JP2005171207A - Resin sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a resin sheet, which is excellent in dynamic physical properties, dimensional stability, heat-resistance, transparency, low water absorbing property, flame-resistance, laser-processing property, and the like, in particular, excellent in high-temperature physical properties. <P>SOLUTION: This resin sheet comprises a resin composition containing 100 pts.wt. of a thermoplastic resin and/or a light curable resin and 0.1 to 100 pts.wt. of layered silicate, wherein the thickness ranges from 10 to 200μm, the proportion of a portion having post-hardening tensional modulus of elasticity of 2.0 GPa or less is 20 to 70% in thickness from at least one surface, and when such a portion having post-hardening tensional modulus of elasticity of 2.0 GPa or less is present on both surfaces, the total proportion of such portions is 70% or less in thickness from both surfaces. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin sheet excellent in mechanical properties, dimensional stability, heat resistance, transparency, low water absorption, flame retardancy, laser processability, etc., and particularly excellent in high temperature properties.

  2. Description of the Related Art In recent years, electronic devices with high performance, high functionality, and miniaturization are rapidly progressing, and there is an increasing demand for miniaturization and weight reduction of electronic components used in electronic devices. As a result, further improvements in physical properties such as heat resistance, mechanical strength, and electrical characteristics have been demanded for the materials of electronic components. For example, for semiconductor device packaging methods and wiring boards for mounting semiconductor devices. However, higher density, higher functionality, and higher performance are required.

Multilayer printed circuit boards used in electronic devices are composed of a plurality of insulating substrates, and conventionally, as this interlayer insulating substrate, for example, a thermosetting resin prepreg in which a glass cloth is impregnated with a thermosetting resin, Films made of thermosetting resins or photocurable resins have been used. Even in the multilayer printed circuit board, it is desired to make the interlayer extremely thin for high density and thinning, and an interlayer insulating board using a thin glass cloth or an interlayer insulating board not using a glass cloth is required. ing.
As such an interlayer insulating substrate, for example, those made of rubber (elastomer), thermosetting resin material modified with acrylic resin, thermoplastic resin material containing a large amount of inorganic filler, etc. are known. In Patent Document 1, a varnish mainly composed of a high molecular weight epoxy polymer and a polyfunctional epoxy resin is blended with an inorganic filler having a predetermined particle diameter, and applied to a support to form an insulating layer. A method for manufacturing an insulating substrate is disclosed.

  However, in the multilayer insulating substrate produced by the above production method, in order to sufficiently improve the mechanical properties such as mechanical strength by securing the interface area between the inorganic filler and the high molecular weight epoxy polymer or polyfunctional epoxy resin. In addition, it is necessary to blend a large amount of an inorganic filler, which makes it difficult to thin the interlayer. In particular, since a large amount of inorganic filler is blended, cracks may occur during reliability tests such as a thermal cycle test.

  In addition, interlayer insulation substrates that use thin glass cloth and interlayer insulation substrates that do not use glass cloth have problems such as insufficient heat resistance and dimensional stability. There was a problem that often occurred. In particular, when glass cloth is not used, it is difficult to reduce the linear expansion coefficient, and because of the difference in linear expansion coefficient between the rigid substrate using the glass cloth and the copper circuit, this is also applied to a thermal cycle test or the like. Cracks sometimes occurred during the reliability test.

  The multilayer printed circuit board is manufactured by a build-up method for obtaining a multilayer laminate by repeating circuit formation and lamination on a layer, a batch lamination method for laminating layers on which circuits are formed, or the like. In any manufacturing method, since the number of processes is large, the quality of the material greatly affects the yield and includes processes such as a plating process, a curing process, a solder reflow process, and a laser drilling process. Solvent resistance, water resistance, heat resistance and dimensional stability at high temperatures are required. Specifically, for example, resistance to acids, alkalis, and organic solvents; low moisture absorption that affects electrical characteristics; dimensional stability at high temperatures and after heating that affects high-precision circuit connections between upper and lower layers; Heat resistance up to 260 ° C. required for mounting with lead-free solder; copper migration that affects connection reliability is required to occur less easily.

For example, build-up boards and printed multilayer boards used in IC packages may be subject to high-temperature conditions due to heat generation, and it is required to maintain high reliability even in such an environment. If it is large, there is a problem that peeling occurs from a metal wiring such as copper forming a circuit, causing a short circuit or disconnection.
In addition, even in a flexible multilayer substrate that has recently attracted attention as a thin substrate, the thermal dimensional change between the adhesive layer that bonds single-layer flexible substrates to each other, the polyimide film that forms the flexible substrate, and the metal wiring such as copper that forms the circuit If the difference is large, the same problem occurs.

  Originally, it has been considered effective to reduce the difference in linear expansion coefficient from the base material in order to prevent cracks from occurring during reliability tests such as a cooling / heating cycle test. In recent years, in order to lower the linear expansion coefficient, a large amount of inorganic filler is often added. In this case, due to the brittleness of the resin composition, if residual stress exists, the linear expansion coefficient decreases, but cracks occur. May occur. Therefore, it has been difficult to obtain a highly reliable material by extending the technology so far.

In addition, when a large amount of inorganic filler is used in the material, a large amount of energy may be required for drilling, in addition to the difficulty in alignment during laser drilling.
Ordinary inorganic compounds have a size of several microns or more, and in that case, it is necessary to evaporate a large mass of inorganic several microns in laser processing. In general, an inorganic compound requires a larger energy for laser treatment than an organic compound. As a result, in order to open a hole of a required size, there was a problem that it had to be processed with a large output or processed multiple times compared to the case of resin alone.
JP 2000-183539 A

  The present invention provides a resin sheet that is excellent in mechanical properties, dimensional stability, heat resistance, transparency, low water absorption, flame retardancy, and the like, and particularly excellent in high temperature properties and laser processability, in view of the above-described present situation. It is for the purpose.

The resin sheet which concerns on this invention is a resin sheet which consists of a resin composition containing 100 weight part of thermosetting resins and / or photocurable resin, and 0.1-100 weight part of layered silicate, Comprising: The portion having a tensile modulus of elasticity of 10 to 200 μm and a post-cure tensile modulus of 2.0 GPa or less has a thickness in the range of 20% to 70% from at least one surface, and the tensile modulus after curing from both surfaces is 2. If there is a portion that is 0 GPa or less, the total is 70% or less.
Preferably, the average linear expansion coefficient (α1) from a temperature 50 ° C. lower than the glass transition temperature of the resin sheet to a temperature 10 ° C. lower than the glass transition temperature of the resin sheet is 5.0 × 10 ⁻⁵ [° C. ^{− 1} ] The following.
In the resin sheet according to the present invention, preferably, the thermosetting resin and / or the photocurable resin is the epoxy resin, the thermosetting modified polyphenylene ether resin, the thermosetting resin. At least one selected from the group consisting of conductive polyimide resin, silicon resin, benzoxazine resin, and melamine resin.
The layered silicate is preferably at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite.
More preferably, the layered silicate contains an alkyl ammonium ion salt having 6 or more carbon atoms, an aromatic quaternary ammonium ion salt or a heterocyclic quaternary ammonium ion salt. In the resin sheet according to the present invention, preferably, the average interlayer distance of the (001) plane measured by the wide-angle X-ray diffraction measurement method is 3 nm or more, and part or all of the laminates are 5 layers or less. As is the case, the layered silicate is dispersed.

In the resin sheet which concerns on this invention, it consists of a resin composition containing 100 weight part of thermosetting resins and / or photocurable resin, and 0.1-100 weight part of layered silicates, and the thickness is the range of 10-200 micrometers. The portion where the tensile modulus after curing is 2.0 GPa or less is at least 20% to 70% in thickness from one surface, and the tensile modulus after curing is 2.0 GPa or less from both surfaces. When there is a certain part, the total is 70% or less, so the coefficient of thermal expansion is low, it is excellent in dimensional stability when given a change, excellent in mechanical properties, heat resistance and transparency. Furthermore, it has low water absorption and is excellent in laser processability.
Therefore, the resin sheet according to the present invention is suitably used for, for example, a multilayer substrate material or an optical material that requires transparency.
In the resin sheet according to the present invention, the average linear expansion coefficient α1 from a temperature lower by 50 ° C. than the glass transition temperature to a temperature lower by 10 ° C. than the glass transition temperature of the resin sheet is 5.0 × 10 ⁻⁵ ° C. ^−1. In the case of the following, it is possible to provide a resin sheet that is less prone to cracks due to temperature changes and has excellent dimensional stability.
Further, in the present invention, the layered silicate is dispersed so that the average interlayer distance of the (001) plane measured by the wide angle X-ray diffraction measurement method is 3 nm and a part or all of the laminate is 5 layers or less. If so, the dispersibility of the layered silicate is effectively enhanced. Therefore, it is possible to provide a resin sheet that is further excellent in high-temperature physical properties, flame retardancy, and laser processability.

In the resin sheet of the present invention, the portion where the tensile modulus after curing is 2.0 GPa or less has a thickness ranging from 20% to 70% from at least one surface, and the tensile modulus after curing from both surfaces is 2 When there is a portion that is 0.0 GPa or less, the total is 70% or less. By being 2.0 GPa or less, the residual stress existing in the vicinity of the adhesive interface can be relaxed, and cracks and the like are hardly generated even in reliability tests such as a thermal cycle test. More preferably, it is 1.5 GPa or less, More preferably, it is 1.0 GPa or less. When the pressure is 1.0 GPa or less, the stress can be relaxed even during the heating process during the process.
When the thickness having a tensile modulus of 2 GPa or less is 20% or less of the sheet from the surface, the stress relaxation property is insufficient, and cracks may occur in a reliability test such as a thermal cycle test.
In addition, when the tensile elastic modulus after curing is 2.0 GPa or less from the surface to a portion having a thickness of 50% or more of the sheet, the breaking strength of the entire resin sheet is reduced or a low linear expansion coefficient is obtained. It becomes difficult to maintain.

In the resin sheet of the present invention, preferably, the average linear expansion from a temperature lower by 50 ° C. than the glass transition temperature (hereinafter also referred to as Tg) of the resin composition to a temperature lower by 10 ° C. than the glass transition temperature of the resin composition. The rate (α1) is 5.0 × 10 ⁻⁵ [° C. ⁻¹ ] or less. By being 5.0 × 10 ⁻⁵ [° C. ⁻¹ ] or less, the resin sheet of the present invention has a small dimensional change at the time of cooling during heating and cooling during a heat cycle test, etc. There is little risk of warping or peeling due to the difference in shrinkage rate when bonded. The average linear expansion coefficient is more preferably 4.5 × 10 ⁻⁵ [° C. ⁻¹ ] or less, more preferably 4.0 × 10 ⁻⁵ [° C. ⁻¹ ] or less. The average linear expansion coefficient can be measured by a method according to JIS K7197. For example, a test of about 3 mm × 15 mm using a TMA (Thermal Mechanical Analysis) apparatus (manufactured by Seiko Denshi, TMA / SS120C). It can be determined by heating the piece at a heating rate of 5 ° C./min.

In the resin sheet of the present invention, the average linear expansion coefficient (α2) from a temperature 10 ° C. higher than the Tg of the resin composition to a temperature 50 ° C. higher than the Tg of the resin composition is preferably 1.2 × 10 ^−4. [° C ^-1 ] or less. By being 1.2 × 10 ⁻⁴ [° C. ⁻¹ ] or less, in the present invention, when heat treatment is performed at Tg or more, a dimensional change during heating is small during cooling such as a cooling cycle test, and a copper foil or the like. There is little warping or peeling due to the difference in shrinkage when bonded. More preferably, it is 9 × 10 ⁻⁵ [° C. ⁻¹ ] or less, more preferably 7.0 × 10 ⁻⁵ [° C. ⁻¹ ] or less.

In the resin sheet of the present invention, the portion where the tensile modulus after curing is 2.0 GPa or less has a thickness ranging from 20% to 70% from at least one surface, and the tensile modulus after curing from both surfaces is 2 When there is a portion that is 0.0 GPa or less, the total is 70% or less. Any method may be used as long as this mechanical property is expressed. For example, a multilayer extrusion method in which a resin is fed from a plurality of extruders to one mold, or a single coating die. In addition, in the multilayer coating method in which a plurality of coating liquids are supplied and applied, the method of extruding and laminating a resin into a resin thin film sheet that has been created once, the sequential coating method in which coating is performed again on a resin thin film sheet that has been once created, etc. And a method of using a low elastic modulus component together with a low linear expansion coefficient component.
The part where the tensile modulus after curing from the at least one surface to a thickness of 20 to 50% is 2.0 GPa or less, that is, the low modulus part can be designed by devising the structure of the resin. In addition, it can also be configured by controlling the amount of additive such as layered silicate added to the resin.
Preferably, the addition amount of the layered silicate is 15 parts by weight or less with respect to 100 parts by weight of the thermosetting resin and / or the photocurable resin. More preferably, it is 10 parts by weight or less. If it is 15 parts by weight or more, it becomes quite difficult to control the elastic modulus to 1.0 GPa.

When designing the low elastic component with a resin structure, a flexible epoxy resin is used.
The epoxy thermosetting resin composition near the surface having a tensile modulus after curing of 2.0 GPa or less according to the present invention is composed of a flexible epoxy resin, a thermosetting resin curing agent, and a layered silicate. It is preferable that Here, the layered silicate is dispersed in a matrix made of a flexible epoxy resin and a thermosetting resin curing agent.
Since the flexible epoxy resin is used in the resin composition according to the present invention, the epoxy thermosetting resin composition and the cured product thereof have sufficient flexibility. Therefore, high elongation is expressed over a wide temperature range from a low temperature range to a high temperature range. That is, after the resin sheet comprising the thermosetting resin composition according to the present invention is cured, the elongation at room temperature is 3% or more, preferably 5% or more, and more preferably 7% or more.

The flexible epoxy resin is not particularly limited as long as it can exhibit flexibility even after being cured with a thermosetting resin curing agent. Examples of flexible epoxy resins that can be used include diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, polyoxyalkylene glycols and polytetrakis containing alkylene groups having 2 to 9 carbon atoms (preferably 2 to 4 carbon atoms). Mainly a copolymer of a long-chain polyol polyglycidyl ether or glycidyl (meth) acrylate containing methylene ether glycol, etc., and a radical polymerizable monomer such as ethylene, vinyl acetate or (meth) acrylic acid ester, or a conjugated diene compound. Polyester having one or more, preferably two or more epoxy groups per molecule, obtained by epoxidizing unsaturated carbon double bonds in the (co) polymer of the (co) polymer or partially hydrogenated product thereof Resin, urethane bond and polycaprolactone bond In the molecule of rubber component such as urethane modified epoxy resin, polycaprolactone modified epoxy resin, dimer acid modified epoxy resin in which epoxy group is introduced into the molecule, NBR, CTBN, polybutadiene, acrylic rubber, etc. Rubber modified epoxy resin having an epoxy group introduced therein.
Examples of the flexible epoxy resin preferably used include compounds having an epoxy group and a butadiene structure in the molecule.
More preferably, the flexible epoxy resin is a dimer acid-modified epoxy resin in which an epoxy group is introduced into the molecule of dimer acid or a derivative thereof, or an epoxy in the molecule of a rubber component such as NBR, CTBN, polybutadiene, or acrylic rubber. A rubber-modified epoxy resin having a group introduced therein is used.

式（Ａ）中、Ｒは、−ＣＨ₂−ＣＨ＝ＣＨ−ＣＨ₂−または−ＣＨ₂−ＣＨ（ＣＨ＝ＣＨ₂）−であり、
Ａは、−φ−Ｃ（ＣＨ₃）₂−φ−Ｏ−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｏ−（Ｃ＝０）− （φはベンゼン環）であり、
Ｂは、−（Ｃ＝Ｏ）−Ｏ−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｏ−φ−Ｃ（ＣＨ₃）₂−φ− （φはベンゼン環）であり、ｍは０または１、ｎは正の整数である。
式（Ａ）中のポリブタジエン成分が少ない場合には、電気的特性が良好となる。具体的には、低誘電率かつ低誘電正接を実現することができる。ポリブタジエン単位の好ましい数ｎは１００以下であり、より好ましくは４０以下である。 In the present invention, more preferably, a flexible epoxy resin represented by the following general formula (A) is used.

In the formula (A), R is —CH ₂ —CH═CH—CH ₂ — or —CH ₂ —CH (CH═CH ₂ ) —,
A _{is, -φ-C (CH 3)} 2 -φ-O-CH 2 -CH (OH) -CH 2 -O- (C = 0) - (φ is a benzene ring), and
B is — (C═O) —O—CH ₂ —CH (OH) —CH ₂ —O—φ—C (CH ₃ ) ₂ —φ— (φ is a benzene ring), and m is 0 or 1 , N is a positive integer.
When the polybutadiene component in the formula (A) is small, the electrical characteristics are good. Specifically, a low dielectric constant and a low dielectric loss tangent can be realized. The preferred number n of polybutadiene units is 100 or less, more preferably 40 or less.

  The resin sheet of the present invention has the above-described excellent high-temperature properties, and contains a thermosetting resin and / or a photocurable resin and a layered silicate. The thermosetting resin or photocurable resin is a liquid, semi-solid or solid at room temperature, and a relatively low molecular weight substance exhibiting fluidity at room temperature or under heating, a curing agent, a catalyst, It means a resin that can be an insoluble and infusible resin that forms a network-like three-dimensional structure while causing a chemical reaction such as a curing reaction or a crosslinking reaction by the action of heat or light to increase the molecular weight.

  Examples of the thermosetting resin include epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, silicon resin, benzoxazine resin, melamine resin, urea resin, allyl resin, phenol resin, unsaturated polyester resin. , Bismaleimide triazine resin, alkyd resin, furan resin, polyurethane resin, aniline resin and the like. Among these, epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicon resins, benzoxazine resins, melamine resins, and the like are preferable. These thermosetting resins may be used alone or in combination of two or more.

  The epoxy resin refers to an organic compound having at least one epoxy group. The number of epoxy groups in the epoxy resin is preferably 1 or more per molecule, and more preferably 2 or more per molecule. Here, the number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy resin by the total number of molecules in the epoxy resin.

  A conventionally well-known epoxy resin can be used as said epoxy resin, For example, the epoxy resin (1)-epoxy resin (11) shown below etc. are mentioned. These epoxy resins may be used independently and 2 or more types may be used together.

  Examples of the epoxy resin (1) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin; phenol novolac type epoxy resin, cresol novolak type Examples thereof include novolak-type epoxy resins such as epoxy resins; aromatic epoxy resins such as trisphenolmethane triglycidyl ether, and hydrogenated products and brominated products thereof.

  Examples of the epoxy resin (2) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexane. Carboxylate, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxy And cycloaliphatic epoxy resins such as cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane and bis (2,3-epoxycyclopentyl) ether. As what is marketed among this epoxy resin (2), the brand name "EHPE-3150" (softening temperature 71 degreeC) by Daicel Chemical Industries, etc. are mentioned, for example.

  Examples of the epoxy resin (3) include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol. Diglycidyl ether, diglycidyl ether of polypropylene glycol, polyglycidyl ether of long-chain polyol containing polyoxyalkylene glycol or polytetramethylene ether glycol containing an alkylene group having 2 to 9 (preferably 2 to 4) carbon atoms, etc. Aliphatic epoxy resins and the like.

  Examples of the epoxy resin (4) include phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, glycidyl ether-glycidyl ester of salicylic acid, and dimer acid. Examples thereof include glycidyl ester type epoxy resins such as glycidyl ester and hydrogenated products thereof.

  Examples of the epoxy resin (5) include triglycidyl isocyanurate, N, N′-diglycidyl derivative of cyclic alkylene urea, N, N, O-triglycidyl derivative of p-aminophenol, N of m-aminophenol, Examples thereof include glycidylamine type epoxy resins such as N, O-triglycidyl derivatives and hydrogenated products thereof.

  Examples of the epoxy resin (6) include a copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer such as ethylene, vinyl acetate, and (meth) acrylic acid ester.

  Examples of the epoxy resin (7) include those obtained by epoxidizing unsaturated carbon double bonds in polymers mainly composed of conjugated diene compounds such as epoxidized polybutadiene or partially hydrogenated polymers thereof. It is done.

  Examples of the epoxy resin (8) include a polymer block mainly composed of a vinyl aromatic compound such as epoxidized SBS, a polymer block mainly composed of a conjugated diene compound, or a partially hydrogenated product thereof. Examples thereof include those obtained by epoxidizing an unsaturated carbon double bond of a conjugated diene compound in a block copolymer having a combined block in the same molecule.

  Examples of the epoxy resin (9) include a polyester resin having one or more, preferably two or more epoxy groups per molecule.

  Examples of the epoxy resin (10) include urethane-modified epoxy resins and polycaprolactone-modified epoxy resins in which urethane bonds and polycaprolactone bonds are introduced into the structures of the epoxy resins (1) to (9).

  Examples of the epoxy resin (11) include rubber-modified epoxy resins in which the epoxy resins (1) to (10) contain a rubber component such as NBR, CTBN, polybutadiene, or acrylic rubber. In addition to the epoxy resin, a resin or oligomer having at least one oxirane ring may be added.

  The curing agent used for the curing reaction of the epoxy resin is not particularly limited, and conventionally known curing agents for epoxy resins can be used. For example, amine compounds, compounds such as polyaminoamide compounds synthesized from amine compounds, A tertiary amine compound, an imidazole compound, a hydrazide compound, a melamine compound, an acid anhydride, a phenol compound, a thermal latent cationic polymerization catalyst, a photolatent cationic polymerization initiator, dicyanamide, and derivatives thereof are exemplified. These hardening | curing agents may be used independently and 2 or more types may be used together.

  The amine compound is not particularly limited, and examples thereof include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, and derivatives thereof; Foronediamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8, Cycloaliphatic amines such as 10-tetraoxaspiro (5,5) undecane and derivatives thereof; m-xylenediamine, α- (m / paminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, dia Roh diphenyl sulfone, alpha, alpha-bis (4-aminophenyl)-p-like aromatic amines and derivatives thereof diisopropylbenzene and the like.

  The compound synthesized from the amine compound is not particularly limited. For example, the amine compound and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid, tetrahydroisophthalic acid. Polyaminoamide compounds synthesized from carboxylic acid compounds such as acids and hexahydroisophthalic acid and derivatives thereof; Polyaminoimide compounds synthesized from maleimide compounds such as the above amine compounds and diaminodiphenylmethane bismaleimide; and derivatives thereof Ketimine compounds synthesized from compounds and ketone compounds and derivatives thereof; polyamines synthesized from the above amine compounds and compounds such as epoxy compounds, urea, thiourea, aldehyde compounds, phenol compounds, acrylic compounds, etc. Compounds and derivatives thereof.

  The tertiary amine compound is not particularly limited. For example, N, N-dimethylpiperazine, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) Examples thereof include phenol, 1,8-diazabiscyclo (5,4,0) undecene-1 and derivatives thereof.

  The imidazole compound is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and derivatives thereof.

  The hydrazide compound is not particularly limited, and examples thereof include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, eicosanedioic acid dihydrazide, Examples include adipic acid dihydrazide and its derivatives.

  The melamine compound is not particularly limited, and examples thereof include 2,4-diamino-6-vinyl-1,3,5-triazine and derivatives thereof.

  The acid anhydride is not particularly limited. For example, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol trisanhydro Trimellitate, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, polyazeline acid anhydride, polydodecane Dianhydride, Rorendo anhydride and derivatives thereof.

  The phenol compound is not particularly limited, and examples thereof include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, and derivatives thereof.

  The thermal latent cationic polymerization catalyst is not particularly limited. For example, benzylsulfonium salt, benzylammonium salt, benzylpyridinium salt, benzyl having antimony hexafluoride, phosphorous hexafluoride, boron tetrafluoride and the like as a counter anion. Examples include ionic thermal latent cationic polymerization catalysts such as phosphonium salts; nonionic thermal latent cationic polymerization catalysts such as N-benzylphthalimide and aromatic sulfonic acid esters.

  The photolatent cationic polymerization initiator is not particularly limited. For example, aromatic diazonium salts, aromatic halonium salts, and aromatics having antimony hexafluoride, phosphorous hexafluoride, boron tetrafluoride and the like as counter anions. Ionic photolatent cationic polymerization initiators such as onium salts such as sulfonium salts, and organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes; nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid Nonionic photolatent cationic polymerization initiators such as esters, phenol sulfonates, diazonaphthoquinones, N-hydroxyimide sulfonates, etc. may be mentioned.

  Examples of the thermosetting modified polyphenylene ether resin include resins obtained by modifying the polyphenylene ether resin with a functional group having thermosetting properties such as a glycidyl group, an isocyanate group, and an amino group. These thermosetting modified polyphenylene ether resins may be used alone or in combination of two or more.

  The thermosetting polyimide resin is a resin having an imide bond in the molecular main chain. Specifically, for example, a condensation polymer of aromatic diamine and aromatic tetracarboxylic acid, aromatic diamine and bismaleimide And bismaleimide resin which is an addition polymer of aminobenzoic acid hydrazide and bismaleimide, and bismaleimide triazine resin composed of a dicyanate compound and a bismaleimide resin. Of these, bismaleimide triazine resin is preferably used. These thermosetting polyimide resins may be used alone or in combination of two or more.

  Examples of the silicon resin include those containing a silicon-silicon bond, a silicon-carbon bond, a siloxane bond, or a silicon-nitrogen bond in the molecular chain. Specific examples include polysiloxane, polycarbosilane, and polysilazane. Can be mentioned.

  The benzoxazine resin is obtained by ring-opening polymerization of an oxazine ring of a benzoxazine monomer. The benzoxazine monomer is not particularly limited, and examples thereof include those in which a functional group such as a phenyl group, a methyl group, or a cyclohexyl group is bonded to nitrogen of the oxazine ring.

  The urea resin is a thermosetting resin obtained by addition condensation reaction of urea and formaldehyde. The curing agent used for the curing reaction of the urea resin is not particularly limited. For example, an apparent curing agent composed of an acidic salt such as an inorganic acid, an organic acid, or acidic sodium sulfate; a carboxylic acid ester, an acid anhydride, or a chloride. Examples include latent curing agents such as salts of ammonium and ammonium phosphate. Among these, a latent curing agent is preferable from the viewpoint of shelf life.

  The allyl resin is obtained by polymerization and curing reaction of diallyl phthalate monomer. Examples of the diallyl phthalate monomer include an ortho isomer, an iso isomer, and a tele isomer. Although it does not specifically limit as a catalyst of hardening reaction, For example, combined use of t-butyl perbenzoate and di-t-butyl peroxide is suitable.

  The resin sheet of this invention can add polyvinyl acetal resin and rubber | gum as an additive compound suitably. Rubbers that can be used as the additive compound are not particularly limited, and examples thereof include styrene elastomers, olefin elastomers, urethane elastomers, and polyester elastomers. In order to enhance the compatibility with the resin, these thermoplastic elastomers may be functional group-modified. These thermoplastic elastomers may be used alone or in combination of two or more.

  The crosslinked rubber is not particularly limited, and examples thereof include isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, and urethane rubber. In order to enhance the compatibility with the resin, it is preferable that these crosslinked rubbers are functional group-modified. The functional group-modified crosslinked rubber is not particularly limited, and examples thereof include epoxy-modified butadiene rubber and epoxy-modified nitrile rubber. These crosslinked rubbers may be used alone or in combination of two or more.

  The resin sheet of the present invention contains layered silicate as an essential component. The layered silicate means a layered silicate mineral having an exchangeable metal cation between layers, and may be a natural product or a synthetic product.

  Examples of the layered silicate include smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite and nontronite, swelling mica, vermiculite, and halloysite. Among these, at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite is preferably used. These layered silicates may be used alone or in combination of two or more.

The upper limit of the average length of the layered silicate is 2 μm, the preferred upper limit is 1 μm, and the more preferred upper limit is 0.5 μm. When the average length is 2 μm or less, the transparency is improved, and alignment with the lower substrate or the like can be facilitated during the operation. When the average length is 1 μm or less, residues are hardly left during laser processing, and laser processability is improved. When the average length is 0.5 μm or less, it can be used as an optical material or a material for an optical waveguide.
The other crystal shapes are not particularly limited, but the preferable lower limit of the average length is 0.01 μm, the preferable lower limit of the thickness is 0.001 μm, the upper limit is 1 μm, the preferable lower limit of the aspect ratio is 20, and the upper limit is 500, A more preferable lower limit of the average length is 0.05 μm, a more preferable lower limit of the thickness is 0.001 μm, an upper limit is 0.5 μm, a more preferable lower limit of the aspect ratio is 50, and an upper limit is 200.
In the layered silicate, the ratio of the layered silicate having a major axis exceeding 2 μm is preferably 20% or less. More preferably, the ratio of the layered silicate exceeding 1 μm is 20% or less, and more preferably the ratio of the layered silicate exceeding 0.5 μm is 20% or less. The maximum length of the layered silicate is preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 100 μm or less. When the ratio of the layered silicate exceeding 2 μm is 20% or less and the maximum length is 500 μm or less, the transparency is improved, and alignment with the lower substrate or the like can be facilitated during the operation, Residues hardly remain during laser processing, and laser processability is improved. That is, when a substrate made of the resin composition of the present invention is perforated by a laser such as a carbon dioxide laser, the resin component and the layered silicate component are simultaneously decomposed and evaporated, and the target size is obtained by low energy laser processing. Can be drilled. Compared to the case of a resin composition using a normal inorganic filler, the number of shots for laser processing can be reduced. Moreover, the residue which consists of a resin composition which remains partially becomes only a small thing of several micrometers or less, and can be easily removed by desmear processing. Thereby, it is possible to prevent the occurrence of defective plating due to the residue generated by the drilling process.

  The layered silicate preferably has a large shape anisotropy effect defined by the following formula (1). By using a layered silicate having a large shape anisotropy effect, the resin sheet of the present invention has excellent mechanical properties.

  Shape anisotropy effect = surface area of laminated surface of flaky crystals / surface area of laminated surface of flaky crystals (1)

  The exchangeable metal cation existing between the layers of the layered silicate means a metal ion such as sodium or calcium existing on the surface of the lamellar crystal of the layered silicate, and these metal ions are cations with the cationic substance. Since it has exchangeability, various substances having cationic properties can be inserted (intercalated) between the crystal layers of the layered silicate.

  Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, A preferable minimum is 50 milliequivalent / 100g, and an upper limit is 200 milliequivalent / 100g. When the amount is less than 50 milliequivalents / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate is reduced by cation exchange, so that the crystal layers are not sufficiently depolarized (hydrophobized). Sometimes. When it exceeds 200 milliequivalents / 100 g, the bonding force between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off.

As the layered silicate, those having improved dispersibility in the resin by chemical treatment are preferable. Hereinafter, such a layered silicate is also referred to as an organic layered silicate.
As said chemical treatment, it can implement by the chemical modification (1) method-chemical modification (6) method shown below, for example. These chemical modification methods may be used alone or in combination of two or more.

  The chemical modification (1) method is also called a cation exchange method using a cationic surfactant. Specifically, when the resin sheet of the present invention is obtained using a low-polarity resin, the layer of the layered silicate is previously made cationic. In this method, cation exchange is performed with a surfactant to make it hydrophobic. By making the layers of the layered silicate hydrophobic in advance, the affinity between the layered silicate and the low polarity resin is increased, and the layered silicate can be finely dispersed in the low polarity resin more uniformly.

  The cationic surfactant is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts. Especially, since the crystal | crystallization layer of layered silicate can fully be hydrophobized, a C6 or more alkyl ammonium ion salt, aromatic quaternary ammonium ion salt, or heterocyclic quaternary ammonium ion salt is used suitably.

  The quaternary ammonium salt is not particularly limited, and examples thereof include trimethyl alkyl ammonium salt, triethyl alkyl ammonium salt, tributyl alkyl ammonium salt, dimethyl dialkyl ammonium salt, dibutyl dialkyl ammonium salt, methyl benzyl dialkyl ammonium salt, and dibenzyl dialkyl ammonium salt. , Trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt; benzylmethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride A quaternary ammonium salt having an aromatic ring such as: a quaternary ammonium salt derived from an aromatic amine such as trimethylphenylammonium; an alkylpyridinium salt, an imidazoli A quaternary ammonium salt having a heterocyclic ring such as a dimethyl salt; a dialkyl quaternary ammonium salt having two polyethylene glycol chains, a dialkyl quaternary ammonium salt having two polypropylene glycol chains, and a trialkyl quaternary having one polyethylene glycol chain Examples include ammonium salts and trialkyl quaternary ammonium salts having one polypropylene glycol chain. Among them, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N N-dimethylammonium salt and the like are preferred. These quaternary ammonium salts may be used alone or in combination of two or more.

  The quaternary phosphonium salt is not particularly limited. For example, dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylmethylphosphonium salt, distearyldimethylphosphonium salt, distearyl And dibenzylphosphonium salts. These quaternary phosphonium salts may be used alone or in combination of two or more.

  In the chemical modification (2) method, a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method has a chemical affinity with a functional group or a hydroxyl group capable of chemically bonding to the hydroxyl group. This is a method of chemical treatment with a compound having at least one functional group having a large molecular weight at the molecular end.

The functional group capable of chemically bonding to the hydroxyl group or the functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, a carboxyl group (including dibasic acid anhydrides), A hydroxyl group, an isocyanate group, an aldehyde group, etc. are mentioned.
The compound having a functional group capable of chemically bonding to the hydroxyl group or the compound having a functional group having a large chemical affinity with the hydroxyl group is not particularly limited. For example, a silane compound, titanate compound, or glycidyl compound having the functional group. , Carboxylic acids, alcohols and the like. These compounds may be used independently and 2 or more types may be used together.

  The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-amino. Propyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltri Ethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ- Minopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri An ethoxysilane etc. are mentioned. These silane compounds may be used independently and 2 or more types may be used together.

  In the chemical modification (3) method, the hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method has a functional group capable of chemically bonding to the hydroxyl group or a chemical affinity with the hydroxyl group. This is a chemical treatment method using a large functional group and a compound having at least one reactive functional group at the molecular end.

  The chemical modification (4) method is a method in which the crystal surface of the organically modified layered silicate chemically treated by the chemical modification (1) method is chemically treated with a compound having an anionic surface activity.

  The compound having an anionic surface activity is not particularly limited as long as the layered silicate can be chemically treated by ionic interaction. For example, sodium laurate, sodium stearate, sodium oleate, higher alcohol sulfate ester salt , Secondary higher alcohol sulfates, unsaturated alcohol sulfates and the like. These compounds may be used independently and 2 or more types may be used together.

  The chemical modification (5) method is a method of chemically treating a compound having one or more reactive functional groups in addition to the anion site in the molecular chain among the compounds having anionic surface activity.

  In the chemical modification (6) method, an organically modified layered silicate chemically treated by any one of the chemical modification (1) method to the chemical modification (5) method is further used, for example, maleic anhydride-modified polyphenylene ether resin. This is a method using a resin having a functional group capable of reacting with the layered silicate.

  In the resin sheet of the present invention, the layered silicate has an average interlayer distance of (001) plane measured by wide-angle X-ray diffraction measurement method of 3 nm or more, and part or all of the laminates are 5 layers or less. It is preferable to be dispersed so that The interfacial area between the resin and the layered silicate is sufficiently large because the layered silicate is dispersed such that the average interlayer distance is 3 nm or more and a part or all of the laminate is 5 layers or less. It is large and the distance between the flaky crystals of the layered silicate becomes moderate, and the improvement effect by dispersion can be sufficiently obtained in high temperature physical properties, mechanical physical properties, heat resistance, dimensional stability, laser workability, etc. .

A preferable upper limit of the average interlayer distance is 5 nm. If it exceeds 5 nm, the lamellar silicate crystal flakes are separated into layers and the interaction becomes so weak that the interaction is negligible. Therefore, the binding strength at high temperatures becomes weak, and sufficient dimensional stability may not be obtained.
In the present specification, the average interlayer distance of the layered silicate means the average distance between layers when the flaky crystal of the layered silicate is regarded as a layer, and X-ray diffraction peak and transmission electron microscope photography That is, it can be calculated by a wide-angle X-ray diffraction measurement method.

Specifically, the layered silicate is dispersed so that the part or all of the laminate is 5 layers or less. Specifically, the interaction between the flaky crystals of the layered silicate is weakened and the flaky crystals This means that a part or all of the laminate is dispersed. Preferably, 10% or more of the layered silicate laminate is dispersed in 5 layers or less, and 20% or more of the layered silicate laminate is dispersed in 5 layers or less.
In addition, the ratio of the layered silicate dispersed as a laminate of 5 layers or less is a layered silicic acid that can be observed in a fixed area by observing the resin composition at a magnification of 50,000 to 100,000 times with a transmission electron microscope. It can be calculated from the following formula (2) by measuring the total number of layers X of the salt laminate and the number of layers Y of the laminate dispersed as a laminate of 5 layers or less.

  Ratio of layered silicate dispersed as a laminate of 5 layers or less (%) = (Y / X) × 100 (2)

  The number of layers in the layered silicate laminate is preferably 5 layers or less, more preferably 3 layers or less, and even more preferably 1 layer in order to obtain the effect of dispersion of the layered silicate. is there.

  In the present invention, the layered silicate is used as the inorganic compound, the average interlayer distance of the (001) plane measured by wide angle X-ray diffraction measurement is 3 nm or more, and a part or all of the laminates are 5 layers or less. When the layered silicate is dispersed, the interface area between the resin and the layered silicate is sufficiently increased, the interaction between the resin and the surface of the layered silicate is increased, and the melt viscosity is increased. In addition to improved thermoformability such as heat press, it is easy to retain shaped shapes such as embossing and embossing, and mechanical properties such as elastic modulus improve in a wide temperature range from room temperature to high temperature, The mechanical properties can be maintained even at a high temperature equal to or higher than the Tg or melting point of the resin, and the linear expansion coefficient at a high temperature can be kept low. The reason for this is not clear, but it is considered that even in the temperature range above Tg or the melting point, these physical properties are manifested because the finely dispersed layered silicate acts as a kind of pseudo-crosslinking point. On the other hand, since the distance between the lamellar crystals of the layered silicate is also appropriate, the lamellar crystals of the lamellar silicate move during combustion, and it becomes easy to form a sintered body that becomes a flame retardant coating. Since this sintered body is formed at an early stage during combustion, not only the supply of oxygen from the outside world but also the flammable gas generated by the combustion can be blocked, and the resin sheet of the present invention Exhibits excellent flame retardancy.

  Further, in the resin sheet of the present invention, since the layered silicate is finely dispersed at a nanometer size and there is no post-mineralization product of several microns size, a carbon dioxide laser or the like is applied to the substrate made of the resin sheet of the present invention. When the drilling process is performed with the laser, the resin component and the layered silicate component are simultaneously decomposed and evaporated, and a hole having a desired size can be formed by laser processing with low energy. Compared to the case of a resin composition using a normal inorganic filler, the number of shots for laser processing can be reduced. Moreover, the residue which consists of a resin composition which remains partially is only a small thing of several micrometers or less, and can be easily removed by desmear processing. Thereby, it is possible to prevent the occurrence of defective plating due to the residue generated by the drilling process.

  The method for dispersing the layered silicate in the resin is not particularly limited, for example, a method using an organically modified layered silicate, a method of foaming the resin with a foaming agent after mixing the resin and the layered silicate by a conventional method, Examples thereof include a method using a dispersant and a method of mixing a layered silicate with a resin or monomer in a state where the layered silicate is dispersed in a solvent. By using these dispersion methods, the layered silicate can be more uniformly and finely dispersed in the resin.

  In the method in which the resin and the layered silicate are mixed by a conventional method and the resin is foamed with a foaming agent, the energy of foaming is used for the dispersion of the layered silicate. It does not specifically limit as said foaming agent, For example, a gaseous foaming agent, an easily volatile liquid foaming agent, a heat decomposable solid foaming agent etc. are mentioned. These foaming agents may be used independently and 2 or more types may be used together.

  The method of foaming the resin with a foaming agent after mixing the resin and the layered silicate by a conventional method is not particularly limited. For example, a gaseous foaming agent is added to a resin composition comprising the resin and the layered silicate under high pressure. A method in which the gaseous foaming agent is vaporized in the resin composition to form a foam after impregnation with the above-mentioned method; a thermally decomposable foaming agent is previously contained between the layers of the layered silicate, and the thermally decomposable foaming agent And a method of decomposing the foam by heating to form a foam.

  The lower limit of the layered silicate with respect to 100 parts by weight of the thermosetting resin and / or the photocurable resin is 0.1 parts by weight, and the upper limit is 100 parts by weight. If it is less than 0.1 parts by weight, the effect of improving high-temperature properties and hygroscopicity is reduced. When it exceeds 100 parts by weight, the density (specific gravity) of the resin sheet of the present invention is increased, and the mechanical strength is also lowered, so that the practicality is poor. The preferred lower limit is 3 parts by weight and the upper limit is 80 parts by weight. If it is less than 3 parts by weight, the thermal expansion coefficient (α1) of Tg or less can be reduced to some extent, but it becomes difficult to reduce the thermal expansion coefficient (α2) of Tg or more, and the resin sheet of the present invention is thinned. In some cases, sufficient improvement of high temperature properties may not be obtained. Further, the water absorption cannot be improved. If it exceeds 80 parts by weight, the moldability may deteriorate. A more preferred lower limit is 5 parts by weight and an upper limit is 70 parts by weight. When the amount is from 5 to 70 parts by weight, there is no problem in terms of process suitability such as mechanical properties and laser processability, and sufficient high-temperature properties, transparency, flame retardancy, gas barrier properties, and low water absorption are obtained.

  The resin sheet of the present invention has thermoplastic elastomers, cross-linked rubbers, oligomers, nucleating agents, antioxidants as necessary for the purpose of modifying the properties within the range that does not hinder the achievement of the present invention. Additives (anti-aging agents), heat stabilizers, light stabilizers, UV absorbers, lubricants, flame retardant aids, antistatic agents, antifogging agents, fillers, softeners, plasticizers, colorants, etc. You may mix | blend. These may be used alone or in combination of two or more.

  It does not specifically limit as a method to manufacture the resin sheet of this invention, For example, each predetermined amount of resin and an inorganic compound and each predetermined amount of 1 type, or 2 or more types of additives mix | blended as needed are normal temperature Direct kneading method of directly blending and kneading under heating or heating, and a method of removing the solvent after mixing in a solvent; a predetermined amount or more of an inorganic compound is blended in advance with the resin or a resin other than the resin A master batch kneaded in advance is prepared, and the master batch, the remainder of the predetermined amount of the resin, and each predetermined amount of one or two or more additives blended as necessary are at room temperature or under heating. And a master batch method of kneading or mixing in a solvent.

  In the master batch method, a master batch in which an inorganic compound is blended with the resin or a resin other than the resin, and a master batch dilution resin containing the resin used when the master batch is diluted to a predetermined inorganic compound concentration The compositions may be the same composition or different compositions.

  Although it does not specifically limit as said masterbatch, For example, at least 1 sort (s) of resin selected from the group which consists of a polyamide resin, polyphenylene ether resin, polyether sulfone resin, and polyester resin with which dispersion | distribution of an inorganic compound is easy, for example It is preferable to contain. Although it does not specifically limit as said resin composition for masterbatch dilution, For example, it is preferable to contain the at least 1 sort (s) of resin selected from the group which consists of a thermosetting polyimide resin excellent in the high temperature physical property, and an epoxy resin.

  Although the compounding quantity of the inorganic compound in the said masterbatch is not specifically limited, The preferable minimum with respect to 100 weight part of resin is 1 weight part, and an upper limit is 500 weight part. When the amount is less than 1 part by weight, the convenience as a master batch that can be diluted to an arbitrary concentration is reduced. If it exceeds 500 parts by weight, the dispersibility in the master batch itself, and particularly the dispersibility of the inorganic compound when diluted to a predetermined blending amount by the master batch dilution resin composition may deteriorate. A more preferred lower limit is 5 parts by weight and an upper limit is 300 parts by weight.

  Further, for example, by using an inorganic compound containing a polymerization catalyst (polymerization initiator) such as a transition metal complex, a thermoplastic resin monomer and an inorganic compound are kneaded, and the above monomer is polymerized, thereby thermoplastic resin. You may use the method of performing simultaneously superposition | polymerization and manufacture of a resin composition collectively.

The method for kneading the mixture in the method for producing a resin sheet of the present invention is not particularly limited, and examples thereof include a method for kneading using a kneader such as an extruder, two rolls, and a Banbury mixer.
By applying a shearing force, the average length of the layered silicate may be shortened.

The resin sheet of the present invention is a combination of a resin and a layered silicate and has a low linear expansion coefficient at high temperature due to an increase in Tg and heat-resistant deformation temperature due to molecular chain restraint. Excellent mechanical properties and transparency.
Furthermore, gas molecules are much easier to diffuse in the resin than inorganic compounds, and when diffusing in the resin, the gas molecules diffuse while bypassing the inorganic compound, so the gas barrier properties are also improved. Similarly, barrier properties against other than gas molecules are improved, and solvent resistance, hygroscopicity, water absorption and the like are improved. Thereby, for example, copper migration from a copper circuit in a multilayer printed wiring board can be suppressed. Furthermore, it is possible to suppress the occurrence of defects such as defective plating due to bleed-out of trace additives in the resin on the surface.

  Although it does not specifically limit as a use of the resin sheet of this invention, For example, a core layer, a buildup layer, etc. of a multilayer board | substrate are formed by melt | dissolving in a suitable solvent or shape | molding and processing it into a film form. It is suitably used for substrate materials, sheets, laminates, resin-coated copper foils, copper-clad laminates, TAB films, printed boards, prepregs, varnishes, optical waveguide materials, and the like. Such a substrate material using the resin sheet of the present invention is also one aspect of the present invention.

  The molding method is not particularly limited. For example, an extrusion molding method in which an extruder is melted and kneaded and then extruded and formed into a film using a T die or a circular die; dissolved in a solvent such as an organic solvent or There is a casting molding method in which, after being dispersed, casting is performed to form a film. Of these, the extrusion molding method and the casting molding method are suitable for reducing the thickness of the multilayer substrate.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Example 1)
100 parts by weight of an epoxy resin composition consisting of 50 parts by weight of a bisphenol A type epoxy resin (D.R. 331L manufactured by Dow Chemical Japan Co., Ltd.) and 50 parts by weight of a solid epoxy resin (manufactured by Toto Kasei Co., Ltd., YP55), dicyan azide ( Adeka Co., Adeka Hardener EH-3636) 3.5 parts by weight, modified imidazole (Adeca Co., Adeka Hardener EH-3366) 1.5 parts by weight, synthetic octet treated with trioctylmethylammonium salt After adding 5 parts by weight of light (layered silicate; manufactured by Corp Chemical Co., Lucentite STN) and 200 parts by weight of dimethylformamide (made by Wako Pure Chemicals, special grade) as an organic solvent to a beaker, the mixture was stirred for 1 hour with a stirrer. , Defoamed to obtain a resin composition solution A bisphenol A type epoxy resin (Dainippon Ink & Chemicals, Inc.) Epoxy resin comprising 64.4 parts by weight of Ebiclone 850, epoxy equivalent: 190), 35.6 parts by weight of phenolic compound (Dainippon Ink Chemical Co., Ltd., Phenolite TD-2090, hydroxyl equivalent: 105) To 100 parts by weight of the composition, 1.1 parts by weight of 2-ethyl-4-methylimidazole [manufactured by Shikoku Kasei Kogyo Co., Ltd.] is used as a curing accelerator, and the organic compound is treated with trioctylmethylammonium salt as an inorganic compound. 40 parts by weight of synthetic hectorite (layered silicate; manufactured by Corp Chemical Co., Lucentite STN) and 480 parts by weight of dimethylformamide (made by Wako Pure Chemicals, special grade) as an organic solvent were added to a beaker, and 1 After stirring for a period of time, defoaming was performed to obtain a resin composition solution B.
The solvent was removed in a state where the obtained resin composition solution A was applied on a polyethylene terephthalate sheet to form a film having a thickness of 25 microns. (1a)
Similarly, the solvent was removed while the resin composition solution B was coated on a polyethylene terephthalate sheet to form a film having a thickness of 50 microns. (1b)
Subsequently, the obtained two kinds of films were laminated in the order of 1a, 1b, and 1a, and heat-laminated using a hot rubber laminator heated to 100 ° C. to prepare a three-layer film having a thickness of 100 microns. (1c)
The film was heated at 110 ° C. for 3 hours, and further cured by heating at 170 ° C. for 30 minutes to produce a 100 μm plate-like molded body.

(Example 2)
Epoxy-modified polybutadiene resin (manufactured by Nippon Soda Co., Ltd., product number: “EPB-13”, epoxy equivalent 598) 58.3 parts by weight, phenol compound (manufactured by Nippon Petrochemical Co., Ltd., PP-1000-240, hydroxyl group equivalent: 420) 41 Synthetic hectorite (layered silicate; manufactured by Corp Chemical Co., Lucentite STN) 8 obtained by subjecting 100 parts by weight of an epoxy resin composition comprising 7 parts by weight to an organic compound with trioctylmethylammonium salt as an inorganic compound 8 400 parts by weight of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., special grade) as an organic solvent was added to a beaker and stirred for 1 hour with a stirrer, and then defoamed to obtain a resin composition solution C.
After removing the solvent in a state where the obtained resin composition solution C was applied on a polyethylene terephthalate sheet to form a film (2a) having a thickness of 30 microns, the resin composition solution B was applied on the sheet, The solvent was removed to produce a bilayer film with a total thickness of 100 microns. (2b)
The film was heated at 110 ° C. for 3 hours, and further cured by heating at 170 ° C. for 30 minutes to produce a 100 μm plate-like molded body.

(Comparative Example 1)
After removing the solvent in a state where the obtained resin composition solution B was applied on a polyethylene terephthalate sheet to form a film (3a) having a thickness of 30 microns, the resin composition solution B was further applied on the sheet. The solvent was removed, and a film having a total thickness of 100 microns was prepared in the same manner as in Example 2. (3b)
This film was heated at 110 ° C. for 3 hours and further cured by heating at 170 ° C. for 30 minutes to produce a 100 μm plate-like molded body.

(Evaluation)
The following items were evaluated for the performance of the plate-like molded bodies produced in Examples 1-2 and Comparative Example 1. The results are shown in Table 1.

(1) Measurement of thermal expansion coefficient A test piece cut to 3 mm × 25 mm by cutting a plate-shaped molded body was heated at a rate of 5 ° C. using a TMA (thermomechanical analysis) apparatus (manufactured by Seiko Denshi, TMA / SS120C). The temperature was increased at a rate of 1 minute, the average linear expansion coefficient was measured, and the following items were evaluated.
The average linear expansion coefficient (α1) [° C. ⁻¹ ] at a temperature 10 ° C. to 50 ° C. lower than the glass transition temperature of the resin composition.
The average linear expansion coefficient (α2) [° C.-1] at a temperature 10 ° C. to 50 ° C. higher than the glass transition temperature of the resin composition.

(2) Average interlayer distance of layered silicate Using an X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation), a diffraction peak obtained from diffraction of the layered surface of the layered silicate in a 2 mm thick plate-shaped body. 2θ was measured, the (001) plane distance d of the layered silicate was calculated by the black diffraction formula of the following formula (3), and the obtained d was defined as the average interlayer distance (nm).
λ = 2 dsin θ (3)
In the above formula (3), λ is 0.154 (nm), and θ represents a diffraction angle.

(3) Ratio of layered silicate dispersed as a laminate of 5 layers or less A plate-shaped molded body having a thickness of 100 μm is observed with a transmission electron microscope at a magnification of 100,000 times, and is a layered silicate that can be observed in a certain area. The total number of layers X in the laminate and the number Y of layered silicate dispersed in 5 layers or less are measured, and the ratio of the layered silicate dispersed as a laminate of 5 layers or less according to the following formula (2) ( %) Was calculated.

Ratio of layered silicate dispersed as a laminate of 5 layers or less (%) = (Y / X) × 100 (2)
(4) Measurement of tensile modulus and elongation at break The portions corresponding to the tensile modulus after curing of 2.0 GPa or less correspond to 1a, 2a, and 3a in Examples 1 and 2 and Comparative Example 1, respectively. Therefore, each of these was cured under the curing conditions of each example or comparative example, and then the obtained plate-shaped molded body was cut into 10 mm × 80 mm to prepare a measurement sample. These were measured for tensile properties at room temperature with a tensile tester (Orientec Co., Ltd., trade name: “Tensilon”) at a distance between chucks of 60 mm and a crosshead speed of 5 mm / min.
As another method for preparing the measurement sample, the surface opposite to the surface to be measured is fixed to a jig such as an aluminum plate with double-sided tape, and the cured product is carefully up to 50% or 80% of the thickness A desired thickness portion can be obtained by polishing.
(5) Evaluation of non-peelability An uncured film (1c, 2b, 3b) is placed on the copper foil side of a 0.6 mm thick core substrate (with glass cloth, double-sided board with copper foil, manufactured by Risho Kogyo Co., Ltd.) at 100 ° C. After being pressure-bonded at 0.3 MPa for 1 minute with a pressure press machine heated to 1, it was cured under the respective curing conditions.
The cured sample was cut into 10 mm × 100 mm, the cross section was observed with an electron microscope, and after confirming that there was no peeling between the copper foil and the resin sheet of the present invention, 10 ° C. 4.5 hours, 100 ° C. 4.5 A thermal cycle test of 40 cycles was performed over time, and the cross section was observed in the same manner to evaluate the peeling of the bonded surface with the copper foil.
The case where peeling did not occur was marked with ◯, and the case where peeling occurred was marked with ×.

(6) Measurement of water absorption Weight (W1) after preparing a test piece in which a plate-like molded body having a thickness of 100 μm was formed into a 3 × 5 cm strip and dried at 80 ° C. for 5 hours under reduced pressure at 50 Torr. Was measured. Next, the test piece was immersed in water, left in 100 ° C. boiling water for 1 hour, then taken out, and the weight (W2) after carefully wiping with a waste was measured. The water absorption was determined by the following formula (4).
Water absorption rate (%) = (W2−W1) / W1 × 100 (4)

(7) Measurement of total light transmittance The total light transmittance of a 1 mm-thick plate-like molded article was measured using a spectrophotometer (U-4000 manufactured by Hitachi, Ltd.).
(8) Evaluation of laser processability A resin sheet having a thickness of 100 μm is applied to a 0.6 mm-thick core substrate (with a glass cloth, a double-sided substrate with copper foil, manufactured by Risho Kogyo Co., Ltd.) and a vacuum laminator (manufactured by Meiki Seisakusho, MLB-5000) was vacuum laminated at 80 ° C., 40 seconds, and a pressure of 0.6 MPa. After laminating, the PET resin sheet was removed and heat cured at 170 ° C. for 60 minutes. The thermally cured substrate was subjected to CO ₂ laser processing to form a via. Thereafter, the cross-sectional shape of the via and the desmear state of the bottom of the via were observed. When forming the via, a CO ₂ laser processing apparatus (ML605GTX) manufactured by Mitsubishi Electric Corporation was used, the output was 1.00 mA, the pulse width was 7 μsec, the mask diameter was 0.9 mm, and the target diameter was The upper portion of the via is 100 μm and the bottom portion of the via is 70 μm. In addition, the via bottom diameter was set such that the opening was 70% as described above with respect to the via upper diameter.
About each resin sheet obtained in Examples 1-2 and the comparative example 1, the said laser workability was evaluated. The results are shown in Table 1 below.

Claims (6)

  A resin sheet comprising a resin composition containing 100 parts by weight of a thermosetting resin and / or a photocurable resin and 0.1 to 100 parts by weight of a layered silicate, having a thickness of 10 to 200 μm and after curing The portion where the tensile modulus is 2.0 GPa or less is at least 20% to 70% in thickness from one surface, and there is a portion where the tensile modulus after curing is 2.0 GPa or less from both surfaces. In that case, the total is 70% or less. Average linear expansion coefficient (α1) from a temperature lower by 50 ° C. than the glass transition temperature of the resin sheet to a temperature lower by 10 ° C. than the glass transition temperature of the resin sheet is 5.0 × 10 ⁻⁵ [° C. ⁻¹ ] or less. The resin sheet according to claim 1, wherein:   The thermosetting resin and / or the photocurable resin is at least one selected from the group consisting of epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicon resins, benzoxazine resins, and melamine resins. The resin sheet according to claim 1 or 2.   4. The resin sheet according to claim 1, wherein the layered silicate is at least one selected from the group consisting of montmorillonite, hectorite, swellable mica, and vermiculite.   The layered silicate contains an alkyl ammonium ion salt having 6 or more carbon atoms, an aromatic quaternary ammonium ion salt, or a heterocyclic quaternary ammonium ion salt, according to any one of claims 1 to 4. Resin sheet. The layered silicate is dispersed such that the average interlayer distance of the (001) plane measured by the wide-angle X-ray diffraction measurement method is 3 nm or more, and part or all of the laminates are 5 layers or less. The resin sheet according to any one of claims 1 to 5, which is characterized by the following.