defined as the alkali metal ion content.

[3] Ratio of the organic solvent in the aggregate (G) The ratio of the organic solvent in the aggregate (G) is determined by the solid content concentration (SC) of the aggregate (G) obtained by the methods of Examples and Comparative Examples. The water content (WC) was measured by the following method and calculated by the following formula.
Ratio of organic solvent in aggregate (G) = 100− (SC + WC)
[3-1] Measurement of solid content concentration (SC) of aggregate (G) A predetermined amount of the aggregate (G) is collected and dried in a hot air dryer, and the aggregate (G ) Solid content concentration (SC) was calculated.

[3-2] Measurement of water content (WC) of aggregate (G) A predetermined amount of the aggregate (G) was collected and dispersed in a soluble solvent, and then the aggregate (G) was analyzed by Karl Fischer method. The water content was measured, and the water content (WC) relative to the entire aggregate (G) was calculated.

[4] Quantification of the core-shell polymer (B) component contained in the aqueous phase A part of the aqueous phase discharged by the method described in Examples and Comparative Examples is taken and sufficiently dried at 120 ° C. to obtain a residue This was defined as the amount of the core-shell polymer (B) component contained in the aqueous phase.

[5] Volatile component in epoxy resin composition In Examples and Comparative Examples, in order to obtain an epoxy resin composition, vacuum distillation was continued until the volatile component defined below reached 5000 ppm. After precisely weighing about 3 g of the epoxy resin composition, it was heated in a hot air dryer at a set temperature of 170 ° C. for 20 minutes, the mass before and after heating was measured, and the ratio of the mass loss due to volatilization was calculated as the volatile component (ppm) .

[6] Dispersion state of core-shell polymer in epoxy resin composition [6-1] Preparation of cured epoxy resin 100 parts by mass of prepared epoxy resin, phenol resin as curing agent (PSM-4261 manufactured by Gunei Chemical Industry) 50 parts by mass (Examples 1 and 2 using ortho-cresol novolac type epoxy resin) or 85 parts by mass of phenol resin (Mirex XLC-LL manufactured by Mitsui Chemicals) as a curing agent (Example 3 using phenol type epoxy resin) 4) As a curing accelerator, 2 parts by mass of triphenylphosphine (TPP) (manufactured by Kei-I Kasei), 2 parts by mass of carnauba wax (manufactured by Toa Kasei), 900 parts by mass of fused silica (FB-940A manufactured by Denki Kagaku Kogyo), 5 parts by weight of coupling agent (Shin-Etsu Chemical KBM-403) was added to the Ishikawa-type stirring crusher (Ishikawa Factory Co., Ltd.) After premixing for 10 minutes we had was kneaded for 5 minutes at 100 ° C. using two rolls for kneading (Co. Inoue Seisakusho). The obtained epoxy resin molding material was prepared using a transfer molding machine (manufactured by Maru Nantu Iron Works Co., Ltd.) with a charge amount of 45 g, a molding temperature of 175 ° C., a molding pressure of 70 kgf / cm ² , a transfer ram speed of 5 cm / sec, and molding. Transfer molding was carried out under conditions of 3 minutes to produce a strip-shaped (10 × 70 × 3 mm) cured product.

[6-2] Observation of dispersion state of core-shell polymer by transmission electron microscope A part of the obtained cured product was cut out, the core-shell polymer or rubber particles were dyed with osmium oxide, and then a slice was cut out to obtain a transmission electron microscope ( The dispersion state of the core-shell polymer or the rubber particles in the cured epoxy resin was determined as follows by observation using a JEM 1200EX type manufactured by JEOL Ltd. at a magnification of 10,000 times.
◯: 90% (number basis) The number of individual core-shell polymer particles is not agglomerated with each other in the epoxy resin and is dispersed independently.
○ to Δ: 70% (number basis) or more and less than 90% (number basis) of individual core-shell polymer particles do not aggregate with each other in the epoxy resin and are dispersed independently.
Δ: Core-shell polymer particles having a number of 10% (number basis) or more and less than 70% (number basis) do not aggregate with each other in the epoxy resin and are dispersed independently.
X: Core-shell polymer particles having a number of less than 10% (number basis) do not aggregate with each other in the epoxy resin and are dispersed independently of each other.

Production Example 1 Production of Core-Shell Polymer (B) Latex In a 100 L pressure-resistant polymerization machine, 200 parts by mass of water, 0.03 parts by mass of tripotassium phosphate, 0.25 parts by mass of potassium dihydrogen phosphate, 0 ethylenediaminetetraacetic acid 0.002 part by mass, ferrous sulfate 0.001 part by mass and sodium dodecylbenzenesulfonate 1.5 part by mass were charged with sufficient nitrogen substitution while stirring to remove oxygen, and then 75 parts by mass of butadiene and 25 parts by mass of styrene was charged into the system, and the temperature was raised to 45 ° C. Polymerization was initiated by adding 0.015 parts by mass of paramentane hydroperoxide and then 0.04 parts by mass of sodium formaldehyde sulfoxylate. Four hours after the start of polymerization, 0.01 part by mass of paramentane hydroperoxide, 0.0015 part by mass of ethylenediaminetetraacetic acid and 0.001 part by mass of ferrous sulfate were added. At 10 hours after the polymerization, the residual monomer was removed by devolatilization under reduced pressure to complete the polymerization. The polymerization conversion was 98%, and the volume average particle size of the obtained styrene-butadiene rubber latex was 0.1 μm.

  Into a 3 L glass container, 1300 g of the rubber latex (containing 420 g of styrene-butadiene rubber particles and 1.5% by mass of sodium dodecylbenzenesulfonate based on the solid content of the rubber as an emulsifier) and 440 g of pure water were charged. It stirred at 70 degreeC, performing substitution. After 1.2 g of azobisisobutyronitrile (AIBN) was added, a mixture of 60 g of styrene, 50 g of methyl methacrylate, 30 g of acrylonitrile, and 40 g of glycidyl methacrylate was continuously added over 3 hours for graft polymerization. After completion of the addition, the reaction was terminated by further stirring for 2 hours to obtain a latex of the core-shell polymer (B). The polymerization conversion rate was 99.5%. The obtained latex was used as it was.

Example 1
126 g of methyl ethyl ketone (water solubility at 20 ° C., 10% by mass) in a 1 L tank with a stirrer (a stirrer in which three flat paddle blades with an inner diameter of 100 mm and a blade diameter of 75 mm are installed in three stages in the axial direction) are placed and stirred at 500 rpm. 126 g of the aqueous latex of the core-shell polymer (B) obtained in Production Example 1 was added. After mixing uniformly, 200 g of water was added at a feed rate of 80 g / min with stirring at 500 rpm. When the stirring was stopped immediately after completion of the supply, a slurry liquid composed of a floating phase (G) and an aqueous phase partially containing an organic solvent was obtained. Next, an agglomerate (G) containing a part of the aqueous phase was left, and 348 g of the aqueous phase was discharged from the discharge port at the bottom of the tank. The aggregate (G) containing a part of the aqueous phase was 104 g, and the ratio of the organic solvent was 39% by mass with respect to the mass of the entire aggregate. Aggregate (G) has floating properties, and the aggregate is a particle having a particle size distribution. When a part of the aggregate (G) was subjected to image analysis, the number average particle size was about 5 mm. Moreover, the density | concentration of the core-shell polymer (B) component in the discharged | emitted aqueous phase was 0.1 mass%. The obtained aggregate (G) was filtered and dehydrated with a filter with a suction bottle, and dried in a nitrogen atmosphere at 40 ° C. for 12 hours using a box dryer to obtain core-shell polymer (B) particles. A part of the obtained aggregate was sampled, methyl ethyl ketone was added to prepare a dispersion dope, and the remaining emulsifier and electrolyte were measured. As a result, the removal rates were 95% and 90%, respectively. 65 g of methyl ethyl ketone was added to 50.0 g of the obtained aggregate and mixed for 30 minutes under a stirring condition of 500 revolutions per minute to obtain a dispersion in which the core-shell polymer was uniformly dispersed. This dispersion was transferred to a 1 L tank equipped with a jacket and a stirrer (stirrer equipped with an anchor blade having an inner diameter of 100 mm and an airfoil of 90 mm), and ortho-cresol novolac type epoxy resin (Sumitomo Chemical Co., Ltd. Sumiepoxy ESCN 195XL-4) 169. After adding 0 g and mixing uniformly, the jacket temperature was set to 110 ° C., and the vacuum pump (oil rotary vacuum pump, TSW-150 manufactured by Sato Vacuum Co., Ltd.) was used, and the volatile components were at a predetermined concentration (5000 ppm) under reduced pressure. Distillation was continued until reached. After introducing nitrogen gas into the tank and returning the internal pressure to atmospheric pressure, the contents are discharged in a molten state onto a fluororesin sheet, allowed to cool and solidify, and pulverized to give a pale yellow flaky epoxy resin A composition (curable resin composition for insulating film) was obtained. The time required for volatilization was 4 hours. The alkali metal ion content in the epoxy resin composition was 9.0 ppm. The residual emulsifier amount was 53 ppm. As a result of observing the dispersion state of the core-shell polymer in the cured product obtained from this epoxy resin composition, it was found that 90% (number basis) individual core-shell polymer particles were uniformly dispersed without aggregation. They did not aggregate with each other in the resin and were dispersed independently).

(Example 2)
Into a 1 L tank with a stirrer (stirrer equipped with a three-way receding blade having an inner diameter of 100 mm and a blade diameter of 56 mm), 144 g of methyl ethyl ketone was added, and 144 g of the aqueous latex of the core-shell polymer (B) obtained in Production Example 1 was added while stirring at 400 rpm. And mixed uniformly. While stirring was stopped, 207 g of water was gently introduced from the outlet at the bottom of the tank, and then stirred for 2 minutes under stirring at 400 rpm. After the completion of stirring, a slurry liquid composed of an aqueous phase containing an aggregate (G) (floating property) and an organic solvent was obtained. Next, agglomerates (G) containing a part of the aqueous phase remained, and 373 g of the aqueous phase was discharged from the discharge port at the bottom of the tank. The aggregate (G) containing a part of the aqueous phase was 122 g, and the ratio of the organic solvent was 45% by mass with respect to the mass of the entire aggregate (G). The number average particle diameter of the aggregate (G) was about 5 mm. Moreover, the density | concentration of the core-shell polymer (B) component in the discharged | emitted aqueous phase was 0.2 mass%. Thereafter, core-shell polymer (B) particles were obtained in the same manner as in Example 1. A part of the obtained aggregate was sampled, methyl ethyl ketone was added to prepare a dispersion dope, and the remaining emulsifier and electrolyte were measured. As a result, the removal rates were 92% and 87%, respectively. 120 g of methyl ethyl ketone was added to 70.0 g of the obtained aggregate and mixed for 30 minutes under a stirring condition of 500 revolutions per minute to obtain a dispersion (E) in which the core-shell polymer (B) was uniformly dispersed. This dispersion (E) was transferred to a 1 L tank with a jacket and a stirrer (stirrer provided with an anchor blade having an inner diameter of 100 mm and a wing shape of 90 mm), and 117.8 g of a biphenyl type epoxy resin (YX4000H manufactured by Japan Epoxy Resin Co., Ltd.) In addition, after uniform mixing, the jacket temperature is set to 90 ° C., and a volatile component reaches a predetermined concentration (5000 ppm) under reduced pressure using a vacuum pump (oil rotary vacuum pump, TSW-150 manufactured by Sato Vacuum Co., Ltd.). Distillation was continued until. After introducing nitrogen gas into the tank and returning the internal pressure to atmospheric pressure, the contents are discharged in a molten state onto a fluororesin sheet, allowed to cool and solidify, and pulverized to give a pale yellow flaky epoxy resin A composition was obtained. The time required for volatilization was 5 hours. The alkali metal ion content in this epoxy resin composition was 19.6 ppm. The residual emulsifier amount was 47 ppm. As a result of observing the dispersion state of the core-shell polymer (B) in the cured product obtained from this epoxy resin composition, it was uniformly dispersed without aggregation (90% (number basis) or more individual core-shell polymer particles) However, they did not aggregate with each other in the epoxy resin and were dispersed independently).

(Comparative Example 1)
500 g of the aqueous latex of the core-shell polymer (B) of Production Example 1 was placed in a 1 L tank with a stirrer (stirrer in which four flat paddle blades having an inner diameter of 100 mm and a blade diameter of 75 mm were installed in three stages in the axial direction), and coagulated with stirring at 400 rpm. As an agent, 13 g of 35% by mass calcium chloride CaCl ₂ aqueous solution was added to form aggregates. The slurry containing the aggregate was heated to 60 ° C. with stirring, and then cooled to 23 ° C. This slurry was filtered and dehydrated with a filter with a suction bottle, and then the agglomerate was dried at 40 ° C. for 12 hours using a box dryer to obtain a core-shell polymer (B) particle powder.

The same procedure as in Example 2 was performed except that the obtained core-shell polymer (B) particle powder was blended at a ratio of 10% by mass with respect to the biphenyl type epoxy resin component. The alkali metal ion content in this epoxy resin composition was 148 ppm. As a result of observing the dispersion state of the core-shell polymer (B) in the cured product obtained from this epoxy resin composition, core-shell polymer particles having a number of less than 10% (number basis) did not aggregate with each other in the epoxy resin. , Each was distributed independently.

  From the above results, good dispersion of the core-shell polymer can be obtained, and at the same time, the residual amount of emulsifier and metal ions that cause cracking can be reduced, cracking suppression, high insulation, fine shape during exposure Formability can be achieved.

Claims (14)

A dispersion medium (A) and a core-shell polymer (B) having a rubber-like elastic core layer,
At least 70% (based on the number) of the core-shell polymer (B) is dispersed in the state of primary particles in the dispersion medium (A),
The dispersion medium is a thermosetting resin, polymerizable monomers, and polymerizable oligomers over or Ranaru least one selected from the group,
The thermosetting resin is at least one selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a phenol resin, a silicone resin, a cyanate ester resin, and a polyurethane resin;
The polymerizable monomer is at least one selected from the group consisting of monofunctional acrylates, polyfunctional acrylates, epoxy compounds, oxetane compounds, and vinyl ether compounds;
The polymerizable oligomer is composed of epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, copolymer acrylate, polybutadiene acrylate, alicyclic epoxy compound, glycidyl ether type epoxy compound, polyfunctional oxetane compound, and vinyl ether compound. A composition for modifying an insulating film, wherein the composition is one or more oligomers selected from the group.   2. The composition for modifying an insulating film according to claim 1, wherein 80% (based on the number) of the core-shell polymer (B) is dispersed in the form of primary particles.   The composition for insulating film modification according to claim 1 or 2, wherein the core-shell polymer (B) has a volume average particle diameter of 10 nm to 2000 nm.   The composition for insulating film modification according to claim 1, wherein the alkali metal ion content is 200 ppm (mass basis) or less.   The composition for modifying an insulating film according to any one of claims 1 to 4, wherein the anionic emulsifier content is 2000 ppm (mass basis) or less.   The composition for modifying an insulating film according to any one of claims 1 to 5, an epoxy resin, an unsaturated polyester resin, a phenol resin, a silicone resin, a cyanate ester resin, a polyurethane resin, a polymerizable monomer, and a polymerizable oligomer A matrix-forming component that is at least one selected from the group consisting of: and the polymerizable oligomer contains a photopolymerizable prepolymer having a carboxy group or a hydroxyl group and an ethylenically unsaturated group. A curable resin composition for an insulating film. Selected from the group consisting of a core-shell polymer (B) having a rubber-like elastic core layer, an epoxy resin, an unsaturated polyester resin, a phenol resin, a silicone resin, a cyanate ester resin, a polyurethane resin, a polymerizable monomer, and a polymerizable oligomer. that der 1 or more is, and contains a component polymerizable oligomer can always matrixed Ru is selected, the core-shell polymer (B) of at least 70% (number basis) of primary particles in the component that may be matrixed A curable resin composition for an insulating film, wherein the polymerizable oligomer is dispersed in a state of the above, and the polymerizable oligomer contains a photopolymerizable prepolymer having a carboxy group or a hydroxyl group and an ethylenically unsaturated group.   The curable resin composition for an insulating film according to claim 6 or 7, wherein the alkali metal ion content is 30 ppm (mass basis) or less.   The curable resin composition for an insulating film according to any one of claims 6 to 8, wherein an anionic emulsifier content is 100 ppm (mass basis) or less.   The curable composition for an insulating film according to claim 6 or 7, wherein the polymerizable monomer is at least one selected from the group consisting of a monofunctional acrylate, a polyfunctional acrylate, an epoxy compound, an oxetane compound, and a vinyl ether compound. Resin composition.   The polymerizable oligomer is composed of epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, copolymer acrylate, polybutadiene acrylate, alicyclic epoxy compound, glycidyl ether type epoxy compound, polyfunctional oxetane compound, and vinyl ether compound. The curable resin composition for an insulating film according to claim 6 or 7, further comprising at least one oligomer selected from the group.   The curable resin composition for an insulating film according to any one of claims 6 to 11, wherein a polymer of the polymerizable monomer and the polymerizable oligomer contains an alkali-soluble resin.   The curable resin composition for an insulating film according to any one of claims 6 to 11, wherein a polymer of the polymerizable monomer and the polymerizable oligomer contains an alkali-insoluble resin.   The curable resin composition for insulating films according to any one of claims 6 to 13, which is used for a solder resist material, a build-up material, a prepreg material, or an adhesive for a flexible printed circuit board.