JP2001302736A - Polymer insulation material and its manufacturing method, and electronics-related substrate and electronic member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer insulation material excellent in electric characteristics such as a dielectric constant, a dissipation factor, insulation properties, and the like, solvent resistance, heat resistance and thermal shock resistance, to provide a method for manufacturing the polymer insulation material, an electronics-related substrate and an electronic member. SOLUTION: The polymer insulation material is obtained by thermal cure of a monomer composition comprising a fumaric acid diester, a crosslinkable monomer bearing at least two carbon-carbon double bonds in one molecule and a thermally decomposable polymerization initiator. Preferably, the fumaric acid diester is the main component of the monomer composition. Desirably, the content of the thermally decomposable polymerization initiator is 0.1-10 wt.% based on the monomer composition. The electronics-related substrate such as a print wiring board, or the like, and an electronic member such as a build up material, an undercoat material, or the like, are obtained by forming a substituent material containing the polymer insulation material into a desired shape and subsequently heating it to cure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer insulating material comprising a crosslinked fumaric acid diester polymer, a method for producing the same, and an electronic substrate and an electronic member. More specifically, a polymer insulating material having excellent dielectric properties and heat resistance, a method for producing the same, and electronic-related substrates and laminates such as a printed wiring board formed from the polymer insulating material, an adhesive, an underfill material, The present invention relates to an electronic member such as a conductive film, a solder resist, an interlayer insulating film for a semiconductor, a mold material, and a build-up material such as a build-up substrate.

[0002]

2. Description of the Related Art Recently, with the rapid increase of portable information communication devices, there has been an increasing demand for higher performance of information processing devices accompanying an increase in the amount of information communication. That is, in order to process a large amount of digital or analog information in a short time by using a small portable device, a response to a higher frequency of each electronic component constituting the information processing device is being promoted. However, the conventional insulating materials have limitations on the transmission speed and transmission loss of electric signals, and as a result, the dimensions of devices and their information processing capabilities have been limited.

[0003] Therefore, a material having a low dielectric constant has been proposed to increase the transmission speed, and a material having a low dielectric loss has been proposed to reduce the transmission loss. In order to satisfy these requirements, the present inventors have proposed a low dielectric polymer material comprising a fumaric acid diester polymer having a specific structure in Japanese Patent Application Laid-Open No. 9-208627. This low dielectric polymer material has good adhesion or adhesion to a conductor and a glass woven cloth, has a thin film forming ability, and has excellent electric characteristics in a high frequency range (low dielectric constant and dielectric loss tangent). Furthermore, it is excellent in workability.

With the demand for high-density mounting, a build-up method of forming a multilayer printed board by alternately laminating a wiring board and an organic insulating resin layer has been widely adopted. In this build-up method, it is important to form electroless plating with good adhesion on the organic insulating resin layer. However, it is very difficult to perform electroless plating with good adhesion on the organic insulating resin layer. Furthermore, the organic insulating resin itself is shifting from the conventional relatively easy-to-roughen epoxy resin to a more heat-resistant, solvent-resistant, and difficult-to-roughen resin. It is becoming difficult to roughen the surface.

[0005]

SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open No.
The low-dielectric polymer material having good electric properties disclosed in Japanese Patent No. 208627 does not have a cross-linked structure, and thus has excellent workability as a varnish, but has a problem in heat resistance.
For example, when used as a material for electrical insulation, there has been a problem that portions that come into contact with various organic solvents and coating materials may swell.

Further, the low dielectric polymer material is dissolved in an organic solvent at the time of processing, and then molded into a desired shape and used. However, at this time, the following organic solvent is required. Such a problem may occur. For example, when used as an adhesive for a laminate or a substrate such as a printed wiring board, the organic solvent used at the time of lamination or bonding is apt to remain, so that the laminate or the substrate swells at the time of solder reflow, or the solvent resistance. There was a problem that the property is low.

Further, when used as an underfill material, an anisotropic conductive film, or an interlayer insulating film for semiconductors used between an electronic component and a substrate, the coefficient of linear expansion changes significantly during solder reflow, resulting in poor insulation and poor conduction. There was a problem that defects occurred. Furthermore, in order to form a thick object, the number of times of application and drying must be increased. As a result, the internal stress tends to remain, resulting in a decrease in strength and thermal shock resistance. And uniformity were limited.

In addition, even if a monomer composition comprising a fumaric acid diester containing no crosslinking monomer is polymerized with a polymerization initiator, there is a high possibility that the monomer remains. For example, when used as an encapsulating material for semiconductors, there is a high possibility that monomers will remain, and this is considered as one of the factors that affect the properties such as insulating properties of electronic elements and circuit boards.

Further, when used as a solder resist material for a circuit board, there is a high possibility that the monomer remains in the same manner, and this is one of the factors that affect the properties such as the insulating properties of electronic elements and circuit boards. Is considered as.

The present invention has been made in view of the above-mentioned problems existing in the prior art. The object is to provide a polymer insulating material excellent in electric properties such as dielectric constant, dielectric loss tangent, and insulating property, solvent resistance, heat resistance and thermal shock resistance, a method of manufacturing the same, and an electronic-related substrate and an electronic member. Is to do.

[0011]

This and other objects are achieved by the present invention described below. That is, the polymer insulating material of the first invention is a monomer composition containing a fumaric acid diester, a monomer having two or more carbon-carbon double bonds in one molecule, and a thermal decomposition type polymerization initiator. It is obtained by heat curing.

A polymer insulating material according to a second aspect of the present invention is the polymer insulating material according to the first aspect, wherein the fumaric acid diester is a main component in the monomer composition. A polymer insulating material according to a third aspect is the polymer insulating material according to the first or second aspect, wherein the content of the thermal decomposition type polymerization initiator with respect to the monomer composition is 0.1 to 10% by weight.

A method for producing a polymer insulating material according to a fourth aspect of the present invention is a method for producing a polymer insulating material, comprising mixing a fumaric acid diester, a monomer having two or more carbon-carbon double bonds in one molecule, and a pyrolytic polymerization initiator. It is characterized in that a monomer composition is prepared, molded into a desired shape, and then cured by heating.

An electronic-related substrate according to a fifth aspect of the present invention is formed of a constituent material including the polymer insulating material according to any one of the first to third aspects. An electronic member according to a sixth aspect is formed of a constituent material including the polymer insulating material according to any one of the first to third aspects.

A build-up material according to a seventh aspect of the present invention is formed from the constituent material containing the polymer insulating material and the filler according to any one of the first to third aspects.

[0016]

Embodiments of the present invention will be described below in detail. The polymer insulating material of the present invention includes a fumaric acid diester, a monomer having two or more carbon double bonds in one molecule (hereinafter, abbreviated as a crosslinkable monomer), and a thermal decomposition type polymerization initiator (hereinafter, referred to as a crosslinkable monomer). , An initiator) is obtained by heating and curing a monomer composition containing as an essential component (hereinafter, abbreviated as a monomer composition).

The content of the fumaric acid diester in the monomer composition is usually in the range of 20 to 95% by weight, preferably the main component, more preferably 50 to 90% by weight. When the content of the fumaric acid diester is less than 20% by weight, the dielectric constant and the dielectric loss tangent of the polymer insulating material increase, and the heat resistance decreases.
If the amount is larger, the solvent resistance of the polymer insulating material decreases.

The fumaric acid diester has two ester groups in the molecule and is represented by the following general formula (1).

[0019]

Embedded image R ₁ and R ₂ in the general formula (1) are ester residues, and can be variously selected according to required properties such as low dielectric property and heat resistance. Specifically, R ₁ is an alkyl group or a cycloalkyl group, R ₂ is an alkyl group,
It is preferably a cycloalkyl group or an aryl group. R ₁ and R ₂ may be the same or different ester groups.

As the alkyl group for R ₁ or R ₂ ,
Those having a total carbon number of 2 to 12 are preferable, and may be linear or branched, and may further have a substituent. Examples of the substituent having a substituent include a halogen atom (F, Cl), an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group), and an aryl group (such as a phenyl group).

Specific examples of the alkyl group include an ethyl group,
n-propyl group, isopropyl group, n-butyl group, sec
-Butyl group, tert-butyl group, pentyl group (n-amyl group), sec-amyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 4
-Methyl-2-pentyl group, heptyl group, octyl group,
Nonyl group, decyl group, undecyl group, dodecyl group trifluoroethyl group, hexafluoroisopropyl group, perfluoroisopropyl group, perfluorobutylethyl group,
Perfluorooctylethyl group, 2-chloroethyl group,
Examples thereof include a 1-butoxy-2-propyl group, a methoxyethyl group, and a benzyl group.

The cycloalkyl group as R ₁ or R ₂ is preferably a cycloalkyl group having 3 to 14 carbon atoms, and may be a single ring or a group having a bridged ring. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a dimethyladamantyl group.

The aryl group represented by R ₂ is preferably an aryl group having 6 to 18 carbon atoms in total, and is preferably a single ring from the viewpoint of polymerizability, but may be a polycyclic (condensed ring or ring assembly). You may have. In this case, the substituents are the same as those exemplified for the alkyl group and the cycloalkyl group. Specific examples of the aryl group include a phenyl group.

Preferred examples of the fumaric acid diester include diethyl fumarate, di-n-propyl fumarate, di-n-hexyl fumarate and isopropyl-n-fumarate.
Hexyl fumarate, diisopropyl fumarate, di-
n-butyl fumarate, di-sec-butyl fumarate, di-tert-butyl fumarate, di-sec-amyl fumarate, n-butyl-isopropyl fumarate, isopropyl-sec-butyl fumarate, ter
t-butyl-4-methyl-2-pentyl fumarate, isopropyl-tert-butyl fumarate, isopropyl-sec-amyl fumarate, di-4-methyl-2-pentyl fumarate, di-isoamyl fumarate, di-
Dialkyl fumarate such as 4-methyl-2-hexyl fumarate, tert-butyl-isoamyl fumarate; dicyclopentyl fumarate, dicyclohexyl fumarate, dicyclohebutyl fumarate, cyclopentyl-cyclohexyl fumarate, bis (dimethyladamantyl) ) Dicycloalkyl fumarate such as fumarate and bis (adamantyl) fumarate; alkyl such as isopropyl-cyclohexyl fumarate, isopropyl-dimethyl adamantyl fumarate, isopropyl-adamantyl fumarate, tert-butyl-cyclohexyl fumarate Alkylaryl fumarate such as isopropyl-phenyl fumarate; tert-butylbenzyl fumarate, isopropyl-benzyl fumarate Alkyl aralkyl fumarate such as difluoroethyl fumarate, dihexafluoroisopropyl fumarate, bisperfluoroisopropyl fumarate, bisperfluorobutyl ethyl fumarate, etc .; isopropyl-perfluoro Alkylfluoroalkyl fumarate such as octylethyl fumarate and isopropyl-hexafluoroisopropyl fumarate; 1
And other substituted alkylalkyl fumarate such as -butoxy-2-propyl-tert-butyl fumarate, methoxyethyl isopropyl fumarate and 2-chloroethyl-isopropyl fumarate.

Among them, diisopropyl fumarate, dicyclohexyl fumarate, di-s
ec-butyl fumarate, di-tert-butyl fumarate, isopropyl-cyclohexyl fumarate, te
Particularly preferred are rt-amyl-isopropyl fumarate, n-hexyl-isopropyl fumarate and the like.

In obtaining the polymer insulating material of the present invention, only one type of the above fumaric acid diester may be used.
More than one species may be used in combination. Further, these fumaric acid diesters can be synthesized by combining ordinary esterification techniques and isomerization techniques.

Next, the crosslinkable monomer imparts an improvement in the solvent resistance and mechanical strength of the polymer insulating material by copolymerizing with the fumaric acid diester. The content of the crosslinkable monomer in the monomer composition is preferably 5 to 80% by weight, and more preferably 10 to 60% by weight. When the content is less than 5% by weight, the solvent resistance of the polymer insulating material decreases, and when it exceeds 80% by weight, the dielectric constant and the dielectric loss tangent tend to increase.

The crosslinkable monomer used in the present invention is a monomer having two or more carbon-carbon double bonds in one molecule, that is, a vinyl group, an acryloyl group, a methacryloyl group, a maleimide group, a vinyl ether group, a vinyl ester. Is a crosslinkable monomer having a group, an allyl ether group, an allyl ester group and the like. Among these functional groups, a vinyl group, a maleimide group or an allyl ester group is preferable because of its excellent copolymerizability.

Specifically, polyfunctional olefins such as butadiene and isoprene, diethylene glycol diacrylate, 1,3-butanediol diacrylate, bisphenol A type diacrylate, urethane diacrylate, epoxy diacrylate, trimethylolpropane triacrylate, Multifunctional acrylates such as pentaerythritol tetraacrylate, phenol novolak type epoxy acrylate, diethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, bisphenol A type dimethacrylate, urethane dimethacrylate, epoxy dimethacrylate, trimethylolpropane trimethacrylate, Pentaerythritol tetramethacrylate, phenol novolak type epoxy methacrylate, etc. Polyfunctional vinyl monomers such as polyfunctional methacrylate, divinylbenzene and bisphenol A type vinylbenzyl ether; polyfunctional maleimides such as 1,3-phenylenebismaleimide and 4,4′-diphenylmethanebismaleimide; Polyfunctional vinyl ethers such as cyclohexane dimethanol divinyl ether, 2,2-dimethylhexanediol divinyl ether, diethylene glycol divinyl ether, trimethylolpropane trivinyl ether, divinyl adipate, divinyl 1,4-cyclohexanedicarboxylate,
Polyfunctional vinyl esters such as divinyl phthalate and divinyl isophthalate, cyclohexane dimethanol diallyl ether, 2,2-dimethylhexanediol diallyl ether, diethylene glycol diallyl ether, trimethylolpropane triallyl ether, bisphenol A diallyl ether, triallyl Examples include polyfunctional allyl monomers such as isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and diallyl ester of phthalic polyester. These crosslinkable monomers may be used alone or in combination of two or more. Next, as the initiator used in the present invention, one or more of an organic peroxide and an azo compound are used. Since these initiators do not contain metals, they do not affect the electrical performance of the resulting polymeric insulating material. Such initiators include, for example, benzoyl peroxide, diisopropylperoxydicarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, dicumyl peroxide, tert-butylhydrogen. Peroxide, tert-butyl peroxypivalate, lauroyl peroxide, 1,1-bis (tert-
Butylperoxy) -3,3,5-trimethylcyclohexane, tert-butylperoxyisopropyl carbonate, tert-butylperoxybenzoate,
Di-tert-butylperoxyisophthalate, 2,
Organic peroxides such as 5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyro) Nitrile), azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-
Azo compounds such as 1-carbonitrile), 2,2′-azobis (isobutyric acid) dimethyl, and 2,2′-azobis (2,4-dimethylpareronitrile).

Of these initiators, benzoyl peroxide, dicumyl peroxide, 1,1-bis (tert
-Butylperoxy) -3,3,5-trimethylcyclohexane, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 or 2,2′-azo Bisisobutyronitrile is preferred because of its high polymerization initiating ability.

The amount of the initiator used is usually 0.1 to 10% by weight, preferably 1 to 10% by weight, more preferably 1 to 7% by weight, based on the monomer composition. If the amount is less than 0.1% by weight, the polymerization initiation function is not sufficiently exhibited, and if it exceeds 10% by weight, the initiator remains in the polymerized insulating material after polymerization, and Physical properties may decrease.

In the present invention, fumaric acid diester,
In addition to the crosslinking monomer and the initiator, other vinyl monomers or other polymers can be added to the monomer composition. These additives are the viscosity of the monomer composition,
It can be added for the purpose of adjusting the mechanical strength and smoothness of the molded polymer insulating material and the adhesion between the coating film and the substrate.

Specific examples of the other vinyl monomers include vinyl esters such as vinyl acetate, vinyl pivalate, p-tert-butyl vinyl benzoate and vinyl benzoate; styrene, o-, m-, and vinyl esters. aromatic vinyls such as p-chloromethylstyrene, α-methylstyrene, o-, m-, p-methylstyrene, p-chlorostyrene and α-vinylnaphthalene; tert-butyl vinyl ether;
Vinyl ethers such as isobutyl vinyl ether and cyclohexyl vinyl ether; alkyl vinyl ketones such as methyl vinyl ketone and isobutyl vinyl ketone; olefins such as isobutylene and 1-butene; methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) Acrylate, 2-ethylhexyl (meth)
(Meth) acrylic acid such as acrylate and phenyl (meth) acrylate or esters thereof; vinyl cyanes such as acrylonitrile; maleic anhydride, maleic acid, itaconic acid, itaconic anhydride, dimethyl itaconate, diethyl itaconate, and itaconic acid Known radically polymerizable monomers such as unsaturated dibasic acids such as dibutyl and dicyclohexyl itaconate and esters thereof can be preferably exemplified.

Examples of the other polymer include homopolymers or copolymers of other vinyl monomers, and thermosetting resins such as phenol resins, epoxy resins, diallyl phthalate resins, unsaturated polyesters, and cyanate ester resins. Polyolefins such as polyethylene resin, polypropylene, polyisobutylene, polybutene, polyimide resin precursor, butyral resin, polyphenylene oxide, polyphenylene sulfide, polyester, polycarbonate, styrene-butadiene block copolymer, and styrene-isoprene block copolymer. Examples include thermoplastic resins such as thermoplastic elastomers such as polymers, hydrogenated styrene-butadiene block copolymers, and hydrogenated styrene-isoprene block copolymers. When adding other additives, they may be added to the monomer composition using an organic solvent that dissolves other polymers. Such other vinyl monomers or other polymers may be used alone or in combination of two or more.

The amount of the other vinyl monomer or other polymer is preferably at most 30% by weight, more preferably at most 10% by weight, based on the monomer composition. When the addition amount is more than 30% by weight, the dielectric constant and the dielectric loss tangent increase when a vinyl monomer is used, and further, the heat resistance decreases, and when a polymer is used, the viscosity increases. It is not preferable because it causes a decrease in the properties, adhesion of the coating film to the substrate, and mechanical strength of the film.

Further, in order to improve the coating property, a leveling agent such as silicone oil is added to the mixture as necessary so as not to affect the curing, or the mixture is dissolved and dispersed in an organic solvent or emulsified and dispersed in water. A thing may be used.

Further, dyes, pigments, thixotropic agents, plasticizers,
Surfactants, ultraviolet absorbers, antioxidants, flame retardants, coupling agents and the like may be included in the monomer composition.

A filler may be added to adjust the coefficient of linear expansion, heat resistance, adhesion to a conductor and workability,
Examples of the filler include inorganic compounds such as silica, barium sulfate, and calcium carbonate, thermosetting resin powders such as phenol resin, melamine resin, and polyimide, polyolefin resin, polystyrene resin, nylon, polyethylene terephthalate, polycarbonate, and styrene-butadiene. Thermoplastic resin powders such as block copolymers, hydrogenated styrene-butadiene block copolymers, and hydrogenated styrene-isoprene block copolymers can be used.

Hereinafter, a method for producing a polymer insulating material formed from the monomer composition of the present invention, its use, and details of the use will be described. <Production Method of Polymer Insulating Material> In the present invention, in order to produce the above-mentioned polymer insulating material, a usual heat curing method can be used. Specifically, fumaric acid diester,
If necessary, other additives, fillers and the like are added to the monomer composition containing the crosslinkable monomer and the initiator, and these are mixed in a pot or the like. Take this for 10 minutes to 20 hours, 30 to 25
By performing a heat polymerization reaction at 0 ° C., a polymer insulating material having a desired shape can be obtained. Heating temperature is 30 ℃
If the heating time is less than 10 minutes, the polymerization reaction may not proceed sufficiently.If the heating temperature exceeds 250 ° C. or the heating time exceeds 20 hours, the polymer may be decomposed, Or lower. In this case, after a prepreg having a predetermined shape is formed in advance, the prepregs are laminated, and heated and pressed by a desired mold to obtain a polymer insulating material.

When a solid fumaric acid diester is used, it is first dissolved in a crosslinkable monomer, mixed with an initiator to prepare a monomer composition, and then cured under the same conditions as described above. Good. Alternatively, the monomer composition may be prepared after dissolving the fumaric acid diester using an organic solvent.In such a case, the organic solvent is removed after forming the desired shape and cured under the same conditions as above. It should be done. As described above, even when an organic solvent is used, the organic solvent is removed before the polymerization reaction is started, so that it is possible to eliminate the influence of the organic solvent during the polymerization reaction and the residual organic solvent after the reaction.

Alternatively, in order to improve the handling, the monomer composition is once pre-cured for 10 minutes to 5 hours at a temperature of 50 to 200 ° C., formed into a desired shape, and then cured again under the above conditions. You may. Here, the pre-curing means
It refers to curing to a state where the polymerization reaction can be advanced to some extent to maintain the shape, and includes the prepreg.

The heating and curing conditions may be changed according to the state of the reaction. Further, it may be cured while applying pressure by a press or the like. Since the hardness increases as the reaction proceeds, a more uniform cured product can be obtained by curing while changing the pressing pressure, the reaction temperature, and the reaction time.

In the conventional method, a polymer was once produced, dissolved in an organic solvent or the like, then formed into a desired shape, and a molded product was obtained by a process of evaporating the organic solvent. On the other hand, according to the present invention, the monomer composition before the reaction is directly molded into a desired shape without using an organic solvent, so that there is no problem caused by the residual organic solvent as in the prior art. Applications of polymer insulating material> The polymer insulating material of the present invention is
It can be used as an insulating film, a film impregnated in a glass woven fabric or the like, or in various forms such as a bulk molded body or a laminated body.

Applications include, for example, electronic components such as high-frequency resonators, filters, capacitors, inductors, and antennas; interlayer insulating films and sealing materials for electronic components such as housings, casings, coatings, and semiconductors of the electronic components. And other electronic members. Further, it is an electronic-related substrate (hereinafter simply referred to as a substrate) such as an on-board substrate for mounting electronic components, a copper-clad laminate for a substrate, a circuit-containing substrate, an antenna substrate, and an on-board substrate for a CPU.

Further, as a material constituting the substrate, for example, a build-up material, a solder resist material, an undercoat material, a back coat material, a top coat material, an interlayer adhesive,
It can be used as a passivation material formed on the surface of an IC substrate, a moisture-proof material for a hybrid IC substrate, and the like. Also,
A matrix of a coating material, an anisotropic conductive film material, and a conductor forming printing material can also be used. In addition, it can be used as an underfill material (a damper for absorbing expansion) or a mold material of an electronic member.

<Details of each application> (Insulating film, laminate, substrate) The monomer composition of the present invention is coated on a substrate such as a resin film, a glass plate, a silicone rubber plate, a metal plate, and heated. By curing, an insulating film or an insulating plate can be formed. As a coating method, a spin coating method, a dip coating method, a curtain coating method, a roll coating method, a screen printing coating method, or the like can be applied.

Further, a film or plate composited with the fibers can be obtained by impregnating the monomer composition with an inorganic fiber, an inorganic filler, an organic fiber or a non-woven fabric and then thermosetting. Various glass fibers such as E glass, C glass, A glass, S glass, D glass, and Q glass as inorganic fibers, fused silica and calcium carbonate as inorganic fillers, and aramid fibers, carbon fibers, and polyester as organic fibers. Fibers and the like and nonwoven fabrics made of aramid, aromatic polyester and the like can be used.

The laminate is formed by laminating the above-mentioned film or plate material to a desired thickness. Specifically, after alternately laminating the cured film or plate material and the monomer composition of the present invention as an interlayer adhesive, or after laminating the precured film or plate material (prepreg), It can be obtained by thermocompression bonding using a press or a roll.

The substrate can be obtained by forming a metal conductor layer on the surface of the laminate. The metal used for the metal conductor layer is not particularly limited as long as it is a metal having conductivity, but a conductor such as copper, nickel, silver, and gold is preferable.
As a forming method, a conductive foil bonding method, an electroless plating method,
An electrolytic plating method, a vacuum evaporation method, a conductive paste coating method, or the like is used, and the thickness of the metal conductor layer is preferably 1 to 100 μm.

When a single-layer printed wiring board is manufactured, a conductor foil is preferable as the metal conductor layer in terms of workability and production cost. The method for laminating the film and the conductive foil can be the same method as the method for producing the substrate. Specifically, the conductive foil is formed by using an interlayer adhesive on one or both sides of an alternate laminate of a cured film and an interlayer adhesive. Or a conductor foil is laminated on one or both sides of the prepreg laminate.

Further, a multilayer printed wiring board can be manufactured by laminating a single-layer printed wiring board formed with a circuit, a through hole, and a plating. When a metal conductor layer is formed in a circuit, a film or substrate having the metal conductor layer on the surface is etched and patterned into a predetermined shape, or a prepreg film having the metal conductor layer on the surface is etched and patterned. After performing the lamination and thermosetting. Alternatively, a method of printing an etching resist according to a circuit pattern on a laminate using a pattern printing machine such as a silk screen printing machine, followed by plating, and peeling off the etching resist to form a circuit pattern is also possible.

(Build-up material)
A circuit board (single-layer printed wiring board or multilayer printed wiring board) having a circuit pattern on its surface has at least one layer composed of a combination of an insulating layer and a conductive layer on at least one surface, and the conductive layers are connected. An insulating layer (insulating material) used for a printed wiring board. When providing an insulating layer of resin only on the upper and lower parts of the substrate, as a method of bonding a copper foil which is a conductor with a conventional material, the organic solvent is removed after bonding the copper foil while leaving a certain amount of the organic solvent . However, according to this method, it is difficult to remove the organic solvent, and problems such as a decrease in heat resistance may occur. On the other hand, the material of the present invention can obtain tackiness even if the organic solvent is removed after the application, so that it is easy to bond the copper foil. Further, if this material is applied to a copper foil in advance, there is an advantage that it is only necessary to bond the material to the base material.

Further, when a conductive layer is formed on the build-up material by plating, the surface of the insulating layer is roughened to improve the adhesion between the insulating layer and the conductive layer (plated layer). Although a method of performing electrolytic plating is generally used, since the build-up material of the present invention contains a filler, chemical etching is easy. As the filler, polystyrene, silica gel, calcium carbonate, or the like is used. Note that the build-up material does not need to include a filler, and the etching may be a physical method.

(Undercoat material) The undercoat material absorbs a step (about ten and several μm) generated when a metal conductor layer, for example, a copper foil is adhered to a base material to produce a substrate, and provides smoothness. Liquid or film-like insulating material. A low-shrinkage material is preferable because it is assumed that the step is eliminated. However, in conventional materials, it is difficult to control the film thickness and the like because it is necessary to consider the volatilization amount of the organic solvent. On the other hand, since the material of the present invention can be made organic solvent-free without using an organic solvent, it is only necessary to consider only shrinkage accompanying the curing reaction. preferable.

(Interlayer adhesive) The interlayer adhesive is an adhesive used for bonding the base material or the substrate and the conductor foil, and is completely cured to bond the substrates or the substrate and the metal conductor film. Used for the purpose of firmly bonding. The substrate is not limited to the one formed of the insulating material of the present invention, and may be another dielectric resin or ceramic.

(Underfill material) The underfill material is a molding material that ensures stability such as adhesion of components by being inserted into gaps between various components mounted on the substrate and the substrate. . It is preferably an organic solvent-free from the viewpoint of adhesion, for example, a method in which the monomer composition is forcibly or poured by utilizing a capillary phenomenon, or thermocompression bonding using a prepreg of the monomer composition. There is a method of curing.

(Anisotropic Conductive Film) An anisotropic conductive film refers to a prepreg obtained by pre-curing in a state where inorganic fine particles and polymer fine particles plated with a conductive powder or a conductive substance are dispersed in an insulating material. This is a molding material that ensures stability such as conduction and adhesion between components and a substrate by being inserted into gaps between various components mounted on the substrate and the substrate. As the conductive powder or conductive material, copper, nickel, aluminum, silver, gold, carbon black, or the like is used. At that time, the intended anisotropic conductive film can be obtained by using the polymer insulating material of the present invention, and excellent insulating properties can be imparted to portions other than the conductive portion after molding.

(Interlayer Insulating Film for Semiconductor) The interlayer insulating film for semiconductor is a film for insulating between wirings arranged in layers in electronic components such as an integrated circuit device, a liquid crystal display device, and a solid-state imaging device. After forming the cured film of the monomer composition of the present invention, a conductor such as copper or aluminum can be provided by a vacuum evaporation method or the like. The semiconductor interlayer insulating film of the present invention is excellent in insulation and heat resistance.

(Semiconductor encapsulant) A semiconductor encapsulant is an insulating material used to protect the electronic component from a chemical and physical environment. It is preferable to use one containing a filler, an epoxy resin precursor or the like, and a transfer molding method or the like can be used as a molding method.

Further, a bulk body can be obtained by molding the monomer composition or its prepreg into a desired shape by a molding method, an extrusion method or the like, and by thermosetting. This bulk body can have excellent environmental resistance after thermosetting.

(Solder resist material) A solder resist is a protective film for preventing solder from adhering to unnecessary parts on a circuit board surface during soldering, and a circuit is directly exposed to air to prevent oxidation and corrosion. It is a permanent resist that functions as a protective film to prevent it from receiving. In the preparation of the solder resist, it is possible to use the monomer composition of the present invention containing the filler such as silica and the epoxy resin precursor. As an application method, a method such as a screen printing method can be used, and excellent environmental resistance can be imparted after thermosetting.

According to the above embodiment, the following effects can be exhibited. The polymer insulating material of the present invention is mainly based on the properties of fumaric diester, and particularly has a frequency band of 500 MHz.
As described above, especially in a high frequency band of 500 MHz to 10 GHz, the dielectric constant (ε) is 2 or more, particularly 2.2 to 3.2, and the dielectric loss tangent (tan δ) is 0.05 or less,
Usually, it has excellent electric characteristics of 0.002 to 0.05.

This polymer insulating material is obtained by forming a monomer composition, which is a raw material, into a predetermined shape without forming a process of once dissolving a polymer in an organic solvent at the time of molding. It is a material that is excellent in moldability or workability because it can be hardened by curing.

Also, since this polymer insulating material has a crosslinked structure by a crosslinkable monomer having two or more carbon-carbon double bonds in one molecule, it has excellent dielectric properties and heat resistance. . Furthermore, since the monomer hardly remains after curing, it is excellent in insulation, solvent resistance, dimensional stability and durability,
Also, it has excellent strength, thermal shock resistance and adhesion.

In addition, by using an organic peroxide or an azo compound as a thermal decomposition type polymerization initiator, when used as an electric insulating film and a substrate on which the same is laminated, a metal compound harmful to electric performance. Is not contained in the polymer, so that the electric properties are very excellent.

Since the polymer insulating material is obtained by heating and curing a monomer composition containing fumaric diester, a crosslinkable monomer, and an initiator, the polymer insulating material can be easily produced. be able to.

As described above, polymer insulating materials include insulating films, laminates, electronic-related substrates, build-up materials, undercoat materials, interlayer adhesives, underfill materials, anisotropic conductive films, and semiconductor materials. It is industrially useful because it is suitable for electronic members such as interlayer insulating films, sealing materials for semiconductors, and solder resist materials.

[0068]

EXAMPLES Hereinafter, the above embodiments will be described more specifically with reference to examples, but the present invention is not limited to these examples. The abbreviations and compound names of fumaric acid diesters, crosslinkable monomers, other vinyl monomers, other polymers, and initiators shown in Examples and Comparative Examples are shown below. Φ in the following compounds represents a phenyl group.

<Fumaric acid diester> DiPF: diisopropyl fumarate DcHF: dicyclohexyl fumarate DcPF: dicyclopentyl fumarate DsBF: disec-butyl fumarate iPcHF: isopropylcyclohexyl fumarate <Crosslinkable monomer> DVB: divinylbenzene DVAd : Divinyl adipate CHDVE: 1,4-cyclohexane dimethanol divinyl ether HDVE: n-hexanediol divinyl ether MHDVE: 2,5-dimethyl-2,5-hexanediol divinyl ether BDA: 1,4-butanediol diacrylate BPDA : CH ₂ = CHCOOCH ₂ CH ₂ OφC (CH ₃ ) ₂ φOCH ₂ CH ₂ OCOCH =
CH ₂ TMPTM: trimethylolpropane trimethacrylate PhBMI: 4,4′-diphenylmethanebismaleimide TMPTE: trimethylolpropane triallyl ether DATP: diallyl terephthalate PDAP: CH ₂ = CHCH ₂ OCOφCOO [CH (CH ₃ ) CH ₂ OCOφCOO] _m CH
₂ CH = CH ₂ (mixture of m = 0 to 5) <Other vinyl monomers> St: styrene VtBB: tert-butylvinylbenzoate VAc: vinyl acetate CHVE: cyclohexyl vinyl ether TAVE: tert-amyl vinyl ether 2EHVE: 2 -Ethylhexyl vinyl ether <Other polymers> PDcHF: DcHF polymer PCHIP: DcHF, DiPF copolymer SIS # 5125: Styrene-isoprene block copolymer manufactured by Kuraray Co., Ltd. (trade name: Hibler 5125) SIS # 2002: Kuraray stock Company-made styrene-isoprene block copolymer (trade name: Septon 2002) <Initiator> BPO: benzoyl peroxide AIBN: azobisisobutyronitrile PH3M: 1,1-bis (tert-butylperoxy)
3,3,5-trimethylcyclohexane DCP: dicumyl peroxide TBPZ: tert-butylperoxybenzoate PHY25: 2,5-dimethyl-2,5-bis (tert-
Butylperoxy) hexyne-3 <Organic solvent> Tol: toluene t-BuBz: tert-butylbenzene Evaluation of polymer insulating material (Example 1) 9.0 g of DcHF, 1.0 g of HDVE
And 0.3 g of BPO were blended to obtain a monomer composition.
Next, this was poured between two glass plates separated by a silicone rubber spacer and cured at 70 ° C. for 10 hours to obtain a sheet having a length of 12 cm, a width of 10 cm and a thickness of 0.8 mm.

On the other hand, a spin coater (Mikasa M
The above-mentioned monomer composition is applied on a silicon wafer (manufactured by Kyodo International) using IKASA SPINCOATER1H-D3) and cured in a nitrogen-substituted glass cell under the same conditions as above, and a film having a thickness of 100 μm is formed. I got

<Evaluation of Insulation Resistance> According to JIS K6911, the sheet was cut and cut into 40 mm × 20 mm × 0.8.
mm strips were created. Two holes each having a diameter of 5 mm were formed so that the center-to-center distance became 15 mm, and a taper pin was pushed into the holes to form a pair of electrodes. The insulation resistance was measured after charging for 1 minute using 500 V DC as the measurement voltage.

<Evaluation of Dielectric Properties> The sheet was cut to prepare a stick of 10 cm × 1.0 mm × 0.8 mm. The relative permittivity and the dielectric loss tangent at a measurement frequency of 2 GHz were measured using a complex resonator permittivity evaluation device (manufactured by Kanto Electronics Co., Ltd.).

<Evaluation of Solder Heat Resistance> The above film was cut to prepare a strip of 50 mm × 3 mm × 100 μm.
This was placed in a 260 ° C solder bath (TAIYOELECTRIC
IND. CO. , LTD POT-200C)
It was immersed for 0 seconds, and the appearance was evaluated. If there was no change in color or shape, it was evaluated as ○, and otherwise, it was evaluated as ×.

<Evaluation of Water Absorption> A film of 50 mm × 50 mm × 100 μm was prepared by cutting the film.
The water absorption (%) was measured according to JISC6481.

<Evaluation of Solvent Resistance> The above film was cut into a 25 mm × 25 mm × 100 μm film, immersed in toluene and methylene chloride in accordance with JIS C6481, and its appearance was evaluated. If there was no change in shape such as swelling and roughness, it was evaluated as ○, and otherwise, it was evaluated as ×. Table 1
Table 2 summarizes the evaluation results.

(Examples 2 to 20) Fumaric acid diester,
A sample was prepared in the same manner as in Example 1 except that the type and the amount of the crosslinking monomer, initiator, and other vinyl monomers were changed,
Each property was evaluated. The formulations are summarized in Table 1 and the evaluation results are summarized in Table 2.

(Comparative Examples 1-4) 100 parts by weight of polyvinyl alcohol (KH-17, manufactured by Nippon Synthetic Chemical Co., Ltd.) was dissolved in a 20-liter stainless steel reaction vessel equipped with a stirrer. 2,000 parts by weight, and DcHF 2,000 in which 60 parts by weight of BPO were further dissolved.
Parts by weight were added and suspension polymerization was performed at 70 ° C. for 10 hours. The obtained PDcHF was immersed in 10,000 parts by weight of methanol and stirred at room temperature for 2 days. After filtration, it was dried in an oven at 70 ° C. for 2 days. The yield at this time was 1850 parts by weight.

10 parts by weight of this PDcHF was added to benzene 10
It was dissolved in 0 ml, poured into a flat petri dish having a smooth bottom with a diameter of about 12 cm, and benzene was evaporated to produce a transparent and uniform sheet having a diameter of 12 cm and a thickness of 0.8 mm.

On the other hand, 1 part by weight of PDcHF was
The mixture was poured into a flat petri dish having a smooth bottom and about 12 cm in diameter, and toluene was evaporated to produce a transparent and uniform film having a diameter of 12 cm and a thickness of 100 μm. Further, a polymer was prepared in the same manner as above except that the raw material fumaric acid diester was changed, and sheets and films were prepared in the same manner. These were evaluated in the same manner as in Example 1, and the formulations were summarized in Table 1 and the evaluation results were summarized in Table 2.

[0080]

[Table 1]

[0081]

[Table 2] As shown in Table 2, the polymer insulating materials of Examples 1 to 20 have good insulation resistance, dielectric properties (relative permittivity, dielectric loss tangent), solder heat resistance, water absorption, and solvent resistance. On the other hand, in Comparative Examples 1 to 4 containing no crosslinkable monomer, the solvent resistance is poor, and the solder heat resistance and the water absorption may decrease.

<Evaluation of Laminated Body> (Example 21) 900 parts by weight of DcHF, 100 parts by weight of PDAP (trade name BA901, manufactured by Showa Denko KK), B
20 parts by weight of PO and 10 parts by weight of DCP were blended to obtain a monomer composition, which was woven on a glass woven fabric (20 cm square, thickness 6 cm).
0 ± 2 μm, 12 sheets of E glass (Asahi Schwebel). Overlapping the sheets of 12 ply further thickness 18μm on the upper and lower sides a copper foil (manufactured by Fukuda conductor Foil & Powder Industry Co. Ltd.), 90 ° C., 1 hour, 4.9 × 10 ^-3 MPa (0.0
After press molding under the condition of 5 kg / cm ² ),
50 ° C., 5 hours, 19.6 × 10 ⁻³ MPa (0.2 kg
/ Cm ² ), then 170 ° C., 2 hours, 49 × 1
Press molding was performed under the conditions of 0 ⁻³ MPa (0.5 kg / cm ² ). As a result, a laminate having a thickness of 0.8 mm was obtained.

<Evaluation of Insulation Resistance> The copper foil on both sides was removed by etching, and 40 mm × 2 in accordance with JIS C6481.
Cut into 0mm sheet and insert 2 holes of 5mm diameter into 15mm
A tapered pin was provided at an interval of mm to serve as a pushing electrode. The insulation resistance was measured after charging for 1 minute using 500 V DC as the measurement voltage.

<Evaluation of Dielectric Characteristics> The copper foil on both sides was removed by etching, and cut into sticks of 10 cm × 1.0 mm. Using a complex permittivity evaluator using a cavity resonator perturbation method, when the measurement frequency was 2 GHz. Was measured for relative permittivity and dielectric loss tangent.

<Evaluation of Solder Heat Resistance> A sheet of 50 mm × 3 mm was cut, immersed in a solder bath at 260 ° C. for 120 seconds, and the appearance was evaluated. If there was no change in color or shape, it was evaluated as ○, and the others were evaluated as ×.

<Evaluation of Water Absorption> The copper foil on both sides was removed by etching, and 50 mm × according to JIS C6481.
The sheet was cut into a 50 mm sheet, and the water absorption (%) was measured.

<Evaluation of Solvent Resistance> The copper foil on both sides was removed by etching, and 25 mm in accordance with JIS C6481.
The sheet was cut into a × 25 mm sheet, immersed in toluene and methylene chloride, and its appearance was evaluated. If there was no change in shape such as swelling or roughness, it was evaluated as ○, and the others were evaluated as ×.

The above formulations are summarized in Table 3 and the evaluation results are summarized in Table 4. (Examples 22 to 25) Samples were prepared in the same manner as in Example 21 except that the types and amounts of the fumaric acid diester, the crosslinkable monomer, the initiator, and other vinyl monomers were changed, and the respective properties were changed. Was evaluated. Table 3 shows the blends, and Table 4 shows the evaluation results.

(Comparative Example 5) 1000 parts by weight of DcHF, B
20 parts by weight of PO and 10 parts by weight of DCP were blended to prepare a sample in the same manner as in Example 21, and each characteristic was evaluated. Table 4 summarizes the results.

(Comparative Example 6) Polymer P prepared in Comparative Example 2
150 parts by weight of CHIP was dissolved in 850 parts by weight of toluene, and a varnish was prepared by filtration under pressure. This varnish was impregnated into 12 glass woven cloths (20 cm square, 60 ± 2 μm thick, E glass manufactured by Asahi Schwebel).

Each sheet was dried in a dryer at 40 ° C. until the residual amount of toluene became 10 to 30% by weight.
Two sheets were superposed, and a copper foil having a thickness of 18 μm was further superposed on both sides thereof.
m ² ). As a result, the thickness 0.8
mm was obtained. Using this laminated body, a sample was prepared in the same manner as in Example 21, and each characteristic was evaluated. The composition is summarized in Table 3 and the evaluation results are summarized in Table 4.

[0092]

[Table 3]

[0093]

[Table 4] As shown in Table 4, the laminates of Examples 21 to 25 had insulation resistance, dielectric properties (relative permittivity, dielectric loss tangent), solder heat resistance,
Both water absorption and solvent resistance are good. On the other hand, Comparative Example 5 containing no crosslinking monomer has poor solder heat resistance and solvent resistance, and Comparative Example 6 containing an organic solvent has poor solvent resistance.

<Evaluation of Build-up Material> (Example 26) DcHF 60 parts by weight, DiPF 25
Parts by weight, 15 parts by weight of PDAP, 2 parts by weight of TBPZ, and 10 parts by weight of silica gel (average particle size: 10 μm) to obtain a monomer composition, and then a pre-treated double-sided copper-clad glass epoxy substrate ( Sumitomo Bakelite FR-4)
The monomer composition was applied thereon using a bar coater. Then, the temperature was raised from 80 ° C. to 130 ° C. in a nitrogen atmosphere over 15 hours to cure, thereby forming an organic resin insulating layer.

Next, 8N KOH kept at 90 ° C.
After immersion in an aqueous solution for 60 minutes, the silica gel on the surface of the organic resin insulating layer was removed to form fine irregularities on the surface, and the surface was observed by SEM. At this time,
A sample having irregularities on the surface was evaluated as ○, and a sample without irregularities was evaluated as ×. Table 5 summarizes the results.

Example 27 An organic resin insulating layer was formed in the same manner as in Example 26 except that calcium carbonate was used instead of silica gel. Then, calcium carbonate on the surface of the organic resin insulating layer was removed by immersion in 10% sulfuric acid at room temperature for 10 minutes to form fine irregularities on the surface of the insulating layer, and the surface was observed by SEM. Table 5 summarizes the results.

(Example 28) 50 parts by weight of DcHF, D
35 parts by weight of iPF, 15 parts by weight of PDAP, TBPZ
2 parts by weight and 10 parts by weight of polystyrene (A & M Styrene Co., Ltd., Dialex HF77) were blended to obtain a monomer composition, which was applied and cured in the same manner as in Example 26 to obtain an insulating material. A layer was formed. Then, a chromic acid mixed solution (chromic acid 200 g / L, concentrated sulfuric acid 550 g / L) kept at 75 ° C. was added for 10 minutes, and an 8N aqueous KOH solution kept at 90 ° C. for 60 minutes, and again at 75 ° C. After immersion in the mixed solution for 10 minutes to remove polystyrene on the surface of the insulating layer and form fine irregularities on the surface of the insulating layer, the surface was observed by SEM. Table 5 summarizes the results.

Example 29 Example 26 was repeated except that silica gel (particle size: 3 μm) was further added to the composition of Example 28.
In the same manner as in the above, the mixture was applied, coated and cured to form an insulating layer. Then, by immersing in a chromic acid mixed solution and an 8N KOH aqueous solution in the same manner as in Example 28, the filler on the surface of the insulating layer was removed to form fine irregularities on the surface of the insulating layer. Observed by SEM. Table 5 shows the results.
Summarized in

[0099]

[Table 5] As shown in Table 5, the insulating layers of Examples 26 to 29 have irregularities on the surface, and the adhesion of plating is improved.

Further, a copper plating having a thickness of 50 μm was applied to the insulating layer of Example 29 according to a plating process of Meltex Co., Ltd., and a peeling test was performed based on JIS C6481. Table 6 summarizes the results.

[0101]

[Table 6] As shown in Table 6, in Example 29, the peel strength of the plating was good, indicating that the adhesion between the insulating layer and the copper plating layer was good.

<Evaluation of Adhesive> (Example 30) 70 parts by weight of DcHF, PDAP 10
Parts by weight, 10 parts by weight of St, 10 parts by weight of SIS # 5125, and 2 parts by weight of PH3M to obtain a monomer composition, from which a surface copper foil was removed by etching to obtain a glass epoxy substrate (FR-4 Sumitomo Bakelite). Co., Ltd.) using a bar coater. Furthermore, a copper foil having a thickness of 18 μm was pressed with a rubber roller while removing air bubbles, and
20 ° C, 10 hours, 0.294 MPa (3 kg / c
m ² ). As a result, the thickness 0.8
mm was obtained.

After removing the conductor by etching in the same manner as in Example 1, the insulation resistance, solder heat resistance, water absorption and solvent resistance were evaluated. Furthermore, JISC5012
The adhesiveness of the copper foil was evaluated by a base test using a cellophane tape. At this time, the case where the copper foil did not peel off from the substrate surface was evaluated as ○, and the case where the copper foil was peeled was evaluated as ×. Table 7 summarizes the results.

(Example 31) 70 parts by weight of DiPF, Ph
BMI 10 parts by weight, St 10 parts by weight, SIS # 20
02 10 parts by weight and PH3M 2 parts by weight were blended to obtain a monomer composition. This was applied on a glass epoxy substrate (FR-4 manufactured by Sumitomo Bakelite Co., Ltd.) from which the surface copper foil was removed by etching, using a bar coater, and further having a thickness of 1 mm.
An 8 μm copper foil was pressed with a rubber roller while removing air bubbles, and was heated at 120 ° C. for 10 hours at 0.294 MPa (3 kg).
/ Cm ² ). As a result, a laminate having a thickness of 0.8 mm was obtained.

After the conductor was removed by etching in the same manner as in Example 1, insulation resistance, solder heat resistance, water absorption and solvent resistance were evaluated. Furthermore, according to JISC5012,
The adhesion of the copper foil was evaluated by a basement test using cellophane tape. At this time, the case where the copper foil did not peel off from the substrate surface was evaluated as ○, and the case where the copper foil peeled was evaluated as ×. Table 7 shows the results.
Summarized in

Comparative Example 7 90 parts by weight of DcHF, SI
A monomer composition was obtained by blending 10 parts by weight of S # 5125 and 2 parts by weight of PH3M. This was applied on a glass epoxy substrate from which the surface copper foil was removed by etching using a bar coater, and further, a copper foil having a thickness of 18 μm was pressure-bonded with a rubber roller while removing air bubbles, at 120 ° C. for 10 hours at 0.294 MPa. (3 kg / cm ² ). As a result, a laminate having a thickness of 0.8 mm was obtained. This was evaluated in the same manner as in Example 26.
Summarized in

[0107]

[Table 7] As shown in Table 7, the adhesives of Examples 30 and 31 have good insulation resistance, solder heat resistance, water absorption, solvent resistance and adhesion, and are excellent in durability. In contrast,
Comparative Example 7, which does not contain a crosslinkable monomer, is inferior in solvent resistance and adhesion.

<Evaluation of Underfill Material> (Example 32) 30 parts by weight of DcHF, 5 parts by weight of PDAP, 5 parts by weight of SIS # 5125, 60 parts of fused silica
By weight, 2 parts by weight of PH3M and 1 part by weight of TBPZ were blended to obtain a monomer composition. Then, a flip chip was placed on a glass epoxy resin having electrode pads via a solder ball, passed through a reflow furnace, and an electrically connected substrate was prepared, and a substrate was formed between the glass epoxy resin and the flip chip. The monomer composition was poured into the gap, and heated and cured at 170 ° C. for 1 hour.

<Thermal shock test> A temperature cycle of the substrate on which the flip chip was mounted at -55 ° C for 30 minutes, then at room temperature for 5 minutes, then at 150 ° C for 30 minutes, and then at room temperature for 5 minutes was repeated 500 times. Then, the adhesion between the semiconductor chip and the substrate and the presence or absence of cracks were examined. As a result, no adhesiveness and cracks between the semiconductor chip and the substrate were observed, and no abnormal appearance was observed.

(Example 33) 30 parts by weight of DiPF, C
HDVE 5 parts by weight, SIS # 5125 5 parts by weight, fused silica 60 parts by weight, PH3M 2 parts by weight and TBP
Z was mixed with 1 part by weight to obtain a monomer composition. On the other hand, a flip chip is placed on a glass epoxy resin having an electrode pad via a solder ball and passed through a reflow furnace,
An electrically connected substrate was prepared. The monomer composition was poured into a gap formed between the glass epoxy resin and the flip chip, and was cured by heating at 170 ° C. for 1 hour. Then, a thermal shock test was performed in the same manner as in Example 32. As a result, no adhesiveness and cracks between the semiconductor chip and the substrate were observed, and no abnormal appearance was observed.

(Comparative Example 8) 35 parts by weight of DiPF, SI
A monomer composition was obtained by mixing 5 parts by weight of S # 5125, 60 parts by weight of fused silica, 2 parts by weight of PH3M, and 1 part by weight of TBPZ as an initiator. This was evaluated in the same manner as in Example 32. As a result, cracks were observed between the semiconductor chip and the substrate.

(Comparative Example 9) 35 parts by weight of PDcHF, SI
S # 5125 5 parts by weight, fused silica 60 parts by weight, To
1200 parts by weight and 10 parts by weight of t-BuBz are blended,
Apply onto a silicon wafer using a spin coater 6
Drying was performed in nitrogen gas at 0 ° C. for 1 minute to remove only toluene. This operation was repeated to prepare a film having a thickness of 25 μm and remaining t-BuBz of 20%. next,
This film was placed on a glass epoxy resin having an electrode pad for flip chip connection, a semiconductor chip was placed thereon, and heated and pressed at 250 ° C. for 1 hour under vacuum. This sample was evaluated in the same manner as in Example 32. As a result, cracks were observed between the semiconductor chip and the substrate.

<Evaluation of Anisotropic Conductive Film> (Example 34) 65 parts by weight of DcHF, PDAP 20
Parts by weight, 10 parts by weight of SIS # 5125, 5 parts by weight of carbon black (average particle size: 0.1 μm) as a conductive powder, 100 parts by weight of Tol as a viscosity modifier, and PH
A monomer composition was obtained by mixing 2 parts by weight of 3M and 1 part by weight of TBPZ. And as a connection test board, 1.6m
A line pattern having a pitch of 125 μm between lines and a line width of 125 μm was formed using a substrate of 35 μm copper foil based on an m-thick glass epoxy material. The monomer composition was applied on the substrate by screen printing, and dried in a nitrogen gas at 60 ° C. for 3 minutes.

Next, 10 minutes in a glass cell purged with nitrogen.
The composition was cured at 0 ° C. for 1 hour to obtain a tack-free film having a thickness of 20 μm. On the film, the same connection test substrate as described above was bonded by performing positional alignment between the corresponding electrodes on both substrates, and was bonded at 0.98 MPa (10 kg / cm ² ).
It was heated and pressed at 180 ° C. for 1 minute.

<Evaluation of contact resistance> Contact area 0.15 × 3.0 mm
Was measured. <Thermal shock test>
55 ° C., 30 minutes, then room temperature, 5 minutes, further 150 ° C.,
By repeating a temperature cycle for 30 minutes and then at room temperature for 5 minutes 500 times, the adhesion between the semiconductor chip and the substrate and the presence or absence of cracks were examined. At that time, those in which no abnormality was observed in appearance were evaluated as ○, and those in which chips fell off or cracks occurred between layers were evaluated as ×.

<PCT (pressure cooker test)
> The substrate on which the semiconductor chip was mounted was left for 30 minutes under conditions of 100% humidity, 105 ° C. and 2 atm, and the adhesion between the semiconductor chip and the substrate and the presence or absence of cracks were examined.
At that time, those in which no abnormality was observed in appearance were evaluated as ○, and those in which chips fell off or cracks occurred between layers were evaluated as ×. Table 8 summarizes the results.

(Example 35) 65 parts by weight of DiPF, C
20 parts by weight of HDVE, 10 parts by weight of SIS # 5125, 5 parts by weight of carbon black, 100 parts by weight of Tol, 2 parts by weight of PH3M, and 1 part by weight of TBPZ were mixed to obtain a monomer composition. Hereinafter, preparation and evaluation were performed in the same manner as in Example 34, and the results are summarized in Table 8.

(Comparative Example 10) 75 parts by weight of DcHF, S
IS # 5125 10 parts by weight, carbon black 5 parts by weight, Tol 100 parts by weight, PH3M 2 parts by weight,
One part by weight of TBPZ was blended to obtain a monomer composition. This was prepared and evaluated in the same manner as in Example 30, and the results were shown in Table 8.
Summarized in

(Comparative Example 11) 20 parts by weight of PCHIP,
A monomer composition was obtained by blending 2 parts by weight of SIS # 5125, 1 part by weight of carbon black, 70 parts by weight of Tol, and 10 parts by weight of t-BuBz. This was prepared and evaluated in the same manner as in Example 30, and the results are summarized in Table 8.

[0120]

[Table 8] As shown in Table 8, the anisotropic conductive films of Examples 34 and 35 have good contact resistance, thermal shock resistance, and PCT, and are excellent in durability. In contrast, Comparative Examples 10 and 1 which did not contain a crosslinkable monomer and contained an organic solvent
In the case of 1, the contact resistance is low, and the thermal shock resistance and the PCT are inferior.

<Evaluation of Interlayer Insulating Film for Semiconductor> (Example 36) 8.5 parts by weight of DcHF, HDVE
1.5 parts by weight, 200 parts by weight of Tol and 0.
The monomer composition was obtained by mixing 2 parts by weight, and the monomer composition was applied on a silicon wafer using a spin coater and dried at 60 ° C. for 30 seconds.
m. This operation was repeated 10 times to produce a 2 μm film. When cut using a microcutter and the cross section was observed with an electron microscope, the change in thickness was 3% or less, and there was no problem in smoothness. Heated at 75 ° C. for 24 hours in a glass cell purged with nitrogen. Next, aluminum was deposited using a vacuum deposition apparatus (VPC-260, manufactured by Vacuum Kiko Co., Ltd.) to form electrodes on the upper and lower parts.

<Measurement of relative permittivity> Dielectric measurement electrode HP1
6451B and Precision LCR Meter HP4285
A (manufactured by Hewlett-Packard Japan) was used to measure the relative dielectric constant of the film at a frequency of 1 MHz.

<Evaluation of Heat Resistance> The film was peeled off from the silicon wafer and subjected to thermogravimetric analysis. And
At 350 ° C., no loss in weight due to thermal decomposition was observed, and 、 was given for the others.

<Evaluation of Adhesion> PC described in Example 34
After testing under T conditions, according to JISC-5012,
Adhesion was evaluated by a basement test using cellophane tape. Then, those that did not peel off from the wafer were rated as ○, and those that peeled off were rated X. Table 9 summarizes the results.

(Example 37) 8.5 parts by weight of DiPF
CHDVE 1.5 parts by weight, Tol 200 parts by weight, B
A monomer composition was obtained by mixing 0.2 parts by weight of PO. The preparation was evaluated in the same manner as in Example 36.
Summarized in

(Comparative Example 12) 10 parts by weight of DcHF, T
ol 200 parts by weight and BPO 0.2 parts by weight were blended to obtain a monomer composition. Then, the preparation was evaluated in the same manner as in Example 36, and the results are summarized in Table 9.

(Comparative Example 13) PDcHF 10 parts by weight,
A varnish consisting of 200 parts by weight of Tol was blended and applied on a silicon wafer using a spin coater.
The film was dried at 30 ° C. for 30 seconds and found to have a thickness of 200 nm. This operation was repeated 10 times to produce a 2 μm film. However, when it was cut using a micro cutter and the cross section was observed with an electron microscope, the change in thickness was 10%.
Rippling was observed. Next, aluminum was deposited using a vacuum deposition apparatus, and electrodes were formed on the upper and lower portions. Using this, evaluation was performed in the same manner as in Example 36, and the results are summarized in Table 9.

[0128]

[Table 9] As shown in Table 9, the interlayer insulating films for semiconductors of Examples 36 and 37 have good relative dielectric constant, heat resistance and adhesion, and are excellent in durability. On the other hand, Comparative Examples 12 and 13 which did not contain a crosslinkable monomer and contained an organic solvent
Is inferior in heat resistance and adhesion.

<Evaluation of sealing material for semiconductor> (Example 38) 60 parts by weight of DcHF, DATP 30
Parts by weight, 10 parts by weight of SIS # 5125, 150 parts by weight of fused silica (average particle size: 5 μm) and 2 parts by weight of DCP were mixed, dispersed and mixed at 80 ° C. using three rolls, and vacuum defoamed.

Next, using this composition, a pin grid array was sealed by a transfer molding method.
The curing condition was to raise the temperature to 150 ° C. in 30 minutes, and
The package was molded by curing at 0 ° C. for 2 hours.

<Evaluation of Heat Resistance> The package was pulverized, and a thermogravimetric analysis of the resin portion was performed. As a result, 350
At ℃, no weight loss due to thermal decomposition was observed.

<PCT> After the test under the PCT conditions described in Example 34, observation was made with an optical microscope (magnification: 30 times). As a result, appearance deterioration such as peeling and cracking was not observed.

Example 39 70 parts by weight of DiPF, T
MPTE 25 parts by weight, SIS # 5125 5 parts by weight,
150 parts by weight of fused silica (average particle size 5 μm) and DCP
2 parts by weight were blended, and dispersed and mixed at 80 ° C. using a three-roll mill, followed by vacuum defoaming. Hereinafter, it was prepared and evaluated in the same manner as in Example 38. As a result, no weight loss or deterioration in appearance due to thermal decomposition was observed.

(Comparative Example 14) DcHF, SIS, fused silica (average particle size: 5 µm) and DCP were blended, dispersed and mixed at 80 ° C using three rolls, and vacuum defoamed. Thereafter, a package was molded in the same manner as in Example 38, and the same physical properties were evaluated. As a result, weight loss due to thermal decomposition was observed.
Further, cracks of the package were recognized by PCT.

<Evaluation of Solder Resist Material> (Example 40) 60 parts by weight of DcHF, DVAd 30
Parts by weight, 10 parts by weight of SIS # 2002, 20 parts by weight of fused silica (average particle size: 5 μm), 100 parts by weight of Tol and 2 parts by weight of DCP, and using a screen printing machine (MT-150RTV, manufactured by Microtech). And 4
Screen printing was performed on the surface of the glass epoxy resin using a silk screen (V60 manufactured by NBC) on which a line & space of 0 μm was drawn.

Next, in an oven purged with nitrogen at 150 ° C.
For 2 hours. Observation of the obtained solder resist with a microscope revealed that the thickness was 50 μm and the thickness was 40 μm.
Line and space were faithfully reproduced.

<Evaluation of Solvent Resistance> A sheet of 25 mm × 25 mm was cut in accordance with JIS C6481.
And immersed in methylene chloride to evaluate its appearance. As a result, no change in shape such as swelling and roughness was observed.

<Evaluation of Adhesion> PC described in Example 34
After testing under T conditions, according to JISC-5012,
The adhesion was evaluated by a grid test using cellophane tape. As a result, the film did not peel off from the substrate.

(Comparative Example 15) 90 parts by weight of DcHF, S
IS # 2002 10 parts by weight, fused silica (average particle size 5
μm) 20 parts by weight, Tol 100 parts by weight and DCP
2 parts by weight were blended, and a resist film was formed on the surface of the glass epoxy resin in the same manner as in Example 40. As a result, the thickness, line and space were faithfully reproduced as in Example 40. Hereinafter, as a result of evaluating solvent resistance and adhesion, To
Both 1 and methylene chloride showed swelling of the coating, and peeling was observed in the adhesion test.

The technical ideas grasped from the above embodiment will be described below. The polymer insulating material according to any one of claims 1 to 3, wherein the thermal decomposition type polymerization initiator is an organic peroxide or an azo compound. In such a configuration, the thermal decomposition-type polymerization initiator does not contain a metal, and thus the electrical characteristics of the obtained polymer insulating material can be favorably maintained.

The polymer according to any one of claims 1 to 3, wherein the monomer composition further contains a polymer or another vinyl monomer other than the monomer. Insulating material. With such a configuration, characteristics such as mechanical strength and smoothness of the polymer insulating material and adhesion between the coating film and the base material can be adjusted.

The method for producing a polymer insulating material according to claim 4, wherein the heat curing is performed in the substantial absence of an organic solvent. According to this manufacturing method, moldability or workability can be improved.

The build-up material according to claim 7, wherein the surface is roughened to form a conductive layer thereon by plating. With this configuration, the adhesion between the build-up material and the conductor layer can be improved.

[0144]

According to the present invention, the following effects can be obtained. The polymer insulating material according to the first aspect of the invention is excellent in electrical properties such as dielectric constant, dielectric loss tangent, and insulating property, solvent resistance, heat resistance, and thermal shock resistance.

According to the polymer insulating material of the second invention, in addition to the effects of the first invention, the electric characteristics can be improved. According to the polymer insulating material of the third invention, in addition to the effects of the first or second invention, a polymer insulating material can be efficiently obtained.

According to the method for producing a polymer insulating material of the fourth invention, a polymer insulating material can be produced efficiently. According to the electronic-related substrate of the fifth invention, the first to third substrates are provided.
The effect of the polymer insulating material of any one of the inventions can be exerted on a printed wiring board, a build-up board, or the like.

According to the electronic member of the sixth aspect, the effect of the polymer insulating material of any one of the first to third aspects can be exerted on an insulating film, a laminate, an undercoat material, and the like.

According to the build-up material of the seventh invention, in addition to the effect of the polymer insulating material of any one of the first to third inventions, after the surface of the build-up material is roughened, When the conductor layer is formed by plating, the adhesion between the build-up material and the conductor layer can be improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 23/31 H05K 3/46 T H05K 1/03 610 (C08F 222/10 3/46 236: 00) / / (C08F 222/10 H01L 23/30 R 23:00) (72) Inventor Mieko Tamura 3-201, Karijuku-cho, Handa-city, Aichi Prefecture (72) Inventor Yukihiro Kato 8 Nishimon, Taketoyocho, Chita-gun, Aichi Prefecture Address (72) Inventor Shiro Shiro 8th west gate, Taketoyo-cho, Chita-gun, Aichi Prefecture (72) Inventor Naoyuki 2-1-1, Shimozen, Toda City, Saitama Prefecture (72) Inventor Hiroaki Hasegawa Nihonbashi 1-chome, Chuo-ku, Tokyo No. 13-1 TDK Corporation (72) Inventor Toshiaki Yamada 1-13-1 Nihonbashi, Chuo-ku, Tokyo TDK Corporation (72) Inventor Shigeru Asami Central Tokyo Nihonbashi chome 13th No. 1 tee Dikei within Co., Ltd.

Claims (7)

[Claims] 1. A polymer obtained by heat-curing a monomer composition containing a fumaric acid diester, a monomer having two or more carbon-carbon double bonds in one molecule, and a thermal decomposition-type polymerization initiator. Insulating material. 2. The polymer insulating material according to claim 1, wherein the fumaric acid diester is a main component in the monomer composition. 3. The polymer insulating material according to claim 1, wherein the content of the thermal decomposition type polymerization initiator based on the monomer composition is 0.1 to 10% by weight. 4. A monomer composition is prepared by mixing fumaric acid diester, a monomer having two or more carbon-carbon double bonds in one molecule, and a thermal decomposition-type polymerization initiator. A method for producing a polymer insulating material, comprising forming into a shape and then heating and curing. 5. An electron-related substrate formed from a constituent material containing the polymer insulating material according to claim 1. 6. An electronic member formed of a constituent material containing the polymer insulating material according to claim 1. 7. A build-up material formed from the constituent material containing the polymer insulating material according to claim 1 and a filler.