JP2002322221A - Photosetting high molecular insulating material, method of producing the same, electronics-related substrate and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosetting high molecular insulating material having excellent electric properties, for example, dielectric constant, dielectric loss tangent, electric insulation and the like, solvent resistance, heat resistance, heat shock resistance, a method of producing the same, electronics-related substrates and electronic parts. SOLUTION: The objective photosetting high molecular insulating substance is produced by photosetting a monomer composition including fumaric diester, two or more carbon-carbon double bonds-bearing cross-linkable monomers and photodecomposition type polymerization initiator. In the preferred embodiment, the fumaric diester is used as the major component. The photodecomposable polymerization initiator preferably includes no metal. The electronics-relating substrates, for example, printed circuit substrates or electronic parts, for example, an insulation film or undercoat material and the like is prepared by forming the constitution material including the high molecular insulating material is formed to a prescribed shape and photoset by irradiating the formed material with light, for example, ultraviolet rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photo-curable polymer insulating material comprising a crosslinked type fumaric acid diester polymer, a method for producing the same, and an electronic-related substrate and an electronic member. More specifically, the present invention relates to a photocurable polymer insulating material having excellent dielectric properties and heat resistance and a method for producing the same. In addition, electronic-related substrates and laminates such as printed wiring boards and build-up boards formed from such polymer insulating materials, adhesives, anisotropic conductive films, solder resists, interlayer insulating films for semiconductors, molding materials, etc. Electronic members.

[0002]

2. Description of the Related Art With the recent rapid increase of portable information communication devices, there has been an increasing demand for higher performance of information processing devices as the amount of information communication increases. That is, in order to process a large amount of digital or analog information in a short period of time using a small portable device, a response to a higher frequency of each electronic component constituting the information processing device is being promoted. However, 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.

[0004]

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 has a problem that it has a low heat resistance although it has excellent workability as a varnish because it does not have a crosslinked structure. Further, for example, when used as a material for electric insulation, there is a problem that a portion in contact with various organic solvents or a coating material may swell.

Further, the low-dielectric polymer material is used after being dissolved in an organic solvent and then molded into a desired shape at the time of processing. 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 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, and insulation failure and conduction failure occur. There was a problem. further,
In order to form a thick material, the number of times of application and drying must be increased. As a result, internal stress tends to remain, resulting in a decrease in strength and thermal shock resistance. There was a limit on gender.

[0007] In addition, when a monomer composition comprising a fumaric acid diester does not contain a crosslinkable monomer, there is a high possibility that the monomer will remain even if it is polymerized with a polymerization initiator.
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 causes affecting characteristics such as electrical insulation 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 causes that affect the characteristics such as the electrical insulation of the electronic element and the circuit board. Is considered as one.

The present invention has been made in view of the above-mentioned problems existing in the prior art. Its purpose is to provide electrical characteristics such as permittivity, dielectric loss tangent, and electrical insulation,
An object of the present invention is to provide a photocurable polymer insulating material having excellent solvent resistance, heat resistance and thermal shock resistance, a method for producing the same, and an electronic-related substrate and an electronic member.

[0010]

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

In a second aspect of the present invention, there is provided a method for producing a photocurable polymer insulating material, comprising mixing a fumaric acid diester, a monomer having two or more carbon-carbon double bonds in one molecule, and a photodecomposition type polymerization initiator. Then, a monomer composition is prepared, formed into a predetermined shape, and then light-cured.

A third aspect of the present invention provides an electronic-related substrate formed of a constituent material including the photocurable polymer insulating material of the first aspect. An electronic member according to a fourth aspect of the present invention is formed of a constituent material including the photocurable polymer insulating material of the first aspect.

[0013]

Embodiments of the present invention will be described below in detail. The photocurable polymer insulating material of the present invention (hereinafter abbreviated as polymer insulating material) includes a fumaric acid diester, a monomer having two or more carbon double bonds in one molecule (hereinafter referred to as a crosslinkable monomer). A monomer composition (hereinafter abbreviated as a monomer composition) containing, as essential components, a photodecomposition type polymerization initiator (hereinafter abbreviated as a polymerization initiator) and a photodecomposable polymerization initiator (hereinafter abbreviated as a monomer). And is obtained by curing by irradiation.

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

[0015]

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, 1-butoxy-2 -Propyl group, methoxyethyl group, benzyl group and the like.

The cycloalkyl group represented by R ₁ or R ₂ is preferably a cycloalkyl group having 3 to 14 carbon atoms in total, and may be a single ring or 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 in R ₂ preferably has 6 to 18 carbon atoms, 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, dicycloheptyl 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 and cycloalkyl 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 these, 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 kind 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.

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.

Next, the crosslinkable monomer is used to improve 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
It is 80% by weight, 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 crosslinkable monomer having two or more carbon-carbon double bonds in one molecule. Examples of such a crosslinkable monomer include a vinyl group, an acryloyl group, a methacryloyl group, a maleimide group, a vinyl ether group, a vinyl ester group, an allyl ether group,
Examples include monomers having a functional group such as an allyl ester group. Among these functional groups, a vinyl group, a maleimide group or an allyl ester group is preferable because of its excellent copolymerizability.

Specific examples of the crosslinkable monomer include polyfunctional olefins such as butadiene and isoprene, diethylene glycol diacrylate, 1,3-butanediol diacrylate, bisphenol A type diacrylate, urethane diacrylate, epoxy diacrylate, and the like. Polyfunctional acrylates such as trimethylolpropane triacrylate, 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, polyfunctional methacrylate such as phenol novolak type epoxy methacrylate, divinylbenzene, polyfunctional vinyl monomer such as bisphenol A type vinylbenzyl ether,
Polyfunctional maleimides such as 1,3-phenylene bismaleimide and 4,4′-diphenylmethane bismaleimide;
4-cyclohexanedimethanol divinyl ether,
2,2-dimethylhexanediol divinyl ether,
Multifunctional vinyl ethers such as diethylene glycol divinyl ether and trimethylolpropane trivinyl ether; polyfunctional vinyl esters such as divinyl adipate, divinyl 1,4-cyclohexanedicarboxylate, divinyl phthalate and divinyl isophthalate; cyclohexane dimethanol diallyl ether; 2-dimethylhexanediol diallyl ether, diethylene glycol diallyl ether, trimethylolpropane triallyl ether, diallyl ether of bisphenol A type, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, phthalic polyester And polyfunctional allyl monomers such as diallyl ester. These crosslinking monomers may be used alone or in combination of two or more.

Next, it is desirable that the polymerization initiator used in the present invention does not contain a metal. Examples of such a polymerization initiator include diethylthioxanthone and 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzoin isopropyl ether, benzoin ethyl ether, benzophenone, benzophenone methyl ether, 2-ethylanthraquinone, 2,4-dimethylthioxanthone, 2,2 -Dimethoxy-2-phenylacetophenone, p-tert-butyltrichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 3,3 ′,
4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4
6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4
4-trimethylpentylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, and the like.

Among these polymerization initiators, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
2,2-dimethoxy-1,2-diphenylethane-1-
On, 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) butanone-1,2-methyl-1
-[4- (Methylthio) phenyl] -2-morpholinopropan-1-one and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are preferred from the viewpoint of polymerization initiation ability.

The amount of the polymerization initiator used is usually 0.1 to 20% by weight, preferably 1 to 1% by weight, based on the monomer composition.
It is 5% by weight, more preferably 1 to 10% by weight. When the amount is less than 0.1% by weight, the polymerization initiation function is not sufficiently exhibited. When the amount is more than 20% by weight, the polymerization initiator fragments remain in the polymerized insulating material after polymerization and the polymerized insulating material remains. The physical properties of the material may decrease.

In the present invention, fumaric acid diester,
In addition to the crosslinking monomer and the polymerization initiator, other vinyl monomers or other polymers can be added to the monomer composition. These additives can be added for the purpose of adjusting the viscosity of the monomer composition, the mechanical strength and smoothness of the formed 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, isobutyl vinyl ether, cyclohexyl vinyl ether and the like Vinyl ethers; alkyl vinyl ketones such as methyl vinyl ketone and isobutyl vinyl ketone; olefins such as isobutylene and 1-butene; methyl (meth)
(Meth) acrylic acid or esters thereof such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and phenyl (meth) acrylate; vinyl cyanides such as acrylonitrile; N-vinylpyrrolidone , Vinyl-type monomers such as N-vinylcaprolactam; unsaturated dibasic acids such as maleic anhydride, maleic acid, itaconic acid, itaconic anhydride, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dicyclohexyl itaconate and esters thereof A known radical polymerizable monomer such as a group can be preferably exemplified.

Examples of the other polymer include homopolymers or copolymers of other vinyl monomers, polyester acrylate, epoxy acrylate, urethane acrylate, polybutadiene acrylate, polystyryl methacrylate, polyether methacrylate and the like. Photopolymerizable oligomers, phenolic resins, epoxy resins, diallyl phthalate resins, unsaturated polyesters, resin precursors such as cyanate ester resins, polyethylene, polypropylene, polyisobutylene, polyolefins such as polybutene, polyimide resin precursors, butyral resins, Polyphenylene oxide, polyphenylene sulfide, polyester, polycarbonate, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated Len - butadiene block copolymer, hydrogenated styrene - can be exemplified thermoplastic resins such as a thermoplastic elastomer such as isoprene block copolymer. 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 to be added is preferably 30% by weight or less, more preferably 10% by weight or less, 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 needed so as not to affect the curing, or the mixture is dissolved and dispersed in an organic solvent or emulsified and dispersed in water. You may use a thing.

Further, dyes, pigments, thixotropy-imparting agents, plasticizers, surfactants, ultraviolet absorbers, antioxidants, flame retardants, and the like are added to such an extent that they do not affect the electrical insulation.
A coupling agent or 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, phenol resins, melamine resins, thermosetting resin powders such as polyimide, polyolefin resins, polystyrene resins, nylon, polyethylene terephthalate, polycarbonate, and styrene. Thermoplastic resin powders such as butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, and hydrogenated styrene-isoprene block copolymer can be used.

Hereinafter, a method for producing a polymer insulating material formed from the monomer composition according to the present invention, its use, and details of its 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 photo-curing method can be used. Specifically, if necessary, other additives, fillers, and the like are added to a monomer composition containing a fumaric acid diester, a crosslinkable monomer, and a polymerization initiator, and these are mixed in a pot or the like. After shaping this into a predetermined shape, a photopolymerization reaction is performed by irradiating a light beam such as an ultraviolet ray at room temperature to 100 ° C. so as to give an energy amount of 0.1 to 10 J / cm ^2. A molecular insulating material can be obtained. In this case, the polymerization reaction may be performed by irradiation with an active energy ray such as an electron beam, X-ray, or γ-ray.

When the temperature is equal to or lower than room temperature or the light irradiation amount is 0.1
If it is less than J / cm ² , the polymerization reaction may not proceed sufficiently. When the heating temperature exceeds 100 ° C., a part of the monomer composition may volatilize or foam due to a rapid curing reaction. Light dose of 10 J / cm
^In the case of ^two or more, the polymer may be decomposed or the polymerization efficiency may be reduced. In this case, after a prepreg having a predetermined shape is formed in advance, the prepregs are laminated, and pressure and heat are applied by a predetermined mold to complete the curing, whereby a polymer insulating material can be obtained. Further, in order to sufficiently cure, it is preferable to perform heating (post-curing) at 100 to 200 ° C. for 1 to 5 hours.

When a solid fumaric acid diester is used, it is once dissolved in a crosslinkable monomer, mixed with a polymerization initiator to prepare a monomer composition, and 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 preliminarily cured in the range of 0.1 to 1 J / cm ² and room temperature to 100 ° C., and is shaped into a predetermined shape. It may be cured again. Here, the term "pre-curing" refers to photo-curing to a state in which the polymerization reaction can proceed to some extent to maintain the shape, and includes the prepreg.

The photocuring conditions may be changed according to the state of the reaction. Further, the resin may be heated and pressurized by a press or the like so as to be sufficiently cured. 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 molded product is obtained by a process of once producing a polymer material and dissolving it in an organic solvent or the like, then molding it into a desired shape and evaporating the organic solvent. On the other hand, according to the present invention, since the monomer composition before the reaction is directly molded into a desired shape without using an organic solvent, the conventional problems caused by the residual organic solvent do not occur. <Use 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, and housings, casings, coatings, insulating films, and interlayer insulating films for electronic members such as semiconductors. , A laminate, an electronic member such as a sealing material. In addition, printed wiring boards for mounting electronic components, build-up boards, on-board boards, copper-clad laminates for boards, circuit-embedded boards, antenna boards, and electronic-related boards such as CPU on-board boards (hereinafter simply referred to as boards). ).

Further, the material constituting the substrate (electronic member)
As, for example, build-up material, solder resist material,
Undercoat material, backcoat material, topcoat material,
It can be used as an interlayer adhesive, a passivation material formed on the surface of an IC substrate, a moisture-proof material for a hybrid IC substrate, and the like. Further, 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 a mold material for electronic members. <Usage of each application> (Insulating film, laminate, substrate) The above monomer composition is applied on a substrate such as a resin film, a glass plate, a silicone rubber plate, and a metal plate, and is photocured. By doing so, 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 fibers may be obtained by impregnating the monomer composition with inorganic fibers, inorganic fillers, organic fibers or non-woven fabric and then photo-curing. 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 predetermined thickness. Specifically, after the photocured film or plate material and the monomer composition are alternately laminated using the interlayer composition as an interlayer adhesive, or after the preliminary photocured film or plate material (prepreg) is laminated. And 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 preferred as the metal conductor layer in terms of workability and production cost. The method for laminating the film and the conductor foil can be the same method as the method for producing the substrate. Specifically, the conductor 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 press molding. Also, after printing the etching resist according to the circuit pattern using a pattern printer such as a silk screen printer on the laminate,
It is also possible to form a circuit pattern by forming plating and removing the etching resist. (Build-up material) A build-up material is a layer composed of a combination of an insulating layer and a conductor layer on at least one surface of a circuit board (single-layer printed wiring board or multilayer printed wiring board) having a circuit pattern on the surface. The above is an insulating material used for a printed wiring board in which conductive layers are connected. 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 polymer insulating material of the present invention can be adhered even if the organic solvent is removed after the application, so that it is easy to attach 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. (Undercoat material) An undercoat material is a liquid for absorbing a step (about several tens of μm) generated when a metal conductor layer, for example, a copper foil is laminated to a base material to produce a substrate, and for obtaining smoothness. Or a 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 polymer insulating material of the present invention can be made organic solvent-free without using an organic solvent, it is only necessary to consider only the shrinkage accompanying the curing reaction. It is also preferable from the viewpoint. (Interlayer adhesive) The interlayer adhesive is an adhesive used for bonding the base material or the substrate and the conductive foil, and is completely cured to firmly bond the substrates or the substrate and the metal conductive film. Used for the purpose of 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. (Anisotropic conductive film) An anisotropic conductive film is a pre-preg prepared by pre-curing a state in which inorganic fine particles or polymer fine particles plated with a conductive powder or a conductive substance are dispersed in an insulating material. It is a mold material that ensures stability such as conduction and adhesion between the component and the substrate by being inserted into the gap between the various components and the substrate. As the conductive powder or conductive material, copper, nickel, aluminum, silver, gold,
And carbon black. At that time, the intended anisotropic conductive film can be obtained by using the polymer insulating material of the present invention as the insulating material, and excellent electrical insulation can be provided to the 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, a conductor such as copper or aluminum can be provided on the interlayer insulating film for semiconductor by a vacuum deposition method or the like. The obtained interlayer insulating film for semiconductors has excellent electrical insulation properties and heat resistance. (Semiconductor encapsulant) The semiconductor encapsulant is an insulating material used to protect the electronic component from a chemical and physical environment. In this case, it is preferable to use a mixture of the above-mentioned monomer composition and the filler such as the above-mentioned silica, an epoxy resin precursor or the like, and a transfer molding method or the like can be adopted as a molding method.

Further, a bulk body can be obtained by shaping the monomer composition or its prepreg into a predetermined shape by a molding method, an extrusion method or the like and curing the same. This bulk body can have excellent environmental resistance after curing. (Solder resist material) Solder resist is a protective film that prevents solder from adhering to unnecessary parts when soldering on the surface of a circuit board, and protects the circuit from oxidation and corrosion due to direct exposure to air. It is a permanent resist that functions as a protective film to prevent it. In preparing the solder resist, the above-mentioned monomer composition containing a filler such as silica, an epoxy resin precursor or the like can be used. As an application method, a method such as a screen printing method can be used, and excellent environmental resistance can be imparted after curing.

The effects exerted by the above-described embodiment will be summarized below. The polymer insulating material described in the embodiment mainly has a dielectric constant, a dielectric tangent,
Excellent electrical properties such as electrical insulation can be exhibited.

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 electric insulation, solvent resistance, dimensional stability and durability, and also excellent in strength, thermal shock resistance and adhesion.

The polymer insulating material does not have a process of once dissolving the polymer in an organic solvent at the time of molding and processing, and the raw material monomer composition is formed into a predetermined shape as it is. The photo-curing is performed, and the polymer insulating material having excellent moldability or workability and having a predetermined shape can be efficiently produced.

In addition, by using a compound containing no metal as a polymerization initiator, when used as an electric insulating film and a substrate on which the film is laminated, a metal compound harmful to electric performance is contained in the polymer. Since it is not included, it is possible to maintain good electric characteristics.

The above-mentioned polymer insulating materials are used for electronic-related substrates such as printed wiring boards and build-up boards,
Suitable for electronic components such as insulating films, laminates, build-up materials, undercoat materials, interlayer adhesives, anisotropic conductive films, interlayer insulating films for semiconductors, sealing materials for semiconductors, solder resist materials, etc. Useful for

[0056]

[Examples] The above embodiment will be further described below with reference to examples.
Although described concretely, the present invention is limited to these examples.
Not something. It should be noted that the fumar shown in Examples and Comparative Examples
Acid diesters, crosslinkable monomers, and other vinyl monomers
Abbreviation and compound name of polymer, other polymer, polymerization initiator
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 <Crosslinking monomer> DVB: divinylbenzene DVAd: adipic acid Divinyl CHDVE: 1,4-cyclohexane dimethanol dibi
Nyl ether HDVE: n-hexanediol divinyl ether MHDVE: 2,5-dimethyl-2,5-hexanedioxide
Divinyl ether BDA: 1,4-butanediol diacrylate BPDA: CH_Two= CHCOOCH_TwoCH_TwoOφC (CH_Three)
_TwoφOCH_TwoCH_TwoOCOCH = CH_Two TMPTM: Trimethylolpropane trimethacrylate
G PhBMI: 4,4'-diphenylmethanebismaleimi
De TMPTE: Trimethylolpropane triallylate
DATP: diallyl terephthalate PDAP: CH_Two= CHCH_TwoOCOφCOO [CH (CH_Three) CH_TwoO
COφCOO] mCH_TwoCH = CH_Two(Mixing of m = 0 to 5
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-isop manufactured by Kuraray Co., Ltd.
Renblock copolymer (trade name: Hibler 5125) SIS # 2002: Styrene-isop manufactured by Kuraray Co., Ltd.
Len block copolymer (trade name: Septon 2002) <Polymerization initiator> HMP: 2-hydroxy-2-methyl-1-phenylp
Lopan-1-one (trade name: Darocur # 117)
3) MPE: 2,2-dimethoxy-1,2-diphenyl eta
N-1-one (trade name: Irgacure # 651) BMAMPB: 2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl) butanone-1 (product
Name: Irgacure @ 369) MMTPMP: 2-methyl-1- [4- (methylthio)
Phenyl] -2-morpholinopropan-1-one (quote
Product name: Irgacure @ 907) MBPPO: Bis (2,4,6-trimethylbenzoyi)
) -Phenylphosphine oxide (Irgacure)
819) BPO: benzoyl peroxide DCP: dicumyl peroxide Evaluation of polymer insulating material (Example 1) 9.0 g of DcHF, 1.0 g of HDVE and
A monomer composition was obtained by blending 0.5 g of HMP. next,
This is divided into two pieces by a silicone rubber spacer
Injected and shaped between glass plates, super high of 20mW / cm
6 J / cm using a mercury pressure lamp ^TwoIllumination with the irradiation energy of
And cured. This is further heated at 150 ° C for 1 hour
12 cm long, 10 cm wide and 0.8 mm thick
I got it.

On the other hand, a spin coater (Mikasa Corporation M
The above monomer composition was applied to a silicon wafer (manufactured by Kyokyo International Co., Ltd.) using IKASA SPINCOATER1H-D3) and cured in a nitrogen-substituted glass cell under the same conditions as above. 10
An insulating film of 0 μm was obtained. <Evaluation of electrical insulation resistance (hereinafter referred to as insulation resistance)> JI
According to SK6911, the sheet was cut into 40 mm ×
A 20 mm x 0.8 mm strip was prepared. 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> 10 cm ×
A 1.0 mm × 0.8 mm stick was prepared. The relative permittivity and the dielectric loss tangent at a measurement frequency of 2 GHz were measured using a complex dielectric constant evaluation device (manufactured by Kanto Electronics Application Development Co., Ltd.) with a cavity resonator perturbation method. <Evaluation of solder heat resistance>
A strip of mm × 3 mm × 100 μm was prepared. This is 2
60 ° C solder bath (POT-20 manufactured by Taiyo Denki Kogyosho)
0C) for 120 seconds to evaluate the appearance. If there was no change in color or shape, it was evaluated as ○, and otherwise, it was evaluated as ×. <Evaluation of water absorption> The insulating film was cut to 50 mm
× 50mm × 100μm insulating film was prepared and JI
The water absorption (%) was measured according to SC6481. <Evaluation of solvent resistance> 25 m
An insulating film of mx 25 mm x 100 μm was prepared and J
It was immersed in toluene and methylene chloride according to ISC6481, 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 ×. The formulations are summarized in Table 1, and the evaluation results are summarized in Table 2. (Examples 2 to 20) Samples were prepared in the same manner as in Example 1 except that the types and amounts of fumaric acid diester, crosslinkable monomer, polymerization initiator, and other vinyl monomers were changed. The properties were evaluated. The formulations are summarized in Table 1 and the evaluation results are summarized in Table 2. (Comparative Examples 1-4) In a 20-liter stainless steel reaction vessel equipped with a stirrer, polyvinyl alcohol (KH-17,
10,000 parts by weight of ion-exchanged water in which 100 parts by weight of NPO was dissolved, and BPO6
2,000 parts by weight of DcHF in which 0 parts by weight were dissolved were added, and suspension polymerization was performed at 70 ° C. for 10 hours. Obtained PDc
HF 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.

[0060]

[Table 1]

[0061]

[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 in addition to the long curing time, and the solder heat resistance and the water absorption may decrease. <Evaluation of laminate> (Example 21) 900 parts by weight of DcHF, 100 parts by weight of PDAP (trade name BA901, manufactured by Showa Denko KK), MPE
50 parts by weight and 10 parts by weight of DCP were blended to obtain a monomer composition, which was woven with a glass woven cloth (20 cm square, thickness 60 ± 2 μm).
m, 12 pieces of E glass manufactured by Asahi Schwebel Co., Ltd.). Each of the sheets was preliminarily cured by irradiating it with an irradiation energy of 1 J / cm ² using the ultrahigh pressure mercury lamp described in Example 1 in a nitrogen gas atmosphere, and 12 sheets were stacked, and the thicknesses were formed on the upper and lower sides. Laminate 18 μm copper foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd.), 150 ° C., 5 hours, 19.6 × 1
0 ^-3 MPa (0.2 kg / cm ² ), then 17
0 ° C., 2 hours, 49 × 10 ⁻³ MPa (0.5 kg / cm
Press molding was performed under the conditions of ² ). As a result, thickness 0.8m
m was obtained. <Evaluation of Insulation Resistance> The copper foil on both sides was removed by etching, cut into a sheet of 40 mm × 20 mm according to JIS C6481, two holes having a diameter of 5 mm were formed at an interval of 15 mm, and a tapered pin was used 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 properties> The copper foil on both sides was removed by etching, cut into sticks of 10 cm x 1.0 mm, and the relative dielectric constant was measured using a cavity resonator perturbation complex permittivity evaluator at a measurement frequency of 2 GHz. The modulus and the dielectric loss tangent were measured. <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 otherwise, as ×. <Evaluation of Water Absorption> The copper foil on both surfaces was removed by etching, and cut into a 50 mm × 50 mm sheet in accordance with JIS C6481 to measure the water absorption (%). <Evaluation of Solvent Resistance> The copper foil on both surfaces was removed by etching, cut into 25 mm × 25 mm sheets according to JIS C6481, and immersed in toluene and methylene chloride to evaluate the appearance. 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 fumaric acid diester, crosslinkable monomer, polymerization initiator, and other vinyl monomers were changed. The properties were evaluated. Table 3 shows the blends, and Table 4 shows the evaluation results. (Comparative Example 5) 1000 parts by weight of DcHF, 50 parts by weight of MPE, and 10 parts by weight of DCP were blended, a sample was prepared in the same manner as in Example 21, and each characteristic was evaluated. Table 4 summarizes the results. (Comparative Example 6) Polymer PCHIP15 prepared in Comparative Example 2
0 parts by weight was dissolved in 850 parts by weight of toluene, and a varnish was prepared by filtration under pressure. Apply this varnish to a glass woven cloth (2
Twelve sheets of 0 cm square, 60 ± 2 μm thick, E-glass manufactured by Asahi Schwebel Co., Ltd.) were impregnated.

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, and was heated at 150 ° C. for 2 hours at 0.294 MPa (3 kg / c).
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.

[0064]

[Table 3]

[0065]

[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 a pre-treated glass-epoxy substrate coated on both sides with copper (FR- 4 Sumitomo Bakelite Co., Ltd.)
The monomer composition was applied thereon using a bar coater. Using the ultrahigh pressure mercury lamp described in Example 1 under an atmosphere of nitrogen gas, photocuring was performed at an irradiation energy of 6 J / cm ² and further heated at 150 ° C. for 1 hour to form an organic resin insulating layer.

Then, 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. 10 at room temperature
% Of sulfuric acid for 10 minutes to remove calcium carbonate on the surface of the organic resin insulating layer to form fine irregularities on the surface of the insulating layer. Then, 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. Chromic acid mixture maintained at 75 ° C. (chromic acid 200 g / L, concentrated sulfuric acid 55
0 g / L) for 10 minutes at 8 ° C.
After immersion in an H aqueous solution for 60 minutes and again at 75 ° C. for 10 minutes in chromic acid mixed solution, polystyrene on the surface of the insulating layer was removed to 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. By immersing in a chromic acid mixed solution and 8N KOH aqueous solution in the same manner as in Example 28 to remove the filler 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.

[0070]

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

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.

[0072]

[Table 6] As shown in Table 6, in Example 29, the peel strength of the plating was good. <Evaluation of Adhesive> (Example 30) 70 parts by weight of DcHF, 10 parts by weight of PDAP, 10 parts by weight of St, 10 parts by weight of SIS # 5125,
A glass epoxy substrate (FR-4 Sumitomo Bakelite Co., Ltd.) obtained by mixing 5 parts by weight of HMP and 2 parts by weight of DCP to obtain a monomer composition and removing the surface copper foil by etching.
Co., Ltd.) using a bar coater. Further, it was pre-cured by irradiating it with an irradiation energy of 1 J / cm ² using the ultrahigh pressure mercury lamp described in Example 1 under a nitrogen gas atmosphere, and then removing the air bubbles of a 18 μm thick copper foil with a rubber roller. Crimping, 150 ° C, 5 hours, 19.6x
10 ⁻³ MPa (0.2 kg / cm ² ), then 1
70 ° C., 2 hours, 49 × 10 ⁻³ MPa (0.5 kg / c
m ² ).

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, 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 peeled was evaluated as ×. Table 7 summarizes the results. (Comparative Example 7) 90 parts by weight of DcHF, SIS # 5125
10 parts by weight, 5 parts by weight of MPE and 2 parts by weight of DCP were blended to obtain a monomer composition, which was bar-coated on a glass epoxy substrate (FR-4 manufactured by Sumitomo Bakelite Co., Ltd.) from which the surface copper foil was removed by etching. It was applied using a coater.
Further, it was pre-cured by irradiating it with irradiation energy of 1 J / cm ² using the ultrahigh pressure mercury lamp described in Example 1 in a nitrogen gas atmosphere. Next, a copper foil having a thickness of 18 μm was pressure-bonded with a rubber roller while removing air bubbles, and was heated at 150 ° C.
5 hours, 19.6 × 10 ⁻³ MPa (0.2 kg / c
m ² ), then 170 ° C., 2 hours, 49 × 10 ⁻³
Press molding was performed under the conditions of MPa (0.5 kg / cm ² ). This was evaluated in the same manner as in Example 30.
Summarized in

[0074]

[Table 7] As shown in Table 7, the adhesive of Example 30 had insulation resistance,
The solder heat resistance, water absorption, solvent resistance, and adhesion are all good, and the durability is excellent. On the other hand, Comparative Example 7 containing no crosslinkable monomer is inferior in solvent resistance and adhesion. <Evaluation of Anisotropic Conductive Film> (Example 31) 65 parts by weight of DcHF, 20 parts by weight of PDAP, 10 parts by weight of SIS # 5125, 5 parts by weight of carbon black (average particle size: 0.1 μm) as a conductive powder, and as a viscosity modifier 100 parts by weight of toluene, 3 parts by weight of HMP, and 1 part by weight of DCP were blended to obtain a monomer composition.
As a connection test substrate, a substrate having a glass epoxy material base having a thickness of 1.6 mm and a copper foil having a thickness of 35 μm was used, and a line pattern having a line pitch and a line width of 125 μm was formed. The monomer composition was applied on the substrate by screen printing, and dried in a nitrogen gas at 60 ° C. for 3 minutes.

Next, Example 1 was performed under a nitrogen gas atmosphere.
The film was pre-cured by irradiating light with an irradiation energy of 1 J / cm ² using an ultrahigh pressure mercury lamp described in (1) to obtain a tack-free film having a thickness of 20 μm. The same connection test substrate as described above was bonded on this film by performing positional alignment between the corresponding electrodes on both substrates, and was bonded at 0.98 MPa (10 kg /
cm ² ) at 180 ° C. for 1 minute. <Evaluation of Contact Resistance> The contact area was measured at 0.15 × 3.0 mm. <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 and / or cracks occurred between layers were evaluated as ×. <PCT (Pressure Cooker Test)> The substrate on which the semiconductor chip was mounted was subjected to a humidity of 100%, a temperature of 105 ° C.
It was left for 30 minutes under the condition of 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 and / or cracks occurred between layers were evaluated as ×. Table 8 summarizes the results. (Example 32) A monomer composition was obtained by mixing 65 parts by weight of DiPF, 20 parts by weight of CHDVE, 10 parts by weight of SIS # 5125, 5 parts by weight of carbon black, 100 parts by weight of toluene, 3 parts by weight of HMP, and 1 part by weight of DCP. . Hereinafter, preparation and evaluation were performed in the same manner as in Example 31, and the results were shown in Table 8.
Summarized in (Comparative Example 8) 75 parts by weight of DcHF, SIS # 5125
10 parts by weight, carbon black 5 parts by weight, toluene 10
0 parts by weight, 3 parts by weight of HMP and 1 part by weight of DCP were blended to obtain a monomer composition. This was prepared and evaluated in the same manner as in Example 30, and the results are summarized in Table 8. (Comparative Example 9) 20 parts by weight of PCHIP, SIS # 5125
2 parts by weight, 1 part by weight of carbon black, toluene 70
By weight, 10 parts by weight of tert-butylbenzene was mixed to obtain a monomer composition. This was prepared and evaluated in the same manner as in Example 27, and the results are shown in Table 8.

[0076]

[Table 8] As shown in Table 8, the anisotropic conductive films of Examples 31 and 32 had good contact resistance, thermal shock resistance and PCT, and were excellent in durability. On the other hand, Comparative Examples 8 and 9, which do not contain a crosslinkable monomer and contain an organic solvent, have low contact resistance and are inferior in thermal shock resistance and PCT. <Evaluation of Interlayer Insulating Film for Semiconductor> (Example 33) 8.5 parts by weight of DcHF, HDVE1.5
Parts by weight, 200 parts by weight of toluene, and 1 part by weight of MPE were blended to obtain a monomer composition, and the monomer composition was applied on a silicon wafer using a spin coater.
After drying for 0 seconds, the film thickness was 200 nm. 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. Using an ultrahigh pressure mercury lamp described in Example 1 and irradiating with light at an irradiation energy of 6 J / cm ^{2 in} a nitrogen gas atmosphere, the composition is cured, and then a vacuum vapor deposition apparatus (VPC-260, manufactured by Vacuum Kiko Co., Ltd.) Was used to deposit aluminum, and electrodes were formed on the upper and lower portions. <Measurement of relative permittivity> Using a dielectric measurement electrode HP16451B and a precision LCR meter HP4285A (manufactured by Hewlett-Packard Japan, Inc.), a frequency of 1 MHz was used.
Was measured for the relative dielectric constant of the film. <Evaluation of heat resistance> The film was peeled off from the silicon wafer and subjected to thermogravimetric analysis. Then, a case where no weight loss due to thermal decomposition was observed at 350 ° C. was evaluated as ○, and the others were evaluated as ×. <Evaluation of Adhesion> After the test under the PCT conditions described in Example 31, the adhesion was evaluated by a basement test using a cellophane tape in accordance with JISC5012. And
The sample that was not peeled off from the wafer was rated as ○, and the one that was peeled was rated as ×. Table 9 summarizes the results. (Example 34) 8.5 parts by weight of DiPF, CHDVE1.
5 parts by weight, 200 parts by weight of toluene and 0.2 parts by weight of BPO were blended to obtain a monomer composition. And the third embodiment
Preparation and evaluation were performed in the same manner as in Example 3, and the results were summarized in Table 9. Comparative Example 10 A monomer composition was obtained by mixing 10 parts by weight of DcHF, 200 parts by weight of toluene, and 0.2 parts by weight of BPO. And it prepared and evaluated like Example 33, and the result was put together in Table 9. (Comparative Example 11) 10 parts by weight of PDcHF and toluene 20
A varnish consisting of 0 parts by weight was blended, applied to a silicon wafer using a spin coater, and dried at 200 ° C. for 30 seconds. As a result, the film thickness was 200 nm. This operation was repeated 10 times to produce a 2 μm film. However,
The film was cut with a microcutter, and the cross section was observed with an electron microscope. As a result, it was observed that the thickness was changed by 10% and the surface was wavy. Next, aluminum was deposited using a vacuum deposition apparatus, and electrodes were formed on the upper and lower portions. Using this, evaluation was made in the same manner as in Example 33, and the results were shown in Table 9.
Summarized in

[0077]

[Table 9] As shown in Table 9, the interlayer insulating films for semiconductors of Examples 33 and 34 have good relative dielectric constant, heat resistance and adhesion, and are excellent in durability. On the other hand, Comparative Examples 10 and 11 which did not contain a crosslinkable monomer and contained an organic solvent
Is inferior in heat resistance and adhesion. <Evaluation of encapsulant for semiconductor> (Example 35) 60 parts by weight of DcHF, 30 parts by weight of DATP, 10 parts by weight of SIS # 5125, 150 parts by weight of fused silica (average particle diameter 5 μm), 5 parts by weight of HMP, and DCP
One part by weight was mixed, dispersed and mixed at 80 ° C. using a three-roll mill, and vacuum defoamed.

Next, a pin grid array was sealed using this composition by a transfer molding method.
Using the ultrahigh pressure mercury lamp described in Example 1 under a nitrogen gas atmosphere, light irradiation was performed at an irradiation energy of 1 J / cm ² to perform pre-curing, and the temperature was raised to 150 ° C. in 30 minutes.
The package was molded by heating and curing at 50 ° 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, no weight loss due to thermal decomposition was observed at 350 ° C. <PCT> After the test under the PCT conditions described in Example 31, observation was performed with an optical microscope (magnification: 30 times). As a result, appearance deterioration such as peeling and cracking was not observed. (Example 36) 70 parts by weight of DiPF, 25 parts by weight of TMPTE, 5 parts by weight of SIS # 5125, 150 parts by weight of fused silica (average particle size: 5 μm), 5 parts by weight of HMP, and DCP
One part by weight was mixed, dispersed and mixed at 80 ° C. using a three-roll mill, and vacuum defoamed. Hereinafter, it was prepared and evaluated in the same manner as in Example 35. As a result, no weight loss or deterioration in appearance due to thermal decomposition was observed. (Comparative Example 12) 95 parts by weight of DcHF, SIS # 5125
5 parts by weight, 150 parts by weight of fused silica (average particle size: 5 μm), 5 parts by weight of HMP and 1 part by weight of DCP were blended, dispersed and mixed at 80 ° C. using a three-roll mill, and vacuum defoamed. Thereafter, a package was molded in the same manner as in Example 35, 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 37) 60 parts by weight of DcHF, 30 parts by weight of DVAd, 10 parts by weight of SIS # 2002, 20 parts by weight of fused silica (average particle diameter 5 μm), 100 parts by weight of toluene, HM
P5 parts by weight and DCP1 part by weight are blended, and a screen printing machine (manufactured by Micro-Tech Co., Ltd .: MT-150RT)
Using V), screen printing was performed on the surface of the glass epoxy resin using a silk screen (V60 manufactured by NBC Industries, Ltd.) on which a line and space of 40 μm was drawn.

Next, Example 1 was performed under a nitrogen gas atmosphere.
The composition was pre-cured by irradiation with light at an irradiation energy of 1 J / cm ² using an ultra-high pressure mercury lamp described in 1 above, followed by curing at 150 ° C. for 1 hour. Observation of the obtained solder resist with a microscope revealed that a film thickness of 50 μm and a line & space of 40 μm were faithfully reproduced. <Evaluation of solvent resistance> 25 m according to JIS C6481
The sheet was cut into a sheet of mx 25 mm, immersed in toluene and methylene chloride, and its appearance was evaluated. As a result, no change in shape such as swelling and roughness was observed. <Evaluation of Adhesion> After the test under the PCT conditions described in Example 31, the adhesion was evaluated by a grid test using a cellophane tape in accordance with JISC5012. As a result, the film did not peel off from the substrate. (Comparative Example 13) 90 parts by weight of DcHF, SIS # 2002
10 parts by weight, 20 parts by weight of fused silica (average particle size: 5 μm), 100 parts by weight of toluene, 5 parts by weight of HMP, DCP1
By weight, a resist film was formed on the surface of the glass epoxy resin in the same manner as in Example 37. As a result, the thickness,
Lines and spaces were faithfully reproduced as in Example 37. Further, as a result of evaluating the solvent resistance and the adhesion, swelling of the coating was observed in both toluene and methylene chloride, and peeling was observed in the adhesion test.

The technical ideas grasped from the above embodiment will be described below. The photocurable polymer insulating material according to claim 1, wherein the fumaric diester is a main component in the monomer composition. With such a configuration, it is possible to maintain good electrical characteristics of the polymer insulating material.

The photocurable polymer insulating material according to claim 1, wherein the monomer composition further contains a polymer or another vinyl monomer other than the monomer.
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 photocurable polymer insulating material according to claim 2, wherein the photocuring is performed in the substantial absence of an organic solvent. According to this manufacturing method, moldability or workability can be improved.

[0083]

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

According to the method for producing a photocurable polymer insulating material of the second invention, a photocurable polymer insulating material capable of exhibiting the effects of the first invention can be produced efficiently. According to the electronic-related substrate of the third aspect, the effect of the photocurable polymer insulating material of the first aspect can be exerted on a printed wiring board, a build-up board, and the like.

According to the electronic member of the fourth aspect, the effect of the photocurable polymer insulating material of the first aspect can be exerted on an insulating film, a laminate, an undercoat material, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 35:02 H01L 23/14 R (72) Inventor Naoyuki Amaya 2-1-1 Shimozen, Toda City, Saitama Prefecture No. 5 (72) Inventor Masami Okoo 48-18 Umenogi, Mito-cho, Chita-gun, Aichi Prefecture, Japan 18-72 (72) Inventor Yukihiro Kato 8 West Gate, Taketoyo-cho, Chita-gun, Aichi Prefecture, Japan (72) Inventor Hiroaki Hasegawa 1-13-1 Nihonbashi, Chuo-ku, Tokyo Inside TDC Corporation (72) Inventor Toshiaki Yamada 1-13-1 Nihonbashi, Chuo-ku, Tokyo TDK Corporation (72) Inventor Shigeru Asami 1-1-13 Nihonbashi, Chuo-ku, Tokyo FTD term (reference) 4F071 AA12 A A22 AA30 AA33 AA35 AA36 AA37 AA39 AC07 AC15 BA02 BB01 BB02 BC01 BC02 BC07 4J011 AC04 QA08 QA12 QA13 QA18 QA19 QA20 QA23 QA24 QA26 QA27 QB22 SA01 SA21 SA31 SA64 SA78 SA84 UA01 VA01Q01 AU01 VA01Q01 AQ21Q AS02Q AS03Q BA02Q BA03Q BA04P BA05P BA06P BA42Q BB01P BB07P BC04Q BC43P BC44Q BC45Q CA04 FA03

Claims (4)

[Claims] 1. Photocuring obtained by photocuring a monomer composition containing a fumaric acid diester, a monomer having two or more carbon-carbon double bonds in one molecule, and a photodecomposition type polymerization initiator. Polymer insulating material. 2. A monomer composition is prepared by mixing a fumaric acid diester, a monomer having two or more carbon-carbon double bonds in one molecule, and a photodecomposable polymerization initiator, and then preparing a monomer composition. A method for producing a photo-curable polymer insulating material, wherein the photo-curable polymer insulating material is shaped and then light-cured. 3. An electron-related substrate formed from a constituent material containing the photocurable polymer insulating material according to claim 1. 4. An electronic member formed from a constituent material containing the photocurable polymer insulating material according to claim 1.