JP2014012760A - Prepreg using organic fiber base material and manufacturing method of the same, and laminated plate, metal foil-clad laminated plate, and wiring board using the prepreg - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg expressing low thermal expansion and high adhesiveness and a manufacturing method of the same, and a laminated plate, a metal foil-clad laminated plate, and a wiring board using the prepreg.SOLUTION: A thermosetting resin is obtained by reacting, in an organic solvent, (a) a siloxane resin having hydroxyl groups at its terminals represented by following general formula (I) and (b) a compound having at least two or more cyanate groups in one molecule, and contains 10-70 pts.mass of the siloxane resin (a) and 30-90 pts.mass of the compound (b) based on the sum total 100 pts.mass of the siloxane resin (a) and the compound (b). A prepreg is obtained by immersing in an organic fiber base material the thermosetting resin having a reaction rate of the compound (b) of 40-70 mol% and a thermosetting resin composition containing silica and a compound having at least two or more epoxy groups in one molecule.

Description

  The present invention relates to a prepreg using a thermosetting resin composition excellent in low thermal expansion and high adhesion, a method for producing the same, and a laminate, a metal foil-clad laminate, and a wiring board using the prepreg.

  Thermosetting resin compositions have a cross-linked structure and exhibit high heat resistance and dimensional stability, and thus are widely used in the fields of electronic devices and the like. In particular, it is used as a printed wiring board on which wirings and circuit patterns are printed, a prepreg constituting a copper-clad laminate in which printed wiring boards are multilayered, and an interlayer insulating material.

  In recent years, electronic devices have become smaller and lighter, and the operating frequency has been increased, and printed wiring and circuit patterns have been highly integrated. As high integration methods, proposals have been made for miniaturization of printed wiring and circuit patterns formed on a printed wiring board, multilayering of circuit boards on which circuit patterns are formed, or a combination thereof.

  With the high integration of these printed wirings, low thermal expansion is particularly required for printed wiring boards. Patent Documents 1, 2 and 3 disclose resin compositions comprising a cyanate compound and an inorganic filler and exhibiting a low thermal expansion property. However, since these exhibit a low thermal expansion property, the blending amount of the inorganic filler is disclosed. However, when used as a copper clad laminate or an interlayer insulating material, there are problems such as insufficient drillability and formability.

JP 2003-268136 A JP 2003-073543 A JP 2002-285015 A

  The objective of this invention is providing the prepreg which expresses low thermal expansibility and high adhesiveness, its manufacturing method, a laminated board using this prepreg, a metal foil tension foil laminated board, and a wiring board.

As a result of investigations to solve the above problems, the present inventors have found that a siloxane resin (a) having a hydroxyl group at the terminal represented by the general formula (I) and at least two cyanate groups in one molecule. An organic fiber base material is impregnated with a thermosetting resin obtained by reacting the compound (b) having a compound, a compound having at least two epoxy groups in one molecule and a thermosetting resin composition having silica. It was found that a laminate, a metal foil-clad laminate, and a wiring board using the prepreg produced in this way exhibit low thermal expansion.
The present invention has been completed based on such findings.

The present invention includes the following contents.
(1) A siloxane resin (a) having a hydroxyl group at the terminal represented by the following general formula (I) and a compound (b) having at least two cyanate groups in one molecule are reacted in an organic solvent. It is the obtained thermosetting resin, and the siloxane resin (a) with respect to 100 parts by mass of the total of the siloxane resin (a) and the compound (b) having at least two cyanate groups in one molecule. Compound having 10 to 70 parts by mass and 30 to 90 parts by mass of compound (b) having at least two or more cyanate groups in one molecule, and having at least two or more cyanate groups in one molecule A thermosetting resin having a reaction rate of (b) of 40 to 70 mol%, a compound having at least two epoxy groups in one molecule and silica, and Impregnating the fiber base material, obtained prepreg.

（一般式（Ｉ）中、Ｒ₁は各々独立に炭素数１〜５のアルキレン基又はアルキレンオキシ基、Ａｒ₁は各々独立に単結合、アリーレン基又は炭素数１〜５のアルキレン基であり、ｍは５〜１００の整数である。）
（２）前記有機繊維基材が、アラミド樹脂、液晶ポリエステル（ＰＬＣ）樹脂、パラフェニレンベンゾビスオキサゾール（ＰＢＯ）樹脂、ポリエステル樹脂、芳香族ポリエステル樹脂、ポリイミド樹脂、超高分子量ポリエチレン及びテトラフルオロエチレン樹脂から選ばれる少なくとも１以上の繊維基材である上記（１）に記載のプリプレグ。
（３）前記有機繊維基材が、表面処理されてなる上記（１）又は（２）に記載のプリプレグ。
（４）前記有機繊維基材の表面処理が、シランカップリング剤、コロナ処理及びプラズマ処理のいずれかである上記（３）に記載のプリプレグ。
（５）上記（１）〜（４）のいずれかに記載のプリプレグを、少なくとも１枚以上用いて積層し、成形して得られた積層板。
（６）上記（１）〜（４）のいずれかに記載のプリプレグを、少なくとも１枚以上用い、さらに金属箔を積層し、成形して得られた金属箔張積層板。
（７）前記（６）に記載の金属箔張積層板を配線形成して得られた配線板。
（８）下記一般式（Ｉ）で示される末端に水酸基を有するシロキサン樹脂（ａ）と、１分子中に少なくとも２個以上のシアネート基を有する化合物（ｂ）とを、前記シロキサン樹脂（ａ）と前記１分子中に少なくとも２個以上のシアネート基を有する化合物（ｂ）との総和１００質量部に対し、前記シロキサン樹脂（ａ）１０〜７０質量部及び前記１分子中に少なくとも２個以上のシアネート基を有する化合物（ｂ）３０〜９０質量部を用い、前記１分子中に少なくとも２個以上のシアネート基を有する化合物（ｂ）の反応率が４０〜７０ｍｏｌ％となるよう有機溶媒中で反応し熱硬化性樹脂を製造する工程、
前記熱硬化性樹脂と、１分子中に少なくとも２個以上のエポキシ基を有する化合物とシリカを配合して熱硬化性樹脂組成物を作製する工程、
前記熱硬化性樹脂組成物を、有機繊維基材に含浸する工程、により得られるプリプレグの製造方法。

(In general formula (I), each R ₁ is independently an alkylene group or alkyleneoxy group having 1 to 5 carbon atoms, Ar ₁ is each independently a single bond, an arylene group or an alkylene group having 1 to 5 carbon atoms, m is an integer of 5 to 100.)
(2) The organic fiber base material is an aramid resin, liquid crystal polyester (PLC) resin, paraphenylene benzobisoxazole (PBO) resin, polyester resin, aromatic polyester resin, polyimide resin, ultrahigh molecular weight polyethylene, and tetrafluoroethylene resin. The prepreg as described in (1) above, which is at least one fiber substrate selected from
(3) The prepreg according to (1) or (2) above, wherein the organic fiber substrate is surface-treated.
(4) The prepreg according to (3) above, wherein the surface treatment of the organic fiber substrate is any one of a silane coupling agent, a corona treatment, and a plasma treatment.
(5) A laminate obtained by laminating and molding at least one prepreg according to any one of (1) to (4) above.
(6) A metal foil-clad laminate obtained by using at least one prepreg according to any one of (1) to (4) above and further laminating and forming a metal foil.
(7) A wiring board obtained by wiring the metal foil-clad laminate according to (6).
(8) A siloxane resin (a) having a hydroxyl group at the terminal represented by the following general formula (I) and a compound (b) having at least two cyanate groups in one molecule are combined with the siloxane resin (a). And 10 parts by mass to 70 parts by mass of the siloxane resin (a) and at least 2 parts by mass of the compound (b) having at least two cyanate groups in one molecule Using 30 to 90 parts by mass of the compound (b) having a cyanate group, the reaction is carried out in an organic solvent so that the reaction rate of the compound (b) having at least two cyanate groups in one molecule is 40 to 70 mol%. Manufacturing a thermosetting resin,
A step of blending the thermosetting resin, a compound having at least two epoxy groups in one molecule, and silica to produce a thermosetting resin composition;
A method for producing a prepreg obtained by impregnating an organic fiber substrate with the thermosetting resin composition.

（一般式（Ｉ）中、Ｒ₁は各々独立に炭素数１〜５のアルキレン基又はアルキレンオキシ基、Ａｒ₁は各々独立に単結合、アリーレン基又は炭素数１〜５のアルキレン基であり、ｍは５〜１００の整数である。）

(In general formula (I), each R ₁ is independently an alkylene group or alkyleneoxy group having 1 to 5 carbon atoms, Ar ₁ is each independently a single bond, an arylene group or an alkylene group having 1 to 5 carbon atoms, m is an integer of 5 to 100.)

  According to the present invention, it is possible to provide a prepreg having a low thermal expansion coefficient and high adhesiveness, a method for producing the same, a laminate, a metal foil-clad laminate and a wiring board.

Hereinafter, embodiments of the present invention will be described in detail.
[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises a siloxane resin (a) having a hydroxyl group at the terminal represented by the general formula (I), a compound (b) having at least two cyanate groups in one molecule, and Is obtained by reacting in an organic solvent. The total amount of the siloxane resin (a) and the compound (b) having at least two cyanate groups in one molecule is 100 parts by mass, and the siloxane resin (a) is 10 to 70 parts by mass and in one molecule. 30 to 90 parts by mass of the compound (b) having at least two cyanate groups is contained in the compound, and the reaction rate of the compound (b) having at least two cyanate groups in one molecule is 40 to 70 mol. % Thermosetting resin, a compound having at least two epoxy groups in one molecule, and silica.

  The organic solvent used for the reaction of the siloxane resin (a) with the compound (b) having at least two cyanate groups in one molecule is not particularly limited, but toluene, mesitylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone In particular, toluene and mesitylene are preferable because of high solubility of the siloxane resin (a) and the compound (b) having at least two cyanate groups in one molecule.

The siloxane resin (a) is not particularly limited as long as it is a siloxane resin containing a hydroxyl group having the structure represented by the above general formula (I), but both ends of the siloxane resin (a) are phenolic hydroxyl groups or alcoholic hydroxyl groups. Preferably there is. Examples of the alkylene group having 1 to 5 carbon atoms of R _{1 in} the general formula (I) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentene group, and a structural isomer thereof. Examples thereof include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group. The arylene group which is Ar ₁ in the general formula (I) means a divalent monocyclic or polycyclic aromatic hydrocarbon group, and specific examples thereof include, for example, a 1,2-phenylene group, 1 , 3-phenylene group, 1,4-phenylene group, biphenyl-4,4′-diyl group, diphenylmethane-4,4′-diyl group, 3,3′-dimethylbiphenyl-4,4′-diyl group and the like. Can be mentioned. The alkylene group having 1 to 5 carbon atoms is the same as the alkylene group for R ₁ described above.
As a commercial item of the siloxane resin (a) having phenolic hydroxyl groups at both ends, for example, trade name X-22-1821 (hydroxyl value: 35 KOHmg / g, hydroxyl group equivalent 1600 g / eq) manufactured by Shin-Etsu Chemical Co., Ltd., Trade name X-22-1822 (hydroxyl value: 20 KOHmg / g).
Moreover, as a commercial item of the siloxane resin (a) which has an alcoholic hydroxyl group in both ends, Shin-Etsu Chemical Co., Ltd. make, brand name X-22-160AS (hydroxyl value: 112KOHmg / g), brand name X-, for example. 22-4015 (hydroxyl value: 27 KOHmg / g) and the like. Further, for example, trade name KF-6001 (hydroxyl value: 62 KOHmg / g), trade name KF-6002 (hydroxyl value: 35 KOHmg / g), trade name KF-6003 (hydroxyl value) manufactured by Toray Dow Corning Silicone Co., Ltd. : 20KOHmg / g) and the like.

Examples of the compound (b) having at least two cyanate groups in one molecule include novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol F type cyanate resin, and tetramethylbisphenol F type. Cyanate resin etc. are mentioned, Among these, 1 type or 2 or more types can be mixed and used. Among these, bisphenol A type cyanate resin or novolac type cyanate resin is preferable from the viewpoints of dielectric properties, heat resistance, flame retardancy, low thermal expansion, and low cost. The average number of repeats of the novolak type cyanate resin is not particularly limited, but is preferably 1 to 30. If it is less than 1, it may be easily crystallized and may be difficult to handle. Moreover, when it exceeds 30, hardened | cured material may become weak.
As a commercial product of bisphenol A type cyanate resin that can be used as the compound (b) having at least two or more cyanate groups in one molecule, Lonza Japan Co., Ltd., trade name Arocy B-10 can be mentioned. Moreover, as a commercial item of a novolak-type cyanate resin, Lonza Japan Co., Ltd. make, brand name Primaset PT-30 (weight average molecular weight 500-1,000), brand name Primaset PT-60 (weight average molecular weight 2,000) ~ 3,000).

  The blending amount of the siloxane resin (a) and the compound (b) having at least two cyanate groups in one molecule is preferably as follows. With respect to 100 parts by mass of the total of the siloxane resin (a) and the compound (b) having at least two cyanate groups in one molecule, the amount of the siloxane resin (a) is in the range of 10 to 70 parts by mass. To do. Moreover, the compounding quantity of the compound (b) which has at least 2 or more cyanate group in 1 molecule shall be the range of 30-90 mass parts.

  When the blending amount of the siloxane resin (a) is less than 10 parts by mass, the low thermal expansion property in the surface direction of the obtained base material may be lowered and the thermal expansion coefficient may be increased. Moreover, when the compounding quantity of siloxane resin (a) exceeds 70 mass parts, heat resistance and chemical resistance may fall. Further, when the compounding amount of the compound (b) having at least two or more cyanate groups in one molecule is less than 30 parts by mass, the heat resistance may be lowered, and at least two or more cyanates in one molecule. When the compounding quantity of the compound (b) which has group exceeds 90 mass parts, the low thermal expansion property of the surface direction of the base material obtained may fall, and a thermal expansion coefficient may become high.

In the present invention, the reaction rate of the siloxane resin (a) and the compound (b) having at least two cyanate groups in one molecule and the compound (b) having at least two cyanate groups in one molecule. It is preferable to pre-react in an organic solvent in advance so that (disappearance rate) is 40 to 70 mol%. Examples of the pre-reaction include an imino carbonate reaction and a triazine cyclization reaction.
The iminocarbonation reaction is a reaction in which an iminocarbonate bond (—O— (C═NH) —O—) is generated by the addition reaction of a hydroxyl group and a cyanate group. It is a reaction that quantifies to form a triazine ring.

When the reaction rate of the compound (b) having at least two cyanate groups in one molecule is less than 40 mol%, the compatibility between the obtained thermosetting resin and a general-purpose organic solvent is lowered, and the heat resistance is improved. It may decrease or the copper foil adhesion may decrease. When the reaction rate of the compound (b) having at least two cyanate groups in one molecule is less than 40 mol%, the resulting thermosetting resin is crystallized, and the varnish (thermosetting resin composition) is obtained. It may become impossible to manufacture or tack may occur during coating. In addition, the resulting thermosetting resin may be insufficiently cured, resulting in a decrease in heat resistance.
Moreover, when the reaction rate of the compound (b) having at least two cyanate groups in one molecule exceeds 70 mol%, the resulting thermosetting resin is insolubilized in a general-purpose organic solvent, and the varnish cannot be produced. The moldability of the varnish may be reduced.
In addition, the reaction rate of the compound (b) which has at least 2 or more cyanate groups in 1 molecule is calculated | required from the measurement result of GPC measurement. Specifically, a solution before reaction in which a siloxane resin (a) and a compound (b) having at least two cyanate groups in one molecule are blended, and a solution after reacting this solution, The peak areas of cyanate resin appearing around a predetermined holding time are compared. The disappearance rate of the peak area of the solution after the reaction relative to the peak area of the solution before the reaction corresponds to the reaction rate.

The compound having at least two or more epoxy groups in one molecule used in the present invention may be any compound as long as it has two or more epoxy groups in one molecule. For example, naphthalene type epoxy resin, Naphthalene novolac type epoxy resin, anthracene type epoxy resin, dihydroanthracene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl aralkyl type epoxy resin, phenol novolac type epoxy resin Examples thereof include resins and cresol novolac type epoxy resins, and naphthalene novolac type epoxy resins and biphenyl aralkyl type epoxy resins are particularly preferable. These compounds may have any molecular weight, and several types may be used in combination. The compounding amount of the compound having at least two epoxy groups in one molecule is the sum of the siloxane resin (a) having a hydroxyl group at the terminal and the compound (b) having at least two cyanate groups in one molecule. It is 10-100 mass parts with respect to 100 mass parts, Preferably it is 10-80 mass parts, Most preferably, it is 15-50 mass parts. If it is less than 10 parts by mass, the effect of improving the adhesive strength with the copper foil is poor, and if it exceeds 100 parts by mass, the low thermal expansion properties are not exhibited.
In addition, for these epoxy resins, it is possible to use high-purity products in which alkali metal ions, alkaline earth metal ions, halogen ions, particularly chlorine ions and hydrolyzable chlorine are reduced to 300 ppm or less as impurity ions. This is preferable for preventing migration and corrosion of metal conductor circuits.

  When using the said epoxy resin, a hardening | curing agent can also be used as needed. Examples of the curing agent include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, organic acids. Examples include dihydrazide, boron trifluoride amine complex, imidazoles, and tertiary amines. As the phenolic compound, a phenolic compound having at least two phenolic hydroxyl groups in the molecule is more preferable. Examples of such compounds include phenol novolak, cresol novolak, t-butylphenol novolak, dicyclopentagen cresol novolak, dicyclopentagen phenol novolak, xylylene-modified phenol novolak, naphthol compound, trisphenol compound, tetrakisphenol. Examples include novolak, bisphenol A novolak, poly-p-vinylphenol, and phenol aralkyl resin. Among these, those having a number average molecular weight in the range of 400 to 1500 are preferable.

The silica used in the present invention may have any particle size and shape, but in order to ensure the fluidity of the resin, a spherical shape is preferable, and a spherical fused silica is particularly preferable. The silica particle diameter may be any, but in order to form highly integrated wiring, the average particle diameter is preferably 5 μm or less, more preferably 3 μm or less, and particularly preferably 1 μm or less.
The average particle diameter can be measured with a commercially available apparatus using a dynamic light scattering method or a laser diffraction method.
In the present invention, inorganic fillers other than silica may be blended, and examples thereof include mica, talc, short glass fiber or fine powder, hollow glass, calcium carbonate, and metal hydrate. The blending amount of silica and inorganic filler is preferably 10 to 300 parts by weight, more preferably 100 to 250 parts by weight, and more preferably 150 to 150 parts by weight with respect to 100 parts by weight of the thermosetting resin composition in terms of solid content. It is especially preferable to set it as -250 mass parts. If it is 10-300 mass parts, sufficient rigidity of a base material, moisture heat resistance, a flame retardance, the tolerance with respect to the erosion by a plating solution, etc. will be obtained. In addition, the filler can be treated with a commercially available surface treatment agent such as a coupling agent, or dispersed with a disperser such as a triple roll, bead mill, or nanomizer to improve the dispersibility of the inorganic filler. Good.

  In the thermosetting resin composition used in the present invention, it is desirable to use a curing accelerator for improving heat resistance, flame retardancy, copper foil adhesion, and the like. Examples of curing accelerators include organometallic salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, imidazoles and their derivatives, tertiary amines and quaternary ammonium salts. . In addition, known thermoplastic resins, elastomers, flame retardants, organic fillers and the like can be used in combination. Examples of the thermoplastic resin that can be blended in the thermosetting resin composition used in the present invention include tetrafluoroethylene, polyethylene resin, polypropylene resin, polystyrene resin, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, and polyamide resin. , Polyimide resin, xylene resin, petroleum resin, silicone resin and the like. Examples of elastomers that can be incorporated into the thermosetting resin composition used in the present invention include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile. Examples of organic fillers that can be blended in the thermosetting resin composition used in the present invention include organic powders such as silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether. Examples of flame retardants that can be incorporated into the thermosetting resin composition used in the present invention include triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, phosphazenes, red phosphorus, and other phosphorus-based flame retardants. Examples include inorganic flame retardant aids such as a flame retardant, antimony trioxide, and zinc molybdate. In addition, the thermosetting resin composition used in the present invention may appropriately contain compounding agents such as an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, and an adhesion improver. Examples of compounding agents that can be incorporated into the thermosetting resin composition used in the present invention include ultraviolet absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, benzophenones, and benzyl ketals. And photopolymerization initiators such as thioxanthone, fluorescent whitening agents such as stilbene derivatives, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.

Hereinafter, the prepreg of the present invention will be described in detail.
The prepreg of the present invention is formed by impregnating or coating the above-mentioned thermosetting resin composition on an organic fiber substrate. The prepreg of the present invention can be produced by impregnating or coating the thermosetting resin composition used in the present invention on an organic fiber substrate and semi-curing (B-stage) by heating or the like to produce the prepreg of the present invention. it can. Organic fiber base materials include aramid resin, liquid crystal polyester (PLC) resin, paraphenylene benzobisoxazole (PBO) resin, polyester resin, aromatic polyester resin, polyimide resin, ultrahigh molecular weight polyethylene and tetrafluoroethylene resin. Examples thereof include fiber base materials and mixtures thereof.

These organic fiber base materials have shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and are necessary. Thus, it is possible to combine a single material or two or more materials and shapes. The thickness in particular of an organic fiber base material is not restrict | limited, For example, about 0.03-0.5 mm can be used, and it is preferable that the organic fiber base material is surface-treated. As the surface treatment, those surface-treated with a silane coupling agent, corona, plasma or the like are preferable from the viewpoints of heat resistance, moisture resistance, and workability. After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. And dried for 1 to 30 minutes and semi-cured (B-stage).
Through the above steps, the prepreg of the present invention can be obtained.

  The laminate of the present invention can be produced by laminating a predetermined number of sheets using the prepreg of the present invention described above. A metal foil-clad laminate can be produced by laminating 1 to 20 prepregs of the present invention and laminating them with a configuration in which a metal foil such as copper and aluminum is disposed on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications. The molding conditions may be, for example, a laminated plate for an electrical insulating material and a multilayer plate. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine or the like is used, and the temperature is 100 to 250 ° C. and the pressure is 0. It can be molded in a range of 2 to 10 MPa and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.

  Next, the present invention will be described more specifically with reference to the following examples, but these examples do not limit the present invention. In the following examples, a thermosetting resin composition was produced, and using these, a prepreg, a laminate, and a copper-clad laminate in which a copper foil was disposed on the laminate were produced. This produced copper clad laminate was evaluated by the following evaluation methods.

[Evaluation method]
<Measurement of linear thermal expansion coefficient>
A 5 mm × 15 mm evaluation board from which the copper foil was removed by immersing the copper clad laminate in a copper etching solution was prepared, and evaluated using a TMA test apparatus “TMA2940” (manufactured by TA Instruments Japan Co., Ltd.). The linear thermal expansion coefficient of 30 to 100 ° C. in the surface direction of the substrate was measured.

<Evaluation of copper foil adhesion (copper foil peel strength)>
The adhesiveness of the copper foil was evaluated by peel strength. A copper foil having a width of 1 cm was formed by immersing the copper clad laminate in a copper etching solution to produce an evaluation substrate, and the peel strength of the copper foil was measured using a tensile tester (90 ° peel, 50 mm / min). ).

<Manufacture of thermosetting resin composition>
A siloxane resin (a) made of siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl group) is placed in a reaction vessel with a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer and a reflux condenser Equivalent: 1600 g / eq., In general formula (I), Ar ₁ is a phenyl group (—C ₆ H ₄ —), R ₁ is a propylene group (—C ₃ H ₆ —), m is an integer of 35-40 ): 500 g, toluene: 1000 g, bisphenol A type cyanate resin (product of Lonza Japan Co., Ltd .; trade name Arocy B-10, 2, 2-) as the compound (b) having at least two cyanate groups in one molecule Bis (4-cyanatophenyl) propane): 500, heated while stirring, and after reaching 120 ° C., an 8% by mass mineral spirit solution of zinc naphthenate was added. And .01g added, after 4 hours reflux the reaction at about 115 to 125 ° C., cooled to room temperature (25 ° C.), to obtain a solution of a thermosetting resin composition.

The solution before the reaction in which the siloxane resin (a) and the compound (b) having at least two cyanate groups in one molecule are blended and the solution after the reaction are taken out little by little, and GPC measurement (elution is performed) for each. Liquid: tetrahydrofuran). Compare the peak area of the bisphenol A-type cyanate resin that has a retention time of about 12.4 minutes between the solution before the reaction and the solution after the reaction, and compare the peak area of the solution after the reaction with the peak area of the solution before the reaction. The disappearance rate of the peak area was calculated. As a result, the disappearance rate of the peak area in the solution after the reaction was 65%. Therefore, the reaction rate of the compound (b) having at least two cyanate groups in one molecule in the thermosetting resin composition was 65 mol%. Moreover, the peak of the product of the thermosetting resin which appears at about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. A peak near 1700 cm ⁻¹ due to the imino carbonate group, a strong peak near 1560 cm ⁻¹ due to the triazine ring, and a strong peak near 1380 cm ⁻¹ were confirmed, confirming that a thermosetting resin was produced. .

  While stirring 200 g of NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., biphenyl novolac type epoxy resin) as a compound having at least two epoxy groups in one molecule in a 200 g methyl isobutyl ketone solution. In addition, an epoxy solution was prepared. In addition, 700 g of silica: SO-G1 (trade name, manufactured by Admatechs Co., Ltd.) and 300 g of methyl isobutyl added with 7 g of KBM-903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., aminopropyltrimethoxysilane) It was added to the ketone solution while stirring to prepare a methyl isobutyl solution of silica. To 300 g of the thermosetting resin solution, 200 g of an epoxy solution and 870 g of a methyl isobutyl solution of silica were added and stirred for 2 hours to prepare a thermosetting resin composition varnish.

[Examples 1 to 3]
The thermosetting resin composition varnish was impregnated with a resin so that the organic fiber substrate shown in Table 1 had the mass ratio shown in Table 1. This was dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin volume fraction of 72%.

[Comparative Examples 1-3]
Only the epoxy solution was removed from the solution of the thermosetting resin composition, and the organic fiber substrate shown in Table 1 was impregnated with the resin so that the mass ratio shown in Table 1 was obtained. This was dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin volume fraction of 72%.

[Comparative Example 4]
Using a thermosetting resin composition varnish, a glass cloth shown in Comparative Example 4 in Table 1 was impregnated with a resin so as to have a mass ratio shown in Table 1. This was dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin volume fraction of 72%.

  Four prepregs obtained in Examples 1 to 3 and Comparative Examples 1 to 4 are stacked to form a laminate, and an electrolytic copper foil having a thickness of 18 μm is disposed on one surface and the other surface of the laminate. A copper foil-clad laminate was obtained by pressure bonding for 90 minutes under the conditions of a pressure of 2.45 MPa and a temperature of 230 ° C.

  From comparison between Examples 1 to 3 and Comparative Example 4 in Table 1, it can be seen that by using an organic fiber base material for the prepreg, a lower coefficient of thermal expansion can be exhibited than a prepreg using a conventional glass cloth. Moreover, it turns out that copper foil peel strength can be improved by mix | blending the compound which has at least 2 or more epoxy group in 1 molecule from the comparison of Examples 1-3 of Table 1 and Comparative Examples 1-3.

  A prepreg obtained by impregnating or applying an organic fiber substrate with the thermosetting resin composition of the present invention, and a copper foil-clad laminate produced by laminating the prepreg, have a low thermal expansion coefficient and a high copper foil peel. It exhibits strength characteristics and is useful for printed wiring boards for electronic equipment.

Claims (8)

It was obtained by reacting a siloxane resin (a) having a hydroxyl group at the terminal represented by the following general formula (I) with a compound (b) having at least two cyanate groups in one molecule in an organic solvent. 10 to 70 of the siloxane resin (a) with respect to 100 parts by mass of the total of the siloxane resin (a) and the compound (b) having at least two cyanate groups in one molecule. Compound (b) having 30 to 90 parts by mass of compound (b) having at least 2 or more cyanate groups in one molecule and at least 2 or more cyanate groups in the molecule. A thermosetting resin composition containing 40% to 70 mol% of a thermosetting resin, a compound having at least two epoxy groups in one molecule, and silica. Impregnating the wood, resulting prepreg.

(In general formula (I), each R ₁ is independently an alkylene group or alkyleneoxy group having 1 to 5 carbon atoms, Ar ₁ is each independently a single bond, an arylene group or an alkylene group having 1 to 5 carbon atoms, m is an integer of 5 to 100.)   The organic fiber substrate is selected from an aramid resin, a liquid crystal polyester (PLC) resin, a paraphenylene benzobisoxazole (PBO) resin, a polyester resin, an aromatic polyester resin, a polyimide resin, an ultrahigh molecular weight polyethylene, and a tetrafluoroethylene resin. The prepreg according to claim 1, which is at least one fiber substrate.   The prepreg according to claim 1 or 2, wherein the organic fiber substrate is surface-treated.   The prepreg according to claim 3, wherein the surface treatment of the organic fiber base material is any one of a silane coupling agent, a corona treatment, and a plasma treatment.   A laminate obtained by laminating and molding at least one prepreg according to claim 1.   A metal foil-clad laminate obtained by using at least one prepreg according to any one of claims 1 to 4 and further laminating and molding a metal foil.   A wiring board obtained by wiring the metal foil-clad laminate according to claim 6. A siloxane resin (a) having a hydroxyl group at the terminal represented by the following general formula (I), a compound (b) having at least two cyanate groups in one molecule, the siloxane resin (a) and the 1 10 to 70 parts by mass of the siloxane resin (a) and at least two or more cyanate groups in one molecule with respect to a total of 100 parts by mass of the compound (b) having at least two or more cyanate groups in the molecule. Using 30 to 90 parts by mass of the compound (b) having the compound, the compound (b) having at least two cyanate groups in one molecule is reacted in an organic solvent so as to have a reaction rate of 40 to 70 mol%, and is thermoset. A process for producing a functional resin,
A step of blending the thermosetting resin, a compound having at least two epoxy groups in one molecule, and silica to produce a thermosetting resin composition;
A method for producing a prepreg obtained by impregnating an organic fiber substrate with the thermosetting resin composition.

(In general formula (I), each R ₁ is independently an alkylene group or alkyleneoxy group having 1 to 5 carbon atoms, Ar ₁ is each independently a single bond, an arylene group or an alkylene group having 1 to 5 carbon atoms, m is an integer of 5 to 100.)