JP2013189578A - Compatibilization resin, and thermosetting resin composition, prepreg and laminated plate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent all in Tg, low thermal expansion, copper foil adhesivity, heat resistance, moisture resistance, flame retardancy, heat resistance with copper, low dielectric property, low dielectric loss tangent and alkaline liquid resistance, and use of the same, and a prepreg, a laminated plate and the like using the same.SOLUTION: A thermosetting resin composition contains: a compatibilization resin obtained by reacting a compound (A) which is obtained by etherifying a siloxane resin (a) having phenolic hydroxyl groups on terminals thereof and a compound (b) having at least two epoxy groups in one molecule thereof, and which has hydroxyl groups and epoxy groups in the molecular structure with a compound (B) having at least two isocyanate groups in one molecule thereof, using an organometal salt (C) as a reaction catalyst; and a fused silica surface-treated with the compatibilization resin and an N-phenyl-3-aminopropyltrimethoxysilane compound.

Description

  The present invention exhibits particularly excellent low thermal expansion, dielectric properties, flame retardancy, adhesiveness, heat resistance, and alkali liquid resistance, and is suitable for electronic parts that are low in toxicity and excellent in safety and work environment. The present invention relates to a compatibilizing resin that becomes a thermosetting resin. Moreover, it is related with the thermosetting resin composition using such a compatibilizing resin, the prepreg using this thermosetting resin, and a laminated board.

  Thermosetting resins are widely used in the field of electronic components, etc., because the cross-linked structure unique to thermosetting resins expresses high heat resistance and dimensional stability, especially in copper-clad laminates and interlayer insulation materials, Due to recent demands for higher density and higher reliability, high copper foil adhesion, heat resistance, good low thermal expansion, and the like are required. Moreover, due to recent environmental problems, mounting of electronic parts using lead-free solder and flame resistance using halogen-free are required, and therefore higher heat resistance and flame resistance than conventional ones are required. 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 only of low-toxic components and does not generate toxic gases.

  The cyanate compound, a thermosetting resin, is a resin with low dielectric properties and excellent flame retardancy, but when used as it is in an epoxy curable thermosetting resin, there is a problem of insufficient heat resistance and toughness. . Moreover, the low thermal expansion property corresponding to the next generation is insufficient. Patent Documents 1, 2, 3 and the like disclose resin compositions comprising a cyanate compound and an inorganic filler and exhibiting low thermal expansion. However, since these exhibit low thermal expansion, the amount of inorganic filler used is limited. In many cases, when used as a copper clad laminate or an interlayer insulating material, drillability and formability are insufficient. Moreover, although the example regarding the thermosetting resin which contains cyanate resin and an aralkyl modified epoxy resin as an essential component is indicated by patent document 4, patent document 5, etc., cyanate resin which is an essential component is toughness and hardening reactivity. Because it is an inferior resin, the improvement in curing reactivity and toughness of this thermosetting resin is still insufficient, and even when these are used as copper-clad laminates or interlayer insulation materials, heat resistance, reliability, workability There was a problem of lacking.

JP 2003-268136 A JP 2003-73543 A JP 2002-285015 A JP 2002-309085 A JP 2002-348469 A

  The object of the present invention is thermosetting excellent in all of low thermal expansion, copper foil adhesion, heat resistance, moisture resistance, flame resistance, alkali liquid resistance, heat resistance with copper, low dielectric properties, and low dielectric loss tangent. While providing the compatibilizing resin which is a thermosetting resin from which the resin composition is obtained, the use of such a thermosetting resin composition, for example, a prepreg and a laminated board is provided.

  As a result of studying to solve the above problems, the present inventors have reacted a siloxane resin having a phenolic hydroxyl group at the terminal with an epoxy resin in the presence of an organic phosphine, and then reacting with a cyanate resin. The inventors have found that a thermosetting compatibilizing resin that can be used as a thermosetting resin composition excellent in all the above-mentioned properties is obtained, and the present invention has been completed.

（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から１００までの数である）
（２）この相容化樹脂と、下記式（II）で示されるトリメトキシシラン化合物により表面処理（湿式処理）された溶融シリカと、を含有する熱硬化性樹脂組成物に関する。

また、本発明は、（３）上記の熱硬化性樹脂組成物を用いて形成されたプリプレグおよび（４）このプリプレグを用いて積層成形された積層板に関するものである。 That is, the present invention provides (1) a siloxane resin (a) having a hydroxyl group at the terminal represented by the following formula (I) and a compound (b) having at least two epoxy groups in one molecule: Compound (A) having a hydroxyl group and an epoxy group in the molecular structure obtained by etherification using 2.0 mol% or more of organic phosphines (c) as a catalyst with respect to the compound having an epoxy group of b) A compound (A) having a hydroxyl group and an epoxy group in the obtained molecular structure and a compound (B) having at least two cyanate groups in one molecule are used as a reaction catalyst with an organometallic salt ( Using (C), an iminocarbonation reaction and a triazine cyclization reaction are performed, and the reaction rate (disappearance rate) of the compound having a cyanate group in (B) is 30 to 70 mol%. Compatibilizer resin obtained by, and

(Wherein R ₁ is each independently a saturated hydrocarbon group having 1 to 5 carbon atoms, and m is a number from 5 to 100)
(2) The present invention relates to a thermosetting resin composition containing this compatibilizing resin and fused silica surface-treated (wet treatment) with a trimethoxysilane compound represented by the following formula (II).

The present invention also relates to (3) a prepreg formed using the above-mentioned thermosetting resin composition and (4) a laminate formed by lamination using this prepreg.

  The thermosetting resin composition prepared by using the compatibilizing resin of the present invention has a high Tg, and a prepreg obtained by impregnating or coating the base material on the base material, and laminating the prepreg. The manufactured laminate is excellent in low thermal expansion, copper foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with copper (T-300), low dielectric properties, low dielectric loss tangent, and alkali liquid resistance. It is useful as a printed wiring board for electronic equipment.

Hereinafter, the present invention will be described in detail.
Laminate materials require high copper foil adhesion, heat resistance, good low thermal expansion, etc. due to recent demands for higher density and higher reliability. The peel strength of the copper foil is desirably 1.0 kN / m or more, and more desirably 1.2 kN / m or more.
In addition, it is necessary to increase the number of layers using a build-up material or the like for high density, and high reflow heat resistance is required. However, heat resistance with copper (T- 300) is preferably free from blistering for 30 minutes or more.
Furthermore, as the density increases, the base material tends to be thinner, and it is necessary for the base material to be less warped during heat treatment. In order to reduce warpage, it is effective that the surface direction of the base material has low thermal expansion, and the thermal expansion coefficient is preferably 7 ppm / ° C. or less, more preferably 5 ppm / ° C. or less.
In addition, when manufacturing a multi-layer material, since it is exposed to various chemical treatments, it is important that the chemical resistance, particularly the desmear resistance is good, and the weight reduction rate after treatment with the desmear liquid is 0. It is desirable that it is 1-1.5g / m < ² >. When it is 0.1 or more and g / m ² , smear is satisfactorily removed, and when it is 1.5 g / m ² or less, the exposure of the inorganic filler on the substrate surface is suppressed and the plating property is good.
Furthermore, the demand for high-speed response continues to increase. The relative dielectric constant of the base material is 4.7 or less, further 4.5 or less, and the dielectric loss tangent is 0.009 or less, and further 0.008 or less. It is desirable that
Under such circumstances, the present invention described below has been made through intensive research.

The present invention relates to a siloxane resin (a) having a phenolic hydroxyl group at the terminal represented by the above formula (I) and a compound having at least two epoxy groups in one molecule (hereinafter also referred to as an epoxy resin) (b ) And (b) an epoxy group-containing compound (epoxy resin) in an amount of 2.0 mol% or more of the organic phosphine (c) as a catalyst, an etherification reaction, that is, the epoxy group is opened with a phenolic hydroxyl group. A compound (A) having a hydroxyl group and an epoxy group in the molecular structure obtained by addition, and a compound (B) having at least two cyanate groups in one molecule, preferably an organometallic salt ( C), a thermosetting compatibilizing resin obtained by iminocarbonate reaction and triazine cyclization reaction in an aromatic organic solvent. .
The present invention also provides a thermosetting resin composition comprising the compatibilizing resin and fused silica surface-treated (wet-treated) with the trimethoxysilane compound represented by the above formula (II) as essential components. is there. Hereinafter, first, the compatibilizing resin will be described in detail.

（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から１００までの数である） The siloxane resin of component (a) used for the compatibilizing resin of the present invention is not particularly limited as long as both ends of the structure represented by the above formula (I) contain a phenolic hydroxyl group.

(Wherein R ₁ is each independently a saturated hydrocarbon group having 1 to 5 carbon atoms, and m is a number from 5 to 100)

  As such a siloxane resin, for example, trade name X-22-1876 (hydroxyl value: 120 KOHmg / g) manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-1875 (hydroxyl value: 60 KOHmg / g), Product name X-22-1821 (hydroxyl value: 30 KOHmg / g), product name X-22-1822 (hydroxyl value: 20 KOHmg / g), product name X-26-1064 (hydroxyl value: 25 KOHmg / g), Toray Industries, Inc. Examples include trade name BY16-752A (hydroxyl value: 30 KOHmg / g), trade name BY16-799 (hydroxyl value: 60 KOHmg / g), manufactured by Dow Corning. These are commercially available from Shin-Etsu Chemical Co., Ltd. and Toray Dow Corning Co., Ltd. Among these, Shin-Etsu Chemical Co., Ltd., trade name X-22-1876 (hydroxyl value: 120 KOHmg / g), trade name X-22 from the point which is excellent in heat resistance, low thermal expansion property, and solvent solubility. -1875 (hydroxyl value: 60 KOH mg / g), trade name X-22-1821 (hydroxyl value: 30 KOH mg / g), manufactured by Toray Dow Corning Co., Ltd., trade name BY16-752A (hydroxyl value: 30 KOH mg / g), The trade name BY16-799 (hydroxyl value: 60 KOHmg / g) is particularly preferred.

（式中、ｓは１以上の数である）

（式中、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅は各々独立に水素原子、又はメチル基である）

（式中、ｔは１以上の数である） The compound having at least two epoxy groups in one molecule of the component (b) used in the compatibilizing resin of the present invention includes, for example, bisphenol A, bisphenol F, biphenyl, novolac, dicyclopentadiene, Examples include polyfunctional phenol-based, naphthalene-based, aralkyl-modified, alicyclic and alcohol-based glycidyl ethers, glycidylamine-based and glycidyl ester-based epoxy resins, and one or a mixture of two or more types. can do. Among these, naphthalene has high rigidity, dielectric properties, heat resistance, flame resistance, moisture resistance, low thermal expansion, and is solid at room temperature, so it has no tackiness of prepreg and is easy to handle. Ring-containing epoxy resins, biphenyl group-containing epoxy resins, and dicyclopentadiene-type epoxy resins are preferred. From the viewpoint of solubility in aromatic organic solvents, naphthalene-type epoxy resins, biphenyl-type epoxy resins, naphthol aralkyl-cresol copolymer-type epoxies Resin, biphenyl aralkyl type epoxy resin is more preferable. From the viewpoint of moldability when press-molding a multilayer material, naphthol aralkyl / cresol copolymer type epoxy resin represented by the following formula (III), biphenyl represented by the following formula (IV) Type epoxy resin, biphenylaralkylepoxy represented by the following formula (V) Resins are particularly preferred.

(In the formula, s is a number of 1 or more)

(Wherein R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a methyl group)

(Where t is a number of 1 or more)

  The compound (A) having a hydroxyl group and an epoxy group in the molecular structure is obtained by subjecting the component (a) and the component (b) to an etherification reaction. Here, the amount of the siloxane resin (a) having a phenolic hydroxyl group at the terminal represented by the above formula (I) and the compound (b) having at least two epoxy groups in one molecule is as follows: The number of epoxy groups (the amount of (b) used / epoxy group equivalent of (b)) may be used so as to exceed the number of hydroxyl groups of (a) (the amount of (a) used / the hydroxyl equivalent of (a)). Desirably, the ratio of the number of epoxy groups in (b) to the number of hydroxyl groups in (a) (number of epoxy groups in (b) / number of hydroxyl groups in (a)) is more preferably 1.5 or more and 10.0 or less. . When the number of hydroxyl groups in (a) is greater than or equal to the number of epoxy groups in (b), a desired product having an epoxy group in the molecular structure cannot be obtained. If the ratio of the number of epoxy groups in (b) to the number of hydroxyl groups in (a) (number of epoxy groups in (b) / number of hydroxyl groups in (a)) is less than 1.5, insolubilization may occur during synthesis, Moreover, the moisture resistance of the laminated board obtained based on this may fall, and when it exceeds 10.0, it will gelatinize during a synthesis | combination, or copper of the laminated board obtained based on this The foil adhesion may be reduced.

  In addition, an organic solvent may be used for the etherification reaction, and the amount used is preferably 40 to 1000 parts by weight per 100 parts by weight of the total of the components (a) and (b). If the amount of the organic solvent is small, the raw material may be insufficiently soluble or may not be synthesized due to thickening, and if it is too large, the synthesis may take a long time or the production cost may increase. .

  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. S-containing solvents such as petroleum solvents, dimethyl sulfoxide, and ester solvents such as γ-butyrolactone are preferred. These organic solvents can be used alone or in combination of two or more. When using alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and N atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, the moisture resistance of the resulting laminate is It may decrease and may not be preferable. Among these, from the point that it is highly soluble and volatile and does not remain as a residual solvent at the time of manufacturing the prepreg, and from the viewpoint of moisture resistance and heat resistance, copper foil adhesion, and low dielectric constant of the obtained laminate, toluene, Aromatic solvents such as xylene and mesitylene are particularly preferred.

  In this reaction, as a reaction catalyst, an organic phosphine (c) having an addition amount of 2.0 mol% or more with respect to the epoxy resin (b) is essentially used. As the organic phosphines, trialkyl phosphines such as trimethyl phosphine and triethyl phosphine, or triaryl phosphines such as triphenyl phosphine can be used. Triaryl phosphines having high stability in the air can be used. preferable. Examples of triarylphosphines include tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphinetris (4-methylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2, 5-dimethylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, tris (2-methyl-4-methoxyphenyl) phosphine, tris (4-methoxy-3,5- Dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, cyclohexyl phenylphosphine, dicyclohexylphenylphosphine, diphenyl-2-pyridylphosphine, and the like. Among these, it is preferable to use triphenylphosphine from the viewpoint of availability and economy. By using (c) as an essential component, the moisture and heat resistance, copper foil adhesion, and alkali liquid resistance of the resulting laminate are significantly improved. Other reaction catalysts include amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus catalysts, and the like, and these may be used in combination.

  The above-mentioned synthesis raw materials, organic solvent, and if necessary, a reaction catalyst is charged into a synthesis kettle, and if necessary, the mixture is stirred for 0.1 to 10 hours while being heated and kept warm for etherification reaction. The compound (A) which has is manufactured. The synthesis temperature is preferably 25 ° C. to 200 ° C. If the synthesis temperature is too low, the reaction rate becomes too slow, and if the synthesis temperature is too high, a solvent having a high boiling point is required for the synthesis solvent, so a prepreg is produced. At this time, it may be easy to leave a residual solvent, and heat resistance may decrease. The end point of the synthesis reaction and the confirmation of the formation of the compound (A) can be confirmed by taking out a small amount of sample and measuring the acid value by neutralization titration. This can be determined by confirming the decrease in hydroxyl groups. The acid value measurement method by neutralization titration is in accordance with the method according to JIS standards. For example, phenolphthalein is added as an indicator to a small sample taken, and this is titrated with a methanolic potassium hydroxide solution. A method for confirming the neutralization point is desirable. The acid value at the end of the synthesis reaction is desirably 1/2 or less of the acid value at the initial stage of the reaction. When the acid value at the end point is larger than 1/2 of the acid value at the beginning of the reaction, the amount of the compound (A) having a hydroxyl group and an epoxy group in the generated molecular structure is insufficient, and compatibility May be insufficient.

（式中、Ｘ及びＺはグリシジル基が結合する芳香族系又は脂肪族系の残基であり、Ｙは存在しないか又は結合基であり、ｎは０以上の数である）

（式中のＸ、Ｙ、Ｚ、及びｎは、式（VI）と同様であり、Ｒ₁、及びｍは、式（Ｉ）と同様であり、Ａｒ₁はフェニレン基である）

（式中のＸ、Ｙ、Ｚ、及びｎは、式（VI）と同様であり、Ｒ₁、及びｍは、式（Ｉ）と同様であり、Ａｒ₁はフェニレン基である） An example of the compound (b) having at least two epoxy groups in one molecule is shown in the following formula (VI), and examples of the compound (A) produced using this as a raw material are shown in the following formulas (VII) and (VII) VIII).

(In the formula, X and Z are aromatic or aliphatic residues to which a glycidyl group is bonded, Y is not present or is a bonding group, and n is a number of 0 or more)

(Wherein X, Y, Z and n are the same as in formula (VI), R ₁ and m are the same as in formula (I), and Ar ₁ is a phenylene group)

(Wherein X, Y, Z and n are the same as in formula (VI), R ₁ and m are the same as in formula (I), and Ar ₁ is a phenylene group)

（ｕは正の数）
式（IX）で示されるノボラック型シアネート樹脂の平均繰り返し数：ｕは、特に限定されないが、０．１〜３０が好ましい。これより少ないと結晶化しやすくなり取り扱いが困難となる場合がある。また、これより多いと硬化物が脆くなる場合がある。 The compatibilizing resin of the present invention is obtained by further reacting the compound (A) obtained as described above with the compound (B) having a cyanate group. The compound having at least two cyanate groups in one molecule, which is the component (B) of the compatibilizing resin used for producing the compatibilizing resin, is, for example, a novolak type cyanate resin, a bisphenol A type cyanate resin, or a bisphenol. Examples include E-type cyanate resin, bisphenol F-type cyanate resin, and tetramethylbisphenol F-type cyanate resin. One type or a mixture of two or more types can be used. Among these, bisphenol A type cyanate resins and phenol novolac type cyanate resins represented by the following formula (IX) are particularly preferred from the viewpoints of dielectric properties, heat resistance, flame retardancy, low thermal expansion, and low cost.

(U is a positive number)
The average number of repetitions u of the novolak cyanate resin represented by the formula (IX) is not particularly limited, but is preferably 0.1 to 30. If it is less than this, it may be easy to crystallize and it may be difficult to handle. Moreover, when more than this, hardened | cured material may become weak.

  Examples of the organometallic salt (C) component that is a reaction catalyst used in the production of the compatibilizing resin of the present invention include zinc naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate. An amine-based or imidazole-based nitrogen atom-containing reaction catalyst is not preferable because a cured resin obtained is brittle and heat resistance and adhesiveness are lowered.

  In the reaction, the amount of component (A) used per 100 parts by weight of the sum of component (A) of compound A and component (B) of compound B is in the range of 10 to 60 parts by weight, and amount of component (B) used In the range of 40 to 90 parts by weight, these are uniformly dissolved in a solvent in advance, and subjected to imino carbonate reaction and triazine cyclization reaction at a reaction temperature of 80 ° C. to 120 ° C. to obtain a cyanate group of compound (B). It is desirable to carry out the reaction so that the reaction rate (disappearance rate) of the compound having an amount of 30 to 70 mol%. Here, the reaction solvent is particularly preferably an aromatic organic solvent selected from toluene, xylene, and mesitylene, and a small amount of other solvent may be used if necessary, but the desired reaction is slowed down and the heat resistance is reduced. There is a case. In addition, benzene is highly toxic, and an aromatic solvent having a molecular weight larger than that of mesitylene is not preferable because it tends to be a residual solvent during prepreg production coating.

  If the reaction rate is less than 30 mol%, the resulting resin is not compatible, the resin is separated and clouded, and a B-stage coated fabric cannot be produced. On the other hand, if the reaction rate exceeds 70 mol%, the resulting thermosetting compatibilizing resin is insolubilized in the solvent, making it impossible to produce an A-stage varnish (thermosetting resin composition), or shortening the prepreg gel time. In some cases, the moldability may deteriorate during pressing. 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, and the triazine cyclization reaction is a cyanate group. Is a reaction to form a triazine ring by trimerization. In addition, a three-dimensional network structure progresses by a reaction in which the cyanate group is trimerized to form a triazine ring, thereby producing a compatibilizing resin in which the components (A) and (B) are uniformly dispersed. The

  Here, the usage-amount of the (C) component of a reaction catalyst has a preferable 0.0001-0.004 weight part with respect to 100 weight part of the sum total of (A) and (B). Within this range, the reaction does not take a long time, and the reaction rate is too fast to make it difficult to manage the end point. Here, the reaction rate of the compound having the cyanate group (B) is determined by comparing the peak area of the compound having the cyanate group (B) at the start of the reaction with the peak area after the reaction for a predetermined time by GPC measurement. It is obtained from the disappearance rate of the area.

  The compatibilizing resin referred to in the present invention is a resin in which constituent components are uniformly mixed without being separated from each other. Siloxane resin has low polarity and is easily separated from cyanate resin and epoxy resin. However, by using the method of the present invention, it becomes compatible resin mixed with each other, and the low thermal expansion property of siloxane resin is low. To express. The obtained resin solution is dried by heating and visually confirmed, and a uniform and transparent resin cured product is a criterion for compatibilization.

  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 hydrocarbons. Preference is given to solvents based on solvents, petroleum solvents, S atom-containing solvents such as dimethyl sulfoxide, and ester solvents such as γ-butyrolactone. These organic solvents can be used alone or in combination of two or more. When using alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and N atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, the moisture resistance of the resulting laminate is It may decrease and may not be preferable. Among these, from the point that it is highly soluble and volatile and does not remain as a residual solvent at the time of manufacturing the prepreg, and from the viewpoint of moisture resistance and heat resistance, copper foil adhesion, and low dielectric constant of the obtained laminate, toluene, Aromatic solvents such as xylene and mesitylene are particularly preferred.

  Next, thermosetting containing component (1) which is a compatibilizing resin obtained as described above, and component (2) which is fused silica which has been surface-treated (wet-treated) with a trimethoxysilane compound. The functional resin composition will be described in detail.

The fused silica surface-treated (wet-treated) with N-phenyl-3-aminopropyltrimethoxysilane represented by the following formula (II) which is component (2) of the thermosetting resin composition of the present invention is fused silica. Can be obtained by surface treatment (wet treatment) using N-phenyl-3-aminopropyltrimethoxysilane.

  As an example of the production method of this component (2), fused silica is added to 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. After mixing, the trimethoxysilane compound represented by the above formula (II) is added and reacted (surface treatment, so-called wet treatment) at 60 ° C. to 120 ° C. with stirring for about 0.5 to 5 hours. It is done. Thus, the fused silica excellent in dispersibility is obtained by processing using the trimethoxysilane compound represented by the above formula (II). In addition, component (2) can also be obtained commercially from Admatechs Co., Ltd., for example, trade names SC-2050KNK and SC-2050HNK manufactured by Admatechs.

The shape of silica is preferably spherical because of its low thermal expansibility and high fluidity when filled in a resin.
The average particle diameter is preferably from 0.1 to 10 μm, more preferably from 0.3 to 8 μm. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced. Generation of defects due to coarse particles can be suppressed. Here, the average particle size is a particle size at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.

  The amount of the component (2) used is preferably 10 to 300 parts by weight, preferably 100 to 250 parts by weight, per 100 parts by weight of the compatibilizing resin component (1), which is a thermosetting resin converted to solid content. More preferably, it is more preferably 150 to 250 parts by weight. When the amount is less than 10 parts by weight, the rigidity of the base material, moisture and heat resistance, and flame resistance are insufficient, and when it exceeds 300 parts by weight, chemical resistance such as formability and plating solution resistance decreases. There is.

  In the thermosetting resin composition of the present invention, other inorganic fillers may be used as the component (3). For example, crushed silica, mica, talc, short glass fiber or fine powder, hollow glass, calcium carbonate , Quartz powder, metal hydrates, etc. Among these, metal hydrates such as aluminum hydroxide and magnesium hydroxide are preferable from the viewpoint of low thermal expansion, high elasticity, heat resistance, and flame retardancy. Furthermore, among metal hydrates, metal hydrates having a thermal decomposition temperature of 300 ° C. or higher, for example, boehmite type aluminum hydroxide (AlOOH), or gibbsite type hydroxides, because both high heat resistance and flame retardancy are compatible. More preferred are compounds in which the thermal decomposition temperature of aluminum (Al (OH) 3) is adjusted to 300 ° C. or higher by heat treatment, magnesium hydroxide, etc., especially inexpensive and special features of 350 ° C. or higher. And high thermal decomposition temperature, boehmite-type aluminum hydroxide having a high chemical resistance (AlOOH) is particularly preferred. The amount of these inorganic fillers (component (3)) used is preferably 0 to 200 parts by weight, preferably 10 to 150 parts by weight, per 100 parts by weight of the resin component (1) in terms of solid content. It is more preferable that the content be 50 to 150 parts by weight. If it is less than 10 parts by weight, the flame retardancy may be insufficient, and if it exceeds 200 parts by weight, chemical resistance such as plating solution resistance and formability may be deteriorated.

  In the thermosetting resin composition of the present invention, it is desirable to use a curing accelerator for improving heat resistance, flame retardancy, copper foil adhesion, etc., examples of the curing accelerator include zinc naphthenate, Examples include organic metal salts such as cobalt naphthenate, tin octylate, and cobalt octylate, imidazoles and derivatives thereof, tertiary amines, and quaternary ammonium salts. If a curing accelerator is not used, heat resistance, flame retardancy, copper foil adhesion, etc. may be insufficient.

  The thermosetting resin composition of the present invention can optionally be used in combination with other flame retardants, such as halogen-containing flame retardants containing bromine or chlorine, metal hydroxides having a thermal decomposition temperature of less than 300 ° C., etc. Does not meet the purpose of the present invention. Examples of other flame retardant combinations include triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphazenes, phosphorous flame retardants such as red phosphorus, antimony trioxide, zinc molybdate, etc. Inorganic flame retardant aids and the like. In particular, an inorganic flame retardant aid in which zinc molybdate is supported on an inorganic filler such as talc is a particularly preferred inorganic flame retardant aid because it significantly improves not only the flame retardancy but also the drill workability. The amount of zinc molybdate used is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the compatibilizing resin of the present invention. If the amount is less than 5 parts by weight, flame retardancy and drilling workability are not improved. If the amount exceeds 20 parts by weight, the gel time of the varnish becomes too short. May decrease.

In the thermosetting resin composition of the present invention, known thermoplastic resins, elastomers, organic fillers and the like can be used in combination in order to improve toughness and fluidity.
Examples of the thermoplastic resin include tetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.
Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.
Examples of organic fillers include organic powders such as silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

  Moreover, in the thermosetting resin composition of this invention, an ultraviolet absorber, antioxidant, a photoinitiator, a fluorescent whitening agent, an adhesive improvement agent, etc. can be added arbitrarily, and it does not specifically limit. Examples of these include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescence such as stilbene derivatives. Examples include brighteners, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.

  The prepreg of the present invention is obtained by impregnating or coating the base material with the above-described thermosetting resin composition of the present invention. Hereinafter, the prepreg of the present invention will be described in detail.

  The prepreg of the present invention can be produced by impregnating or coating the base material with the thermosetting resin composition of the present invention and semi-curing (B-stage) by heating or the like. As the base material of the present invention, known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and tetrafluoroethylene, and mixtures thereof. These base materials have, for example, 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 if necessary, A single material or two or more materials and shapes can be combined. The thickness of the base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment. However, it is suitable from the aspects 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 weight as the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. Can be heated and dried for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.

The laminate of the present invention can be formed by laminate molding using the prepreg of the present invention described above. The prepreg of the present invention can be produced, for example, by laminating 1 to 20 sheets and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications. In addition, as the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. For example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and It can be molded in a range of ˜100 kg / cm ² 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 in more detail with reference to the following examples, but these examples do not limit the present invention in any way.

（式中、Ｒ₂はプロピレン基であり、ｐは平均して３５〜４０の数であり、フェノール性水酸基はメタ体とパラ体の混合である）

（式中のＲ₂及びｐは、式（XI）と同様である） Production Example 1: Production of compatibilizing resin (1-1) A biphenyl type epoxy represented by the following formula (X) was placed in a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters. Resin (manufactured by Japan Epoxy Resin; trade name YX-4000, epoxy equivalent; 186): 317.4 g and siloxane resin represented by the following formula (XI) (manufactured by Shin-Etsu Chemical; trade name X-22-1821, hydroxyl equivalent) 1,600): 682.6 g, toluene: 1000.0 g, and triphenylphosphine: 8.94 g were added (equivalent ratio of reaction was epoxy group / hydroxyl group = 4.0, use of triphenylphosphine) The amount is 2.0 mol% with respect to the epoxy resin). Next, the temperature was raised to 120 ° C. with stirring, the reaction was performed at about 120 ° C., sampling was performed every hour, and oxidation was measured by neutralization titration. After confirming that the acid value became 0 mg / KOH after the reaction for 5 hours, the solution was cooled to room temperature and the compound (A-1) having a hydroxyl group and an epoxy group in the molecular structure represented by the following formula (XII) Got.

(In the formula, R ₂ is a propylene group, p is an average number of 35 to 40, and the phenolic hydroxyl group is a mixture of a meta isomer and a para isomer)

(R ₂ and p in the formula are the same as in the formula (XI))

Next, in a reaction vessel having a volume of 3 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, the solution of the above compound (A-1): 800.0 g (solid content: 400.0 g) Bisphenol A cyanate resin (Lonza Japan, trade name Primaset BADCy): 600.0 g and toluene: 600.0 g were added. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.06 g of an 8 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing resin (1-1). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared with the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 60%. Moreover, the peak of the product of the thermosetting compatibilizing resin which appears in about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing weight ratio 1: 1) and reprecipitated to take out the purified solid, and FT-IR measurement was performed. imino carbonates due to group 1700 cm ^-1 vicinity of the peak, also around 1560 cm ^-1 due to the triazine ring, and 1380cm vicinity of can strong peak is confirmed ^-1, compatibilizing resin (1-1) is prepared I confirmed. Confirmation that the obtained resin is compatible is made by visually evaluating a cured resin obtained by drying the resin solution with a hot air drier at 170 ° C. for 15 minutes. It was performed by confirming that the cured product was transparent and no separation occurred.

（式中、ｑは平均して５〜１０の数であり、フェノール性水酸基はメタ体とパラ体の混合である）

（式中のｑは、式（XIII）と同様であり、フェノール性水酸基はメタ体とパラ体の混合である） Production Example 2: Production of compatibilizing resin (1-2) A biphenyl type epoxy represented by the above formula (X) was placed in a 2 liter reaction vessel having a thermometer, a stirrer, and a reflux condenser and capable of heating and cooling. Resin (made by Japan Epoxy Resin; trade name YX-4000, epoxy equivalent; 186): 498.0 g and a siloxane resin represented by the following formula (XIII) (made by Shin-Etsu Chemical; trade name X-22-1876, hydroxyl equivalent) 375): 502.0 g, toluene: 1000.0 g, and triphenylphosphine: 14.03 g were added (the equivalent ratio of the reaction was epoxy group / hydroxyl group = 2.0, and the amount of triphenylphosphine used was 2.0 mol% with respect to the epoxy resin). Next, the temperature was raised to 120 ° C. with stirring, the reaction was performed at about 120 ° C., sampling was performed every hour, and oxidation was measured by neutralization titration. Although the acid value was 30 mg / KOH at the start of the reaction, it was confirmed that the acid value became half 15 mg / KOH after the reaction for 2 hours, cooled to room temperature, and the molecular structure of the structure represented by the following formula (XIV) A solution of the compound (A-2) having a hydroxyl group and an epoxy group therein was obtained.

(In the formula, q is a number of 5 to 10 on average, and the phenolic hydroxyl group is a mixture of meta and para)

(Q in the formula is the same as in formula (XIII), and the phenolic hydroxyl group is a mixture of meta and para)

Next, in a reaction vessel having a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser, the solution of the above compound (A-2): 1000.0 g (solid content: 500.0 g) Bisphenol A-type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset BADCy): 500.0 g and toluene: 500.0 g were added. Next, the temperature was raised to 120 ° C. while stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.02 g of an 8 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 3 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing resin (1-2). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared to the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 30%. Moreover, the peak of the product of the thermosetting compatibilizing resin which appears in about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing weight ratio 1: 1) and reprecipitated to take out the purified solid, and FT-IR measurement was performed. imino carbonates due to group 1700 cm ^-1 vicinity of the peak, also around 1560 cm ^-1 due to the triazine ring, and 1380cm vicinity of can strong peak is confirmed ^-1, compatibilizing resin (1-2) is prepared I confirmed.

（式中、ｒは平均して１５〜２０の数であり、フェノール性水酸基はメタ体とパラ体の混合である） Production Example 3: Production of compatibilizing resin (1-3) A naphthol aralkyl represented by the above-mentioned formula (III) was placed in a 2 liter reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser and capable of being cooled and cooled.・ Cresol copolymerization type epoxy resin (Nippon Kayaku Co., Ltd .; trade name NC-7000L, epoxy equivalent: 230): 710.4 g and siloxane resin represented by the following formula (XV) (made by Toray Dow Corning Co., Ltd .; trade name) BY16-799, hydroxyl group equivalent; 750): 289.6 g, toluene: 1000.0 g, and triphenylphosphine: 24.28 g were added (the equivalent ratio of the reaction was epoxy group / hydroxyl group = 8.0, The amount of phenylphosphine used is 3.0 mol% with respect to the epoxy resin). Next, the temperature was raised to 120 ° C. with stirring, the reaction was performed at about 120 ° C., sampling was performed every hour, and oxidation was measured by neutralization titration. After confirming that the acid value became 0 mg / KOH after the reaction for 2 hours, the solution was cooled to room temperature to obtain a solution of the compound (A-3) having a hydroxyl group and an epoxy group in the molecular structure.

(In the formula, r is a number of 15 to 20 on average, and the phenolic hydroxyl group is a mixture of a meta isomer and a para isomer)

Next, in a reaction vessel having a volume of 3 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, a solution of the above compound (A-3): 1000.0 g (solid content: 500.0 g) Bisphenol A-type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset BADCy): 500.0 g and toluene: 500.0 g were added. Next, the temperature was raised to 120 ° C. while stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.05 g of an 8 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing resin (1-3). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared with the peak area of the bisphenol A-type cyanate resin at the time, the disappearance rate of the peak area was 50%. Moreover, the peak of the product of the thermosetting compatibilizing resin which appears in about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing weight ratio 1: 1) and reprecipitated to take out the purified solid, and FT-IR measurement was performed. imino carbonates due to group 1700 cm ^-1 vicinity of the peak, also around 1560 cm ^-1 due to the triazine ring, and 1380cm vicinity of can strong peak is confirmed ^-1, compatibilizing resin (1-3) is prepared I confirmed.

Production Example 4: Production of compatibilizing resin (1-4) Naphthalene type epoxy represented by the following formula (XVI) in a reaction vessel having a volume of 2 liters which can be heated and cooled with a thermometer, a stirrer and a reflux condenser. Resin (made by Japan Epoxy Resin Co., Ltd .; trade name HP-4032, epoxy equivalent; 152): 275.4 g and a siloxane resin represented by the above formula (XI) (made by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl group equivalent) 1,600): 724.6 g, toluene: 1000.0 g, and triphenylphosphine: 9.49 g (the equivalent ratio of the reaction is epoxy group / hydroxyl group = 4.0, and the use of triphenylphosphine) The amount is 2.0 mol% with respect to the epoxy resin). Next, the temperature was raised to 120 ° C. with stirring, the reaction was performed at about 120 ° C., sampling was performed every hour, and oxidation was measured by neutralization titration. Although the acid value was 11 mg / KOH at the start of the reaction, it was confirmed that the acid value became 3 mg / KOH after the reaction for 3 hours, and the mixture was cooled to room temperature and a compound having a hydroxyl group and an epoxy group in the molecular structure (A -4) was obtained.

Next, in a reaction vessel having a volume of 3 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, the solution of the above compound (A-4): 800.0 g (solid content: 400.0 g) Phenol novolac-type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset PT-15, weight average molecular weight 500 to 1,000)): 600.0 g and toluene: 600.0 g were added. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.06 g of an 8 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing resin (1-4). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the novolac-type cyanate resin, which is a synthetic raw material with an elution time of about 12.1 minutes, As compared with the peak area of the phenol novolac type cyanate resin, the disappearance rate of the peak area was 37%. Moreover, the peak of the product of the thermosetting compatibilizing resin which appears in about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing weight ratio 1: 1) and reprecipitated to take out the purified solid, and FT-IR measurement was performed. imino carbonates due to group 1700 cm ^-1 vicinity of the peak, also around 1560 cm ^-1 due to the triazine ring, and 1380cm vicinity of can strong peak is confirmed ^-1, compatibilizing resin (1-4) is prepared I confirmed.

（式中、ｗは１以上の数である） Production Example 5: Production of compatibilizing resin (1-5) A dicyclopentadiene represented by the following formula (XVII) was placed in a reaction vessel having a thermoliter, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters. Type epoxy resin (manufactured by Japan Epoxy Resin; trade name HP-7200H, epoxy equivalent; 280): 344.3 g and a siloxane resin represented by the above formula (XI) (manufactured by Shin-Etsu Chemical; trade name X-22-1821, Hydroxyl equivalent: 1,600): 655.7 g, toluene: 1000.0 g, and triphenylphosphine: 9.66 g (Equivalent ratio of reaction is epoxy group / hydroxyl group = 3.0, triphenylphosphine) Is 3.0 mol% with respect to the epoxy resin). Next, the temperature was raised to 120 ° C. with stirring, the reaction was performed at about 120 ° C., sampling was performed every hour, and oxidation was measured by neutralization titration. After the reaction for 6 hours, it was confirmed that the acid value became 0 mg / KOH, and the mixture was cooled to room temperature to obtain a solution of a compound (A-5) having a hydroxyl group and an epoxy group in the molecular structure.

(Where w is a number of 1 or more)

Next, in a reaction vessel having a volume of 3 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, the solution of the above compound (A-5): 400.0 g (solid content: 200.0 g) Bisphenol A type cyanate resin (Lonza Japan, trade name Primaset BADCy): 800.0 g and toluene: 800.0 g were added. Next, the temperature was raised to 120 ° C. while stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.10 g of an 8 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing resin (1-5). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared to the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 65%. Moreover, the peak of the product of the thermosetting compatibilizing resin which appears in about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing weight ratio 1: 1) and reprecipitated to take out the purified solid, and FT-IR measurement was performed. imino carbonates due to group 1700 cm ^-1 vicinity of the peak, also around 1560 cm ^-1 due to the triazine ring, and 1380cm vicinity of can strong peak is confirmed ^-1, compatibilizing resin (1-5) is prepared I confirmed.

Production Example 6: Production of fused silica (2-1) surface-treated (wet treatment) with a trimethoxysilane compound 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. , Fused silica (manufactured by Admatechs; trade name SO-25R, particle size 0.5 μm, spherical): 700.0 g and propylene glycol monomethyl ether: 1000.0 g were mixed and stirred with N-phenyl-3- Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KBM-573): 7.0 g was added. Next, the temperature was raised to 80 ° C., reacted at 80 ° C. for 1 hour to perform surface treatment of the fused silica (wet treatment), then cooled to room temperature, and surface treatment with N-phenyl-3-aminopropyltrimethoxysilane ( A dispersion of fused silica (2-1) that was wet-treated was obtained.

Comparative Production Example 1: Production of (Comparative 1) A bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset) was added to a reaction vessel with a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. BADCy): 600.0 g and a siloxane resin represented by the above formula (XI) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl group equivalent; 1,600): 200.0 g, biphenyl type epoxy resin (Japan) Product name: YX-4000, epoxy equivalent: 186): 200.0 g and toluene: 1000.0 g were supplied. Next, the temperature was raised to 120 ° C. while stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 1 hour. Then, it cooled to room temperature and obtained the reaction solution of (Comparative 1). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared with the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 18%. In addition, a precipitate was formed in the solution by crystallization the next day.

Comparative Production Example 2: Production of (Comparative 2) A bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset) was added to a reaction vessel having a volume of 3 liters which can be heated and cooled with a thermometer, a stirrer and a reflux condenser. BADCy): 600.0 g and a siloxane resin represented by the above formula (XI) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl group equivalent; 1,600): 200.0 g, biphenyl type epoxy resin (Japan) Product name: YX-4000, epoxy equivalent: 186): 200.0 g and toluene: 1000.0 g were supplied. Next, the temperature was raised to 120 ° C. while stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 120 ° C. The reaction was carried out for 6 hours. Thereafter, the reaction solution was cooled to room temperature (Comparative 2). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared with the peak area of the bisphenol A type cyanate resin at the time, the disappearance rate of the peak area was 76%.

Comparative Production Example 3: Production of (Comparative 3) Bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset) was added to a reaction vessel with a volume of 2 liters which can be heated and cooled with a thermometer, a stirrer and a reflux condenser. BADCy): 600.0 g, a siloxane resin represented by the above formula (XI) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl group equivalent; 1,600): 200.0 g and toluene: 800.0 g I put it in. Next, the temperature was raised to 120 ° C. while stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 4 hours. Thereafter, the reaction solution was cooled to room temperature (Comparative 3). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the bisphenol A type cyanate resin, which is a synthetic raw material and the elution time appears around 12.4 minutes, is the start of the reaction. Compared to the peak area of the bisphenol A-type cyanate resin at the time, the disappearance rate of the peak area was 53%.

Comparative Production Example 4: Production of (Comparative 4) A phenol novolac-type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset) was added to a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. PT-15, weight average molecular weight 500 to 1,000)): 600.0 g and a siloxane resin represented by the above formula (XI) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl group equivalent; 1,600) : 200.0 g and a naphthalene type epoxy resin represented by the above formula (XVI) (manufactured by Japan Epoxy Resin; trade name HP-4032, epoxy equivalent: 152): 200 g and toluene: 800.0 g were added. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.06 g of an 8 wt% mineral spirit solution of zinc naphthenate was added, and the temperature was about 110 ° C. The reaction was carried out for 4 hours. Thereafter, the reaction solution was cooled to room temperature (Comparative 4). A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, the peak area of the phenol novolac-type cyanate resin, which is a synthetic raw material that appears at about 12.1 minutes, is the start of the reaction. Compared with the peak area of the phenol novolac cyanate resin at the time, the disappearance rate of the peak area was 35%.

(Examples 1-6, Comparative Examples 1-5)
Component (1) compatibilizing resin obtained in Production Examples 1-5, resin obtained in Comparative Production Examples 1-4, and fused silica of Production Example 6 or commercially available component (2) If necessary, use methyl ethyl ketone as the inorganic filler, flame retardant aid, curing accelerator, and diluent solvent of component (3), and mix at the blending ratios (parts by weight) shown in Tables 2 and 3. Thus, a uniform varnish having a resin content of 60 wt% was obtained.

Next, the varnish was impregnated and applied to an S glass cloth having a thickness of 0.2 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 55% by weight. Next, 4 sheets of this prepreg were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 25 kg / cm ² and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate. Using the copper-clad laminate thus obtained, copper foil adhesion (copper foil peel strength), glass transition temperature, solder heat resistance, linear thermal expansion coefficient, desmear liquid resistance, flame resistance, ratio The dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) were measured and evaluated by the following methods, and the evaluation results are shown in Tables 4 and 5.

(1) Evaluation of copper foil adhesion (copper foil peel strength) A copper-clad laminate is dipped in a copper etching solution to form a 1 cm wide copper foil to produce an evaluation substrate, and copper is tested using a tensile tester. The adhesiveness (90 ° peel strength) of the foil was measured.

(2) Measurement of glass transition temperature (Tg) A 5-mm square evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (manufactured by DuPont, TMA2940) was used. The evaluation was performed by observing the thermal expansion characteristics in the surface direction of the evaluation substrate.

(3) Measurement of coefficient of linear thermal expansion A copper-clad laminate was immersed in a copper etching solution to produce a 5 mm square evaluation substrate from which the copper foil was removed, and evaluation was performed using a TMA test apparatus (manufactured by DuPont, TMA2940). The linear thermal expansion coefficient of 30 to 100 ° C. in the surface direction of the substrate was measured.

(4-1) Evaluation of solder heat resistance (1)
A copper-clad laminate was dipped in a copper etching solution to produce a 5 cm square evaluation substrate from which the copper foil had been removed, and the pressure cooker test apparatus manufactured by Hirayama Seisakusho was used. After performing the pressure-cooker treatment until the time, the evaluation substrate was immersed in a solder bath having a temperature of 288 ° C. for 20 seconds, and then the heat resistance of the solder was evaluated by observing the appearance.
(4-2) Evaluation of solder heat resistance (2)
A copper-clad laminate was dipped in a copper etching solution to produce a 5 cm square evaluation substrate from which the copper foil had been removed, and the pressure cooker test apparatus manufactured by Hirayama Seisakusho was used. After performing the pressure-cooker treatment until the time, the evaluation substrate was immersed in a solder bath at a temperature of 300 ° C. for 20 seconds, and then the solder heat resistance was evaluated by observing the appearance.

(5) Evaluation of heat resistance with copper (T-300) A 5 mm square evaluation board was produced from a copper clad laminate, and the evaluation board swelled at 300 ° C. using a TMA test apparatus (manufactured by DuPont, TMA2940). It was evaluated by measuring the time to do.

(6) Flame Retardancy Evaluation A test piece cut out to 127 mm in length and 12.7 mm in width was prepared from an evaluation board from which a copper foil was removed by immersing a copper-clad laminate in a copper etching solution, and tested for UL94. Evaluation was made according to the method (Method V).

(7) Measurement of relative dielectric constant and dielectric loss tangent The obtained copper-clad laminate was immersed in a copper etching solution to produce an evaluation substrate from which the copper foil was removed, and a relative dielectric constant measuring device manufactured by Hewlett-Packard Company (product) Name: HP4291B), relative permittivity and dielectric loss tangent at a frequency of 1 GHz were measured.

(8) Resistance to desmear liquid A 40 mm × 40 mm evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was subjected to desmear treatment by the steps shown in Table 1 below. A chemical manufactured by Atotech was used. For evaluation of desmear resistance, the weight loss was calculated from the difference in dry weight before and after desmear treatment at 130 ° C.

The numbers in Tables 2 and 3 are indicated by parts by weight of solid content. * 1: Fused silica surface-treated with 1.0 wt% of N-phenyl-3-aminopropyltrimethoxysilane with respect to fused silica (manufactured by Admatech; trade name SC-2050KNK, particle size 0. 5μm, spherical, diluent solvent; methyl isobutyl ketone)
* 2: Fused silica surface-treated with 1.0 wt% of N-phenyl-3-aminopropyltrimethoxysilane with respect to fused silica (manufactured by Admatech; trade name SC-2050HNK, particle size 0.5 μm, spherical, diluted) Solvent; cyclohexanone)
* 3: Boehmite type aluminum hydroxide (manufactured by Kawai Lime Co., Ltd .; trade name BMT-3L, thermal decomposition temperature: 400 ° C.)
* 4: Inorganic flame retardant aid with zinc molybdate supported on talc (manufactured by Sherwin Williams; trade name Chemguard 1100)
* 5: 8 wt% mineral spirit solution of zinc naphthenate * 6: Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin; trade name YX-4000, epoxy equivalent; 186)
* 7: Fused silica (manufactured by Admatech; trade name SO-25R, particle size 0.5 μm, spherical)
Means.

  As is apparent from the table, the examples of the present invention are Tg, copper foil peel strength, heat resistance, low thermal expansion, flame retardancy, heat resistance with copper (T-300), low dielectric properties, low dielectric loss tangent. Excellent in all desmear liquid resistance. On the other hand, the comparative example satisfies all of Tg, copper foil peel strength, heat resistance, moisture resistance, flame resistance, heat resistance with copper (T-300), low dielectric property, low dielectric loss tangent property, and desmear liquid resistance. There is nothing and it is inferior to one of the characteristics.

Claims (4)

A compound having a siloxane resin (a) having a phenolic hydroxyl group at the terminal represented by the following formula (I), a compound (b) having at least two epoxy groups in one molecule, and an epoxy group of (b) The compound (A) having a hydroxyl group and an epoxy group in the molecular structure obtained by performing an etherification reaction using 2.0 mol% or more of the organic phosphine (c) as a catalyst, and at least 2 in one molecule A compatibilizing resin obtained by reacting a compound (B) having one cyanate group so that the reaction rate of the compound (B) having a cyanate group is 30 to 70 mol%.

(Wherein R ₁ is each independently a saturated hydrocarbon group having 1 to 5 carbon atoms, and m is a number from 5 to 100) A thermosetting resin composition containing the following components (1) and (2).
(1) The compatibilizing resin according to claim 1.
(2) Fused silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane represented by the following formula (II).

  A prepreg formed using the thermosetting resin composition according to claim 2.   A laminate formed by using the prepreg according to claim 3.