JP2015063585A - Thermosetting resin composition and prepreg using the same, laminate board, printed wiring board and mounting substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which suppresses a problem of insufficient curing of a resin and has high elasticity and excellent low thermal expansion, moisture and heat resistance and desmear liquid resistance and further excellent storage stability of varnish and to provide use of the same, for example, a laminate board, a printed wiring board and a mounting substrate.SOLUTION: There is used a thermosetting resin composition which comprises: a compound (A) having a hydroxyl group and an epoxy group in the molecular structure which is obtained by esterification reaction of a siloxane resin (a) having a carboxyl group with a compound (b) having two or more epoxy groups in one molecule; a compound (B) having two or more cyanate groups in one molecule; and an organic metal salt (C).

Description

  The present invention relates to a thermosetting resin composition suitable for use in the electronic field such as a semiconductor package, and a prepreg, a laminated board, a printed wiring board and a mounting board using the same.

  Thermosetting resin compositions have a cross-linked structure and exhibit high heat resistance and excellent dimensional stability, and are therefore widely used in fields such as electronic parts. For example, a laminated board formed from a prepreg impregnated or coated on a base material with a thermosetting resin composition, a printed wiring board having a conductor pattern formed on the surface or surface of the laminated board and the inside thereof, a wiring board, etc. It is used as an interlayer insulation material. In recent years, warping of the printed wiring board has become a problem as the printed wiring board is thinned. In order to suppress this warpage, a thermosetting resin composition that exhibits a high elastic modulus and a low coefficient of thermal expansion is desired.

  Also, in recent years, due to increasing environmental awareness, it is required to use lead-free solder when mounting electronic components, and to use halogen-free substrates as substrates for mounting electronic components. However, lead-free solder has a higher operating temperature than conventional solder, and a halogen-free substrate is inferior in flame retardancy compared to a normal halogen-containing substrate. For this reason, the thermosetting resin composition which expresses still higher heat resistance and a flame retardance is desired. Furthermore, in order to improve the safety of the product and the working environment, there is a demand for a thermosetting resin composition that is composed of components having low toxicity and hardly generates toxic gases.

  Cyanate compounds have attracted attention as such thermosetting resin compositions (see, for example, Patent Documents 1 to 5). The cyanate compound is a resin composition having low dielectric properties and excellent flame retardancy. However, when a cyanate compound is used for the epoxy curable thermosetting resin, there may be a problem that the heat resistance and toughness of the cured resin are insufficient.

  Patent Documents 1 and 2 disclose resin compositions comprising a cyanate compound and an inorganic filler and exhibiting low thermal expansibility. In this resin composition, the blending amount of the inorganic filler is increased in order to exhibit low thermal expansion. For this reason, when this resin composition is used as a copper clad laminated board or an interlayer insulation material, drill workability and moldability may be bad.

  Patent Documents 3 and 4 disclose thermosetting resin compositions containing a cyanate resin and an aralkyl-modified epoxy resin as essential components. Since the cyanate resin which is an essential component is a resin having poor toughness and curing reactivity, the curing reactivity and toughness of this thermosetting resin composition are insufficient. Moreover, when these are used for a laminated board and an interlayer insulation material, the heat resistance of the obtained printed wiring board, reliability, and workability may be inadequate.

  When a thermosetting resin composition is used for a multilayer printed wiring board, the thermosetting resin composition must have properties such as adhesion to a conductor layer, heat resistance, flame resistance, and drillability. become. However, it is difficult to obtain a thermosetting resin composition that sufficiently satisfies these characteristics. In this regard, Patent Document 5 discloses a thermosetting resin composition using a compound having a cyanate group, a siloxane resin, and fused silica. This thermosetting resin composition exhibits excellent low thermal expansion and the like. And this thermosetting resin composition has superior adhesion to the conductor layer, high flame retardancy, good drilling workability and excellent low dielectric constant compared to other general thermosetting resin compositions. It has characteristics etc.

JP 2003-268136 A JP 2003-73543 A JP 2002-309085 A JP 2002-348469 A JP 2012-52110 A

  However, when the thermosetting resin composition described in Patent Document 5 is used for a substrate, the elastic modulus of the substrate is low. Further, even when a phenol novolac type cyanate, which is a highly elastic cyanate compound, is used, it is difficult to increase the elastic modulus of the substrate (for example, the bending elastic modulus at 25 ° C. is 28 GPa or more). This is because, under normal curing conditions (press conditions at 100 to 250 ° C. for 0.1 to 5 hours), the polymerization of the phenol novolak cyanate having poor curing reactivity is insufficient, and the thermosetting resin composition is cured. This is because there is a shortage. Moreover, in the desmear process of the circuit board, the resin in an insufficiently cured state may be eluted in the resin composition, and it is necessary to improve the desmear resistance. Furthermore, storage stability is required for the varnish or prepreg of the resin composition for printed wiring boards.

  The present invention suppresses the problem of insufficient curing of the resin, is highly elastic, has low thermal expansion, moisture and heat resistance, and resistance to desmear liquid, and further has excellent varnish storage stability and An object is to provide a prepreg, a laminate, a printed wiring board, and a mounting board using the same.

（式中、Ｒ₁は、各々独立に炭素数１〜５の飽和炭化水素基であり、ｍは５〜１００の整数である）
［２］分子構造中に水酸基及びエポキシ基を有する化合物（Ａ）と１分子中に２個以上のシアネート基を有する化合物（Ｂ）とを反応させて得られる化合物を含む上記［１］に記載の熱硬化性樹脂組成物。
［３］有機金属塩（Ｃ）が、ナフテン酸金属塩及びオクチル酸金属塩から選ばれる少なくとも１種である、上記［１］又は［２］に記載の熱硬化性樹脂組成物。
［４］上記［１］〜［３］のいずれかに記載の熱硬化性樹脂組成物を基材に含浸又は塗工してなるプリプレグ。
［５］上記［４］に記載のプリプレグを積層してなる積層板。
［６］上記［５］に記載の積層板の表面又は表面及び内部に導体パターンが形成されたプリント配線板。
［７］上記［６］に記載のプリント配線板と、プリント配線板に配置されたプリント部品及び搭載部品とを含む実装基板。 The present invention employs a thermosetting resin composition comprising a compound obtained by esterifying a siloxane resin having a carboxyl group and a compound having an epoxy group, a compound having a cyanate group, and an organic metal salt. Knowledge that it is possible to obtain a thermosetting resin composition having high elasticity, low thermal expansion and moisture and heat resistance, and excellent desmear liquid resistance, and a prepreg, laminate and mounting board using the same. It was made based on.
That is, the present invention is as follows.
[1] Obtained by reacting a siloxane resin (a) having a carboxyl group represented by the following general formula (I) with a compound (b) having two or more epoxy groups in one molecule. A thermosetting resin composition comprising a compound (A) having a hydroxyl group and an epoxy group in a molecular structure, a compound (B) having two or more cyanate groups in a molecule, and an organometallic salt (C).

(Wherein R ₁ is each independently a saturated hydrocarbon group having 1 to 5 carbon atoms, and m is an integer of 5 to 100)
[2] The above [1], which includes a compound obtained by reacting a compound (A) having a hydroxyl group and an epoxy group in the molecular structure with a compound (B) having two or more cyanate groups in one molecule Thermosetting resin composition.
[3] The thermosetting resin composition according to the above [1] or [2], wherein the organic metal salt (C) is at least one selected from naphthenic acid metal salts and octylic acid metal salts.
[4] A prepreg obtained by impregnating or coating the base material with the thermosetting resin composition according to any one of [1] to [3].
[5] A laminate obtained by laminating the prepreg according to [4] above.
[6] A printed wiring board in which a conductor pattern is formed on the surface or the surface and inside of the laminated board according to [5].
[7] A mounting board including the printed wiring board according to [6] above, a printed component and a mounting component disposed on the printed wiring board.

  According to the present invention, a thermosetting resin composition having high elasticity, low thermal expansion and moisture and heat resistance, and excellent desmear liquid resistance, and a prepreg, a laminate, a printed wiring board and a mounting board using the same Can be obtained.

（式中、Ｒ₁は、各々独立に炭素数１〜５の飽和炭化水素基であり、ｍは５〜１００の整数である）
以下、本発明の熱硬化性樹脂組成物を詳細に説明する。 [Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises a carboxyl group-containing siloxane resin (a) (hereinafter sometimes referred to as component (a)) represented by the following general formula (I) and in one molecule. Compound (A) having a hydroxyl group and an epoxy group in the molecular structure obtained by reacting with compound (b) having two or more epoxy groups (hereinafter sometimes referred to as component (b)) (hereinafter referred to as “component (b)”) , Which may be referred to as component (A)), compound (B) having two or more cyanate groups in one molecule (hereinafter also referred to as component (B)), and organometallic salt (C) ( Hereinafter, it may be referred to as component (C)).

(Wherein R ₁ is each independently a saturated hydrocarbon group having 1 to 5 carbon atoms, and m is an integer of 5 to 100)
Hereinafter, the thermosetting resin composition of the present invention will be described in detail.

ここで、耐熱性、低熱膨張性及び溶剤溶解性に優れる熱硬化性樹脂組成物が得られる点から、式中、Ｒ₁は各々独立に炭素数１〜５の飽和炭化水素基であることが好ましい。また、ｍは２〜１００の整数であることが好ましく、１０〜４０であることがより好ましい。成分（ａ）としては、市販品を用いてもよい。市販品としては、例えば、信越化学工業（株）製の商品名「Ｘ−２２−１６２Ａ」（カルボキシル基当量：８６５）、商品名「Ｘ−２２−１６２Ｂ」（カルボキシル基当量：１５００）等が挙げられる。 [Siloxane resin having carboxyl group (a)]
The siloxane resin (a) having a carboxyl group of the present invention is represented by the following general formula (I).

Here, from the point that a thermosetting resin composition excellent in heat resistance, low thermal expansibility and solvent solubility is obtained, in the formula, each R ₁ is independently a saturated hydrocarbon group having 1 to 5 carbon atoms. preferable. M is preferably an integer of 2 to 100, more preferably 10 to 40. A commercial item may be used as a component (a). Examples of commercially available products include trade name “X-22-162A” (carboxyl group equivalent: 865) and trade name “X-22-162B” (carboxyl group equivalent: 1500) manufactured by Shin-Etsu Chemical Co., Ltd. Can be mentioned.

[Compound (b) having two or more epoxy groups in one molecule]
The compound (b) having two or more epoxy groups in one molecule of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. As the component (b), for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, Examples include aralkyl-modified epoxy resins, alicyclic epoxy resins, alcohol-type epoxy resins, glycidyl ether-type epoxy resins, glycidylamine-type epoxy resins, and glycidyl ester-type epoxy resins. These may be used alone or in combination of two or more.

  From the viewpoint of handleability of the prepreg, it is preferable that the prepreg has low tackiness, and for this purpose, the thermosetting resin composition is preferably solid at room temperature. Moreover, from the point that the cured product of the thermosetting resin composition has high elasticity, excellent moisture heat resistance and low thermal expansion, the component (b) includes biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, and It is preferable to use a naphthalene type epoxy resin. Furthermore, the naphthol aralkyl / cresol copolymer type epoxy resin represented by the following formula (II) and the biphenyl type epoxy resin represented by the following formula (III) are more preferable from the viewpoint of moldability when producing the laminate.

[Compound (A) having a hydroxyl group and an epoxy group in the molecular structure]
The compound (A) having a hydroxyl group and an epoxy group in the molecular structure of the present invention can be obtained by reacting the component (a) with the component (b). When component (a) and component (b) are reacted, an esterification reaction involving the generation of a secondary hydroxyl group proceeds. Here, the number of epoxy groups of component (b) (the amount of component (b) / the amount of epoxy groups of component (b)) is the number of carboxyl groups of component (a) (the amount of component (a) / component (a). The above component (a) and component (b) are preferably blended so as to be larger than the carboxyl group equivalent). Thus, the compound which has a hydroxyl group and an epoxy group in molecular structure is obtained by mix | blending said component (a) and component (b) and making it react.

  The ratio of the number of epoxy groups in component (b) to the number of carboxyl groups in component (a) (number of epoxy groups in component (b) / number of carboxyl groups in component (a)) is preferably 1.5 to 10.0. If this ratio is 1.5 or more, the reaction product of component (a) and component (b) is less likely to gel during the reaction. Moreover, if this ratio is 10.0 or less, it is less likely that the component (b) is insolubilized during the reaction and the moisture resistance of the resulting laminate is lowered.

  It is preferable to use an organic solvent for the reaction between the component (a) and the component (b). As a compounding quantity of an organic solvent, it is preferable that it is 40-1000 mass parts per 100 mass parts in total of a component (a) and a component (b), for example. If the compounding amount of the organic solvent is 40 parts by mass or more, the solubility of the component (a) and the component (b) is insufficient and the synthesis of the later-described component (A) is hardly difficult due to thickening. Moreover, if the compounding amount of the organic solvent is 1000 parts by mass or less, it takes less time for synthesis. Examples of the organic solvent used in this reaction include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, and hydrocarbon solvents. Examples include solvents, petroleum solvents, S atom-containing solvents such as dimethyl sulfoxide, and ester solvents such as γ-butyrolactone. These may be used alone or in combination of two or more.

  It is preferable that the organic solvent used for reaction of a component (a) and a component (b) has high solubility with respect to a component (a) and a component (b). The organic solvent is preferably highly volatile and hardly remains in the prepreg as a residual solvent during the production of the prepreg. From such a viewpoint, the organic solvent used for the reaction is preferably an aromatic solvent, and more preferably toluene, xylene, and mesitylene.

  In the reaction of component (a) and component (b), a reaction catalyst can be used as necessary. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more. Among these, it is preferable to use a phosphorus-based catalyst such as triphenylphosphine from the viewpoint of high reactivity with the component (a) and the component (b).

  Component (A) is prepared, for example, by adding component (a), component (b), an organic solvent, and a reaction catalyst to be added as necessary to a synthesis kettle, and stirring for 1 to 10 hours while heating and keeping heat as necessary. , Produced by reacting. The synthesis temperature of this component (A) is preferably in the range of 25 to 200 ° C. If the synthesis temperature is 25 ° C. or higher, the reaction rate is less likely to be too slow. Further, when the synthesis temperature is 200 ° C. or lower, it is not necessary to use a solvent having a high boiling point as the solvent used in the reaction. Therefore, when the prepreg is produced, it is difficult for the solvent to remain and heat resistance is reduced.

  The end point of the reaction and the generation of component (A) are determined, for example, as follows. A small sample is taken from the solvent in which component (a) and component (b) are reacted. And the acid value of a sample is measured by neutralization titration, and the reduction | decrease of the carboxyl group in a component (a) is confirmed. The acid value measurement method by neutralization titration conforms to the method according to JIS standards. Specifically, phenolphthalein is added as an indicator to a small sample taken out, and this is titrated with a potassium hydroxide methanol solution to confirm the neutralization point, thereby measuring the acid value of the sample. The acid value at the end of the reaction is preferably 1/5 or less of the acid value at the beginning of the reaction. If the acid value at the end point is 1/5 or less of the acid value at the beginning of the reaction, the amount of component (A) produced is hardly insufficient and good compatibility can be obtained.

  When a thermosetting resin composition is produced without reacting component (a) and component (b), unreacted carboxyl groups may remain in the thermosetting resin composition. In this case, since the unreacted carboxyl group reacts with the desmear liquid, the desmear liquid resistance may be lowered. On the other hand, when producing the thermosetting resin composition as in the present invention, when the component (a) and the component (b) are reacted in advance, the carboxyl group of the component (a) and the component (b) The reaction with the epoxy group proceeds selectively, and the component (A) obtained by this reaction has a stable structure incorporated in the polymer. Therefore, it is considered that the residual unreacted carboxyl group in the thermosetting resin composition is thereby suppressed, so that the desmear liquid resistance of the thermosetting resin composition is improved. Note that this principle does not limit the present invention.

[Compound (B) having two or more cyanate groups in one molecule]
Although it does not restrict | limit especially as a compound (B) which has 2 or more cyanate groups in 1 molecule of this invention, For example, the phenol novolak-type cyanate resin which has 2 or more cyanate groups in 1 molecule Is preferred, and a phenol novolac type cyanate resin represented by the following formula (IV) is more preferred.

  Further, u in the formula (IV) is preferably a positive number of 0.1 to 30, and more preferably a positive number of 5 to 15. If u is 0.1 or more, the component (B) becomes difficult to crystallize, and the handling of the component (B) becomes easy. Moreover, if u is 30 or less, it can suppress that the hardened | cured material obtained by hardening | curing a resin composition becomes weak.

[Organic metal salt (C)]
The organometallic salt (C) of the present invention is used as a curing accelerator when the component (A) and the component (B) react. The component (C) is preferably a fatty acid metal salt. The fatty acid metal salt may be a linear fatty acid metal salt or a cyclic fatty acid metal salt. Examples of component (C) include linear fatty acids such as stearic acid, lauric acid, ricinoleic acid and octylic acid, or aliphatic metal salts composed of cyclic fatty acids such as naphthenic acid and metal. These 1 type may be used independently, or 2 or more types may be mixed and used for them.

In general, when a curing accelerator is used, the activation energy of the curing reaction becomes small, and the curing reaction easily proceeds. However, if the activation energy is too small, the curing reaction proceeds even at room temperature (20 ° C.), so that the storage stability of the varnish and prepreg deteriorates. However, in the present invention, since the organic metal salt (C) is used as the curing accelerator, the activation energy of the curing reaction does not become too small, and the storage stability of the varnish and prepreg is improved. From the viewpoint of storage stability of varnish and prepreg, the component (C) preferably contains at least one selected from naphthenic acid metal salts and octylic acid metal salts. Furthermore, from the point that the activation energy is relatively small and the curing rate of the resin can be improved, the component (C) is represented by copper naphthenate represented by the following general formula (V) and the following general formula (VI). It is preferable to include at least one selected from tin octylate.

[Reaction between component (A) and component (B)]
The thermosetting resin composition of the present invention is a compound obtained by reacting a compound (A) having a hydroxyl group and an epoxy group in the molecular structure with a compound (B) having two or more cyanate groups in one molecule. It is preferable to contain. As a compounding quantity at the time of making a component (A) and a component (B) react, the compounding quantity of a component (A) shall be 10-60 mass parts per total 100 mass parts of a component (A) and a component (B). It is preferable that the compounding quantity of a component (B) shall be 40-90 mass parts. When the blending amounts of the component (A) and the component (B) are within these ranges, the resulting resin becomes more elastic and has better moisture and heat resistance and desmear resistance. Moreover, the compounding quantity of a component (C) is 0.001-1.0 mass part preferably per 100 mass parts of total of a component (A) and a component (B). When the blending amount of component (C) is 0.001 part by mass or more, the progress of the reaction becomes faster, and it takes less time to make the resin compatible. Moreover, the reaction rate of reaction of a component (A), a component (B), and a component (C) does not become too quick as the compounding quantity of a component (C) is 1.0 mass part or less, and end-point management of reaction is controllable. It becomes easy.

  It is preferable to dissolve these components (A), (B) and (C) in advance in an organic solvent. In an organic solvent, for example, at a reaction temperature of 80 to 120 ° C., the imino carbonate reaction, the triazine cyclization reaction, and the epoxy group insertion reaction of the component (A) and the component (B) can proceed.

  In the reaction between component (A) and component (B), it is preferable to use an organic solvent. The organic solvent used in this case is preferably an aromatic solvent as described above, and more preferably contains at least one selected from the group consisting of toluene, xylene and mesitylene. Moreover, you may mix another organic solvent in the range in which the characteristics, such as heat resistance, do not fall, without preventing progress of a desired reaction.

  The above 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, and the above triazine cyclization reaction is This is a reaction in which a cyanate group is trimerized to form a triazine ring. Thereby, a three-dimensional network structure is formed in the reaction product. Furthermore, the above-described epoxy group insertion reaction proceeds to form isocyanurate or oxazolidinone. By these reactions, a thermosetting resin composition in which component (A) and component (B) are dispersed is produced.

  The end point management of the reaction of the component (A) and the component (B) can be performed, for example, by examining the reaction rate of the component (B). The reaction rate of a component (B) can be calculated | required by the gel permeation chromatography (Gel Permeation Chromatography: GPC) measurement, for example. From the disappearance rate of the peak area calculated by comparing the peak area of the component (B) at the start of the reaction measured by GPC and the peak area of the component (B) after the reaction for a predetermined time, the reaction of the component (B) Rate is required. In this invention, it is preferable to make a component (A) and a component (B) react so that the reaction rate of a component (B) may be 10-50%. When the reaction rate of the component (B) is 10% or more, the component (A) and the component (B) are difficult to separate, and the obtained thermosetting resin composition is in a B-staged (semi-cured) state. It becomes easy to apply to the substrate. If the reaction rate of a component (B) is 50% or less, the obtained thermosetting resin composition will become easy to melt | dissolve in a solvent, and manufacture of a varnish will become easy. Moreover, if the reaction rate of a component (B) is 50% or less, it will reduce that the gelling time of the prepreg produced using the obtained thermosetting resin composition becomes too short. Thereby, the moldability of the prepreg at the time of pressing when producing a laminated board using the prepreg becomes favorable.

[Inorganic filler]
The thermosetting resin composition of the present invention may contain an inorganic filler. Thereby, characteristics, such as low thermal expansibility, high elasticity, heat resistance, or a flame retardance which the thermosetting resin composition of this invention expresses, can be improved further. The inorganic filler to be contained in the thermosetting resin composition can be appropriately selected depending on the characteristics to be improved. Examples of the inorganic filler include fused silica, crushed silica, mica, talc, short glass fiber, fine glass powder, hollow glass, calcium carbonate, quartz powder, and metal hydrate. These may be used alone as the inorganic filler, or two or more of these may be mixed and used.

Since it has a low coefficient of linear thermal expansion, the inorganic filler is preferably fused silica and has good dispersibility. Therefore, N-phenyl-3-aminopropyltrimethoxysilane represented by the following formula (VII) More preferred is fused silica surface treated with

  The above-mentioned surface-treated fused silica can be produced, for example, as follows. Fused silica is added to and mixed with a ketone organic solvent such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, or an alcohol organic solvent such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether to prepare a mixture. Thereafter, a trimethoxysilane compound represented by the above formula (VII) is added to the mixture. While stirring the mixture at a temperature of 60 to 120 ° C. for about 0.5 to 5 hours, the fused silica and the trimethoxysilane compound are reacted to obtain the above-described fused silica.

  The above-mentioned surface-treated fused silica can also be obtained commercially from Admatechs Corporation. Examples of such fused silica include fused silica of trade names “SC-2050KNK” and “SC-2050HNK” manufactured by Admatechs Co., Ltd.

  The blending amount of the inorganic filler is preferably 10 to 300 parts by mass, and 150 to 250 parts by mass with respect to 100 parts by mass in total of the compound (A) and the compound (B) of the thermosetting resin composition of the present invention. More preferably, it is a part. When the blending amount of the inorganic filler is 10 parts by mass or more, the elastic modulus and moisture heat resistance of the obtained resin can be improved. Moreover, it can suppress that the moldability and desmear liquid resistance of a thermosetting resin composition fall by addition of an inorganic filler as the compounding quantity of an inorganic filler is 300 mass parts or less.

[Other ingredients]
The thermosetting resin composition of the present invention includes known thermoplastic resins, elastomers, flame retardants, organic fillers, and the like as desired in order to further improve heat resistance, flame retardancy, copper foil adhesion, and the like. But you can.

  Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin. . These may be used alone or in combination of two or more.

  Examples of the elastomer include acrylonitrile-butadiene-based polymers, carboxy-modified acrylonitrile-butadiene-based polymers, and diene-based elastomers such as polybutadiene, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, and phenol-modified polybutadiene. These may be used alone or in combination of two or more.

  Examples of the flame retardant include phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate compounds, phosphazenes and red phosphorus, and inorganic flame retardants such as antimony trioxide and zinc molybdate. Examples include flame retardants. These may be used alone or in combination of two or more. As the flame retardant, an inorganic flame retardant in which zinc molybdate is supported on an inorganic filler such as talc is preferable because not only flame retardancy is improved but also drilling workability is remarkably improved.

  When using zinc molybdate as a flame retardant, it is preferable that the compounding quantity shall be 5-20 mass parts with respect to a total of 100 mass parts of a compound (A) and a compound (B). When the blending amount of the flame retardant is 5 parts by mass or more, an effect of improving flame retardancy and drilling workability is obtained, and when the blending amount of the flame retardant is 20 parts by mass or less, the gelation time of the varnish is sufficient. It becomes long and the moldability at the time of shape | molding a laminated board with a press improves.

  Examples of the organic filler include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether. These may be used alone or in combination of two or more.

  The thermosetting resin composition of the present invention can further contain an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like. For example, UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals and thioxanthones, fluorescent whitening agents such as stilbene derivatives, In addition, a urea compound such as urea silane and an adhesion improver such as a silane coupling agent may be included.

[Prepreg]
The prepreg of the present invention is obtained by impregnating or coating the base material with the thermosetting resin composition of the present invention. For this reason, when producing a prepreg using the thermosetting resin composition of this invention, it is preferable that the thermosetting resin composition of this invention is a varnish state. Here, the varnish state refers to a state in which the thermosetting resin composition of the present invention is dissolved or dispersed in an organic solvent.

[Base material for prepreg]
As the base material of the prepreg of the present invention, known materials used for various laminates for electrical insulating materials can be used. Examples of the material of the substrate include inorganic fibers such as E glass, D glass, S glass, and Q glass, and organic fibers. These may be used alone or in combination of two or more. From the viewpoint of low thermal expansion, it is preferable to use Q glass and organic fibers as the material of the base material. Examples of the resin constituting the organic fiber include aramid resin, polyester resin, aromatic polyester resin, aromatic polyether ketone resin, polyparaphenylene benzbisoxazole resin, polyamide resin, polyimide resin, polyester resin, and ultrahigh molecular polyethylene. Examples thereof include resins and fluororesins. Commercially available products may be used as the organic fibers. Examples of commercially available products include aramid fiber cloth (trade name: Technora) manufactured by Asahi Kasei E-Materials Co., Ltd., and aromatic polyester fiber cloth (trade name: XXION). And polyparaphenylene benzobisoxazole fiber cloth (trade name: Zylon).

  Examples of the form of these base materials include woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat. The material and shape of the substrate are appropriately selected depending on the intended use and performance of the molded product. As needed, the base material which combined 1 type, or 2 or more types of the above-mentioned material and form can be used for the prepreg of this invention. Although the thickness of a base material is not specifically limited, For example, it is about 0.03 to about 0.5 mm. A substrate surface-treated with a silane coupling agent or the like or a substrate subjected to mechanical opening treatment is preferable from the viewpoint of heat resistance, moisture resistance, workability, and the like.

  Impregnating or coating the substrate with the thermosetting resin composition so that the amount of the thermosetting resin composition attached to the substrate after drying is 20 to 90% by mass of the mass of the prepreg after drying. Is preferred. Thereafter, the base material impregnated or coated is dried by heating at, for example, a temperature of 100 to 200 ° C. for 3 to 15 minutes, and the thermosetting resin composition impregnated or coated on the base material is semi-cured (B-stage). ) To produce a prepreg.

[Laminated board]
The laminate of the present invention is formed by laminating the prepreg of the present invention. For example, 1 to 20 prepregs of the present invention are stacked to form a laminate, and after placing metal foils such as copper and aluminum on one or both sides of the laminate, the laminate of the present invention is formed by laminate molding. Can be obtained. The metal foil is not particularly limited as long as it is used for electrical insulating material applications.

For forming the laminate of the present invention, conventional laminates for electrical insulation materials and multilayer plates can be applied. For example, a multistage press, a multistage vacuum press, a continuous molding, an autoclave molding machine, or the like can be used for molding the laminate of the present invention. For example, the molding temperature when molding the laminate is 100 to 250 ° C., the molding pressure is ² to 100 kg / cm ² , and the heating time is 0.1 to 5 hours.

  The laminated board of the present invention may include other prepregs and wiring boards as long as the prepreg of the present invention is laminated. For example, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to obtain a laminated board.

[Printed wiring board]
The printed wiring board of the present invention is one in which a conductor pattern is formed on the surface or surface and inside of the laminated board of the present invention. For example, a printed wiring board is oxidized by irradiating a laser on the oxide layer formed on the surface of the metal foil and a step of forming an oxide layer of the main component of the metal foil on the surface of the metal foil of the laminated board. A step of forming a hole penetrating the material layer and the metal foil, a step of performing a desmear treatment after removing the oxide layer formed on the surface of the metal foil, a plating treatment, and forming a plating film inside the hole It is produced by the forming step. For example, the metal foil is a copper foil and the oxide layer is a copper oxide layer.

[Mounting board]
The mounting board of the present invention includes the printed wiring board of the present invention, and a printed component and a mounted component arranged on the printed wiring board of the present invention. For example, the printed component is a semiconductor package wiring board, and the mounted component is a semiconductor element.

  Next, the present invention will be described in more detail with reference to the following examples, but these examples are not intended to limit the present invention in any way. Using the thermosetting resin composition in one embodiment of the present invention, a prepreg and a copper-clad laminate were produced, and the produced copper-clad laminate was evaluated. The evaluation method is shown below.

[Evaluation method]
(1) Evaluation of flexural modulus A copper-clad laminate was immersed in a copper etchant to produce a laminate from which the copper foil was removed from the copper-clad laminate, and a 25 mm × 40 mm test piece was cut out from the laminate. Evaluation substrate A was produced. Evaluation substrate A was further heated at 250 ° C. for 2 hours to obtain evaluation substrate B. Bending elasticity of evaluation substrates A and B at 25 ° C. using a 5-ton tensilon device (trade name: RTC-1350A, manufactured by Orientec Co., Ltd.) under measurement conditions of a crosshead speed of 1 mm / min and a span distance of 20 mm. The rate was measured.

(2) Measurement of linear thermal expansion coefficient A copper-clad laminate was dipped in a copper etchant to produce a laminate from which the copper foil was removed from the copper-clad laminate, and a 4 mm x 30 mm test piece was cut out from the laminate Thus, an evaluation substrate C was produced. The linear thermal expansion coefficient in the plane direction at 30 to 100 ° C. of the evaluation substrate C was measured using a TMA test apparatus (trade name: TMA-Q400, manufactured by TA Instruments). The linear thermal expansion coefficient was measured for the following reason. The copper-clad laminate is desired to be further reduced in thickness, and in conjunction with this, the prepreg constituting the copper-clad laminate is also being considered to be thinner. Since the thinned prepreg is likely to warp, it is desired that the prepreg warp during heat treatment be small. In order to reduce the warpage, it is effective that the linear thermal expansion coefficient in the surface direction of the substrate is low.

(3) Evaluation of moisture-absorbing solder heat resistance A copper-clad laminate is dipped in a copper etching solution to produce a laminate from which the copper foil has been removed, and a 40 mm square test piece is cut out from the laminate. An evaluation substrate D was produced. The evaluation substrate D was subjected to a pressure cooker treatment for 5 hours under the treatment conditions of 100% RH, 121 ° C., and 2 atm using a pressure cooker test apparatus manufactured by Hirayama Seisakusho. Thereafter, the evaluation substrate D was immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, the appearance was observed, and the occurrence of blisters and cracks was examined to evaluate the moisture absorption solder heat resistance of the evaluation substrate D.

(4) Evaluation of desmear liquid resistance A laminate obtained by removing a copper foil from a copper-clad laminate by immersing the copper-clad laminate in a copper etching solution, and cutting out a 40 mm square test piece from the laminate Evaluation board E was produced. And the evaluation board | substrate E was immersed for 5 minutes by the swelling aqueous solution (Rohm and Haas Japan Co., Ltd. product name: Circoposit MLB conditioner 211) which has the temperature of 80 degreeC by the dip method. Thereafter, the evaluation substrate E was washed with water at room temperature for 3 minutes, and a strong permanganate aqueous solution having a temperature of 80 ° C. (trade name: Circoposit MLB Promoter 213, manufactured by Rohm and Haas Japan Co., Ltd.) by the dip method. ) For 15 minutes. And the mass reduction | decrease amount (g / m < ² >) before and behind the immersion process of the evaluation board | substrate E was measured.

(5) Evaluation of storage stability of varnish 0.5 ml of varnish was weighed from varnish immediately after production, and the varnish was measured using a gelation tester (manufactured by Nisshin Kagaku Co., Ltd., trade name: TYPEGT-JIS). The gelation time of was measured. The measurement temperature for the gelation time was 160 ° C. Further, after the produced varnish was stored at a temperature of 20 ° C. for 3 days, the gelation time was measured by the same method. The smaller the difference between the gelation time measured immediately after production of the varnish and the gelation time measured after storage for 3 days at a temperature of 20 ° C., the better the storage stability of the varnish.

(6) Calculation of activation energy Ea 0.5 ml of varnish is weighed out from the obtained varnish, and the gel of the varnish is used using a gelling tester (manufactured by Nisshin Kagaku Co., Ltd., trade name: TYPEGT-JIS) The conversion time was measured. The gelation time was measured at 140, 150, 160, 170 and 180 ° C., respectively. Time (Tgel) (s) until the varnish was completely cured at each measurement temperature was measured.

（式中、Ｒは気体定数（Ｊ・Ｋ^-1・ｍｏｌ^-1）、Ｔは測定温度（Ｋ）、Ｅａは活性化エネルギー（ｋＪ／ｍｏｌ）、Ａは温度に依らない定数（ｓ^-1））
したがって、測定温度の逆数を横軸、反応速度の対数を縦軸にとり、得られた近似直線の傾きから、活性化エネルギーＥａ（ｋＪ／ｍｏｌ）を算出した。 When the reaction rate is (1 / Tgel) (s ⁻¹ ), the reaction rate, the reciprocal of the measured temperature, and the activation energy Ea (kJ / mol) have a relationship represented by the following Arrhenius equation (1).

(Wherein R is a gas constant (J · K ⁻¹ · mol ⁻¹ ), T is a measurement temperature (K), Ea is an activation energy (kJ / mol), and A is a temperature independent constant (s ⁻¹ ))
Therefore, taking the reciprocal of the measured temperature on the horizontal axis and the logarithm of the reaction rate on the vertical axis, the activation energy Ea (kJ / mol) was calculated from the slope of the obtained approximate line.

Identification of the thermosetting resin compositions produced in Production Examples and Comparative Production Examples was performed by GPC measurement and FT-IR measurement. Each measurement condition is as follows.
(7) GPC measurement The conditions of GPC measurement were as follows. The apparatus used for the GPC measurement is an autosampler (manufactured by Tosoh Corporation, trade name: AS-8020), a column oven (manufactured by JASCO Corporation, trade name: 860-C0), an RI detector (JASCO). Industrial Co., Ltd., trade name: 830-RI), UV / VIS detector (manufactured by JASCO Corporation, trade name: 870-UV) and HPLC pump (manufactured by JASCO Corporation, trade name: 880-PU). In addition, the column used for the measurement is a column manufactured by Tosoh Corporation having trade names “TSKgel SuperHZ2000” and “TSKgel SuperHZ2300”, the measurement temperature is 40 ° C., and the flow rate is 0.5 ml / min. The solvent was tetrahydrofuran (THF).

(8) FT-IR measurement FT-IR measurement uses a Fourier transform infrared spectrometer (trade name: FT / IR-6300, manufactured by JASCO Corporation), resolution 4 cm ^-1 , measurement range The measurement was performed at 4000 to 400 cm ^-1 and 32 times of integration. A small amount of a reaction solution described later was applied to a thallium plate, the solvent was volatilized with compressed air, and a thin film of a thermosetting resin composition was formed on the thallium plate. And the infrared light was irradiated to the thallium board in which the thin film of the thermosetting resin composition was formed, and the FT-IR measurement was performed.

(Production example)
(1) Production Example 1: Production of Thermosetting Resin Composition (1-1) In a reaction vessel having a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liter, the above general formula (III ) And R ^{2 to} R ⁵ are CH ₃ biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: YX-4000, epoxy equivalent: 186): 180.0 g and the following formula (VIII ) (Made by Shin-Etsu Chemical Co., Ltd., trade name: X-22-162A, carboxyl group equivalent: 865): 120.0 g, toluene: 700.0 g, triphenylphosphine: 1.09 g ( The mixture was prepared by charging 3.0 mol% with respect to the carboxyl group of the siloxane resin. The equivalent ratio of the reaction was the number of epoxy groups / number of carboxyl groups = 7.0.

Next, while stirring the above mixture, the temperature of the mixture was raised to 110 ° C., and the mixture was reacted at about 110 ° C. When the mixture was reacting, sampling was performed every 0.5 hour, and the acid value of the mixture was measured by neutralization titration. After reacting for 3 hours, it was confirmed that the acid value of the mixture became 0 mgKOH / g. The mixture was cooled to room temperature to obtain a solution of the compound (A-1) having a hydroxyl group and an epoxy group in the molecular structure having the structure represented by the following general formula (IX).

  Next, in a reaction vessel having a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser, the solution of the above compound (A-1): 800.0 g (solid content: 240.0 g) Then, phenol novolac-type cyanate resin (Lonza Japan Co., Ltd., trade name: PT-30): 240.0 g was added to prepare a mixture. Then, the temperature of the mixture was raised to 110 ° C. while stirring the mixture, and after confirming that the resin solids were dissolved and the mixture was a uniform solution, 8% by mass mineral spirit of copper naphthenate 0.24 g of the solution was added to the mixture to prepare a reaction solution. And the reaction liquid was made to react at about 110 degreeC for 4 hours. Then, the reaction liquid was cooled to room temperature and the solution of the thermosetting resin composition (1-1) was obtained.

A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). The peak area of the phenol novolac cyanate resin, which is a synthetic raw material that appears at around 12.2 minutes, is compared with the peak area of the phenol novolac cyanate resin at the start of the reaction. 33%. From this, the reaction rate of the phenol novolac type cyanate resin was 33%. Furthermore, when a small amount of the reaction solution was taken out and FT-IR measurement was performed by a thin film formation method, a peak appearing in the vicinity of a wave number of 1560 cm ^{−1 of the} triazine ring produced by the polymerization reaction could be confirmed. It was also possible to confirm a peak appeared in the vicinity of isocyanurate and wave number 1670 cm ^-1 and 1740 cm ^-1 of the oxazolidinone produced by the insertion reaction of the epoxy groups respectively. Thereafter, the resin solution was concentrated under reduced pressure to adjust the resin content to 70% by mass to obtain a thermosetting resin composition (1-1).

(2) Production Example 2: Production of thermosetting resin composition (1-2) Biphenyl type epoxy resin: Naphthol aralkyl-cresol copolymer type epoxy resin represented by the above general formula (II) instead of 180.0 g (Japan) Production similar to the production method of the thermosetting resin composition (1-1) except that Kayaku Co., Ltd., trade name: NC-7000L, epoxy equivalent: 230): 180.0 g was used. A thermosetting resin composition (1-2) was obtained by the method. The equivalent ratio of the reaction changed from the number of epoxy groups / carboxyl groups = 7.0 to the number of epoxy groups / carboxyl groups = 5.6, and the reaction rate of the phenol novolac type cyanate resin changed from 33% to 31%.

(3) Production Example 3: Production of thermosetting resin composition (1-3) Biphenyl type epoxy resin: Naphthol aralkyl-cresol copolymer type epoxy resin instead of 180.0 g (manufactured by Nippon Kayaku Co., Ltd., product) Name: NC-7000L, epoxy equivalent: 230): 226.2 g used, siloxane resin: siloxane resin represented by the following general formula (X) instead of 120.0 g (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) : X-22-162B, carboxyl group equivalent: 1500): The above thermosetting resin except that 150.8 g was used and the blending amount of triphenylphosphine was changed from 1.37 g to 0.79 g. The thermosetting resin composition (1-3) was obtained by the manufacturing method similar to the manufacturing method of a composition (1-1). The equivalent ratio of the reaction changed from the number of epoxy groups / the number of carboxyl groups = 7.0 to the number of epoxy groups / the number of carboxyl groups = 9.7, and the time when it was confirmed that it became 0 mgKOH / g was 3 hours after the reaction and 5 hours after the reaction. The reaction rate of the phenol novolac cyanate resin was changed from 33% to 30%.

(4) Production Example 4: Production of thermosetting resin composition (1-4) Biphenyl type epoxy resin: Naphthol aralkyl-cresol copolymer type epoxy resin instead of 180.0 g (manufactured by Nippon Kayaku Co., Ltd., product) Name: NC-7000 L, epoxy equivalent: 230): 226.2 g, the point that the amount of siloxane resin was changed from 120.0 g to 150.8 g, and 8% by mass mineral spirit solution of copper naphthenate A thermosetting resin composition (1-1) was produced by the same production method as that for the thermosetting resin composition (1-1) except that 0.07 g of tin octylate was added instead of 0.24 g. 4) was obtained. The equivalent ratio of the reaction changed from the number of epoxy groups / the number of carboxyl groups = 7.0 to the number of epoxy groups / the number of carboxyl groups = 5.6, and the reaction rate of the phenol novolac type cyanate resin changed from 33% to 34%.

(5) Production Example 5: Production of thermosetting resin composition (1-5) Biphenyl type epoxy resin: Naphthol aralkyl-cresol copolymer type epoxy resin instead of 180.0 g (manufactured by Nippon Kayaku Co., Ltd., product) Name: NC-7000L, epoxy equivalent: 230): 226.2 g used, siloxane resin compounding amount changed from 120.0 g to 150.8 g, and 8% by weight mineral spirit solution of copper naphthenate A thermosetting resin composition (1-5) was produced by a production method similar to the production method of the thermosetting resin composition (1-1) except that an 8% by mass mineral spirit solution of naphthenic zinc was used instead. ) The equivalent ratio of the reaction changed from the number of epoxy groups / carboxyl groups = 7.0 to the number of epoxy groups / carboxyl groups = 5.6, and the reaction rate of the phenol novolac type cyanate resin changed from 33% to 31%.

(6) Production Example 6: Production of thermosetting resin composition (1-6) Biphenyl type epoxy resin: Naphthol aralkyl-cresol copolymer type epoxy resin instead of 180.0 g (manufactured by Nippon Kayaku Co., Ltd., product) Name: NC-7000 L, epoxy equivalent: 230): 226.2 g, the point that the amount of siloxane resin was changed from 120.0 g to 150.8 g, and 8% by mass mineral spirit solution of copper naphthenate The thermosetting resin composition (1) was produced by the same production method as that for the thermosetting resin composition (1-1) except that 0.12 g of zinc octylate was added instead of 0.24 g. -6) was obtained. The equivalent ratio of the reaction changed from the number of epoxy groups / carboxyl groups = 7.0 to the number of epoxy groups / carboxyl groups = 5.6, and the reaction rate of the phenol novolac type cyanate resin changed from 33% to 31%.

(7) Production Example 7: Production of thermosetting resin composition (1-7) Biphenyl type epoxy resin: Naphthol aralkyl-cresol copolymer type epoxy resin instead of 180.0 g (manufactured by Nippon Kayaku Co., Ltd., product) Name NC-7000L, epoxy equivalent: 230): 226.2 g used, siloxane resin compounding amount changed from 120.0 g to 150.8 g, and 8% by mass mineral spirit solution of copper naphthenate. Thermosetting by the same manufacturing method as the above thermosetting resin composition (1-1) except that 0.48 g of a 6 mass% mineral spirit solution of cobalt naphthenate was added instead of adding 24 g. Resin composition (1-7) was obtained. The equivalent ratio of the reaction changed from the number of epoxy groups / the number of carboxyl groups = 7.0 to the number of epoxy groups / the number of carboxyl groups = 5.6, and the reaction rate of the phenol novolac type cyanate resin changed from 33% to 30%.

(8) Comparative Production Example 1: Production of (Comparative 1) In Comparative Production Example 1, a thermosetting resin composition was produced without esterifying the compound having an epoxy group and the siloxane resin in advance.
In a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser, phenol novolac-type cyanate resin (Lonza Japan Co., Ltd., trade name: PT-30): 240.0 g Siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-162A, carboxyl group equivalent: 865): 96.0 g, naphthol aralkyl-cresol copolymer epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) , Trade name: NC-7000L, epoxy equivalent: 230): 144.0 g and cyclohexanone: 560.0 g were added to prepare a mixture.

  Next, the temperature of the mixture is raised to 120 ° C. while stirring the mixture, and after confirming that the resin solids are dissolved and the mixture is a uniform solution, an 8% by mass mineral spirit solution of copper naphthenate 0.48 g was added, and the reaction was carried out at about 110 ° C. for 6 hours. Then, it cooled to room temperature and obtained the solution of (Comparative 1).

  A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). The peak area of the phenol novolac cyanate resin, which is a synthetic raw material that appears at around 12.2 minutes, is compared with the peak area of the phenol novolac cyanate resin at the start of the reaction. 41%. From this, the reaction rate of the phenol novolac type cyanate resin was 41%.

Furthermore, when a small amount of the reaction solution was taken out and FT-IR measurement was performed by a thin film formation method, a peak appearing in the vicinity of a wave number of 1560 cm ^{−1 of the} triazine ring produced by the polymerization reaction could be confirmed. It was also possible to confirm a peak appeared in the vicinity of isocyanurate and wave number 1670 cm ^-1 and 1740 cm ^-1 of the oxazolidinone produced by the insertion reaction of the epoxy groups respectively. Thereafter, the resin solution was concentrated under reduced pressure to adjust the resin content to 70% by mass to obtain a thermosetting resin composition (Comparative 1).

(9) Comparative Production Example 2: Production of (Comparative 2) In Comparative Production Example 2, a thermosetting resin composition was produced using triethylamine as a curing accelerator instead of an organic metal salt.
Biphenyl type epoxy resin: naphthol aralkyl cresol copolymer type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-7000L, epoxy equivalent: 230): 226.2 g instead of 180.0 g, The amount of siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name: X-22-162A, carboxyl group equivalent: 865) was changed from 120.0 g to 150.8 g, and 8% by mass of copper naphthenate The thermosetting resin composition was produced by the same production method as the above-mentioned production method of the thermosetting resin composition (1-1) except that 21.60 g of triethylamine was added instead of adding 0.24 g of the mineral spirit solution. (Comparison 2) was obtained. The equivalent ratio of the reaction changed from the number of epoxy groups / the number of carboxyl groups = 7.0 to the number of epoxy groups / the number of carboxyl groups = 5.6, and the reaction rate of the phenol novolac type cyanate resin changed from 33% to 35%.

(10) Comparative Production Example 3: Production of (Comparative 3) In Comparative Production Example 3, tetrakis (4-methylphenyl) borane-tetraphenylphosphine complex (TPP-MK) is used as a curing accelerator instead of the organometallic salt. Thus, a thermosetting resin composition was produced.
Biphenyl type epoxy resin: naphthol aralkyl cresol copolymer type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-7000L, epoxy equivalent: 230): 226.2 g instead of 180.0 g, The amount of siloxane resin (trade name: X-22-162A, carboxyl group equivalent: 865, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 120.0 g to 150.8 g, and 8% by mass of copper naphthenate A thermosetting resin is produced by the same production method as that of the thermosetting resin composition (1-1) except that 19.20 g of TPP-MK is added instead of adding 0.24 g of the mineral spirit solution. A composition (Comparative 3) was obtained. The equivalent ratio of the reaction changed from the number of epoxy groups / the number of carboxyl groups = 7.0 to the number of epoxy groups / the number of carboxyl groups = 5.6, and the reaction rate of the phenol novolac type cyanate resin changed from 33% to 34%.

(Production of varnish)
The thermosetting resin compositions obtained by Production Examples 1 to 7 and Comparative Production Examples 1 to 3, fused silica, and cyclohexanone (diluting solvent) were mixed at the blending ratio (parts by mass) shown in Tables 1 to 3. A varnish with a solid content of 70% by mass was prepared. In Examples 1 to 11 and Comparative Example 1, varnishes were obtained, but in Comparative Examples 2 and 3, the resin and fused silica were separated, and varnishes could not be obtained.

(Preparation of prepreg)
The inorganic fiber base material having a thickness of 0.05 to 0.1 mm and the organic fiber base material were impregnated with the varnish and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a solid content of 50% by mass.

(Production of laminates)
Four prepregs are stacked to produce a laminate, 18 μm electrolytic copper foils are placed on the top and bottom of the laminate, and the laminate is pressed for 60 minutes under pressure conditions of 25 kg / cm ² and a temperature of 240 ° C. A tension laminate was obtained. Using the evaluation substrates A to E produced from the laminates thus obtained, the bending elastic modulus, the linear thermal expansion coefficient, the hygroscopic solder heat resistance, and the desmear liquid resistance were evaluated. The evaluation results are shown in Tables 1-3.

The numbers in Tables 1 to 3 are indicated by mass parts of solid content. Each order is
* 1: Product name: SC-2050HNK, manufactured by Admatechs Co., Ltd.
* 2: Nittobo Co., Ltd .; # 2118 Style S glass cloth (95 μm) (GAT-7010)
* 3: Shin-Etsu Quartz Co., Ltd .; # 2116 style Q glass cloth (85 μm) (SQF-2116AC)
* 4: Asahi Kasei E-Materials Corporation; Aramid fiber cloth (60μm) (Product name: Technora)
* 5: Asahi Kasei E-Materials Co., Ltd .; Aromatic polyester fiber cloth (70 μm) (Product name: XXION)
* 6: Asahi Kasei E-Materials Co., Ltd .; polyparaphenylene benzobisoxazole fiber cloth (65 μm) (Product name: Zylon)
* 7: Wako Pure Chemical Industries, Ltd., trade name: copper naphthenate mineral spirit solution (copper 8% by mass)
* 8: Wako Pure Chemical Industries, Ltd., trade name: Tin 2-ethylhexanoate (II)
* 9: Wako Pure Chemical Industries, Ltd., trade name: Naphthenic acid zinc mineral spirit solution (zinc 8% by mass)
* 10: Wako Pure Chemical Industries, Ltd., trade name: zinc 2-ethylhexanoate (II)
* 11: Wako Pure Chemical Industries, Ltd., trade name: cobalt naphthenate mineral spirit solution (cobalt 8% by mass)
* 12: Using a gelation tester manufactured by Nisshin Kagaku Co., Ltd., measuring temperature is 160 ° C
* 13: Wako Pure Chemical Industries, Ltd., trade name: Triethylamine
* 14: Wako Pure Chemical Industries, Ltd., trade name: Tetrakis (4-methylphenyl) borane-tetraphenylphosphine complex (TPP-MK)

[Evaluation results]
As is clear from Tables 1 to 3, the thermosetting resin compositions obtained in Comparative Examples 2 and 3 have a small activation energy, and the curing reaction proceeds even at room temperature (20 ° C.). The thermosetting resin was deposited, the varnish could not be applied to the substrate, and the prepreg could not be produced. The laminated board obtained in Comparative Example 1 had poor moisture-absorbing solder heat resistance and a large amount of mass reduction due to desmear liquid. On the other hand, the laminates obtained in Examples 1 to 11 are highly elastic, excellent in low thermal expansion, moisture and heat resistance, and desmear liquid resistance, and also excellent in storage stability of varnish. In particular, a thermosetting resin composition containing copper naphthenate or tin octylate as an organic metal salt is excellent in storage stability of varnish, and a highly elastic laminate can be obtained even at 185 ° C. pressing conditions. I understand.

Claims (7)

In the molecular structure obtained by reacting a siloxane resin (a) having a carboxyl group and a compound (b) having two or more epoxy groups in one molecule, represented by the following general formula (I) A thermosetting resin composition comprising a compound (A) having a hydroxyl group and an epoxy group, a compound (B) having two or more cyanate groups in one molecule, and an organometallic salt (C).

(Wherein R ₁ is each independently a saturated hydrocarbon group having 1 to 5 carbon atoms, and m is an integer of 5 to 100)   The thermosetting of Claim 1 containing the compound obtained by making the compound (A) which has a hydroxyl group and an epoxy group in molecular structure react with the compound (B) which has a 2 or more cyanate group in 1 molecule. Resin composition.   The thermosetting resin composition according to claim 1 or 2, wherein the organic metal salt (C) is at least one selected from a naphthenic acid metal salt and an octylic acid metal salt.   A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition according to any one of claims 1 to 3.   A laminate obtained by laminating the prepreg according to claim 4.   The printed wiring board by which the conductor pattern was formed in the surface or surface of the laminated board of Claim 5, and the inside. The printed wiring board according to claim 6;
A mounting board including a printed component and a mounted component disposed on the printed wiring board.