JP2013189577A - Thermosetting resin composition, prepreg, and laminated plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition having excellent low thermal expansion and heat resistance, and a prepreg and a laminated plate using the same.SOLUTION: A thermosetting resin composition contains a compatibilization resin (A) obtained by reacting a siloxane resin (a) having hydroxyl groups on terminals thereof, a compound (b) having at least two cyanate groups in one molecule thereof, and a compound (c) having at least two epoxy groups in one molecule thereof, and a compound (B) which contains an imidazole structure in the molecular structure and whose secondary amine moiety is modified. A prepreg and a laminated plate use the composition are also provided.

Description

  The present invention relates to a thermosetting resin composition, a prepreg, and a laminate that exhibit excellent low thermal expansibility and heat resistance and are suitably used for manufacturing electronic components and the like.

  Thermosetting resin compositions have a cross-linked structure and exhibit high heat resistance and dimensional stability, and thus are widely used in the field of electronic components and the like. In particular, copper-clad laminates and interlayer insulation materials are required to have characteristics such as high copper foil adhesion, heat resistance, and good low thermal expansion due to the recent demand for higher density and higher reliability. The Moreover, due to recent environmental problems, mounting of electronic components using lead-free solder and flame resistance using halogen-free materials are required, and therefore higher heat resistance and flame resistance than conventional products are required.

Cyanate compound, which is 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, heat resistance and toughness are not sufficient, Further, low thermal expansion is desired as a thermosetting resin corresponding to the next generation.
For this reason, although the resin composition which expresses the low thermal expansibility which consists of a cyanate compound and an inorganic filler is disclosed (for example, refer patent documents 1, 2, and 3), since these express the low thermal expansibility, they are inorganic filling. The amount of the agent used is large, and when it is used as a copper-clad laminate or an interlayer insulating material, drill workability and formability are insufficient.

  In addition, thermosetting resins containing a cyanate resin and an aralkyl-modified epoxy resin as essential components in order to exhibit low thermal expansibility are disclosed (for example, see Patent Documents 4 and 5). However, since the cyanate resin, which is an essential component, is a resin with poor toughness and curing reactivity, improvement in curing reactivity and toughness is still insufficient, and when these are used as copper-clad laminates and interlayer insulation materials However, heat resistance, reliability, workability, etc. are insufficient.

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 to solve the above problems in the case of using a cyanate compound, which is a thermosetting resin, in view of the current situation, and to provide a thermosetting resin composition having excellent low thermal expansion and heat resistance, and It is to provide the used prepreg and laminate.

As a result of intensive studies to solve the above-mentioned problems, the present invention has revealed that a siloxane resin (a) having a hydroxyl group at the terminal, a compound (b) having at least two cyanate groups in one molecule, and at least in one molecule By blending a compound (B) having a specific imidazole structure with a compatibilizing resin (A) obtained by reacting a compound (c) having two epoxy groups in a specific solvent. The present inventors have found that a thermosetting resin composition having excellent low thermal expansion and heat resistance can be obtained, and have completed the present invention. The present invention has been completed based on such findings.
That is, the present invention provides the following thermosetting resin composition, prepreg and laminate.

1. A siloxane resin having a hydroxyl group at the terminal represented by the following general formula (I) (a), a compound (b) having at least two cyanate groups in one molecule, and a compound having at least two epoxy groups in one molecule (C) per 100 parts by mass of the total amount of components (a) to (c), (a) component 10 to 50 parts by mass, (b) component 40 to 80 parts by mass, (c) component 10 to 50 parts by mass As a phase in which the reaction is carried out at 80 to 120 ° C. in at least one solvent selected from toluene, xylene and mesitylene in the presence of the organometallic salt (d), and the reaction rate of the component (b) is 30 to 70 mol%. A thermosetting resin composition comprising: a resin containing resin (A); and a compound (B) containing a imidazole structure in the molecular structure and having a modified secondary amine moiety.

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

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

2. Furthermore, said 1 thermosetting resin composition containing an inorganic filler (C).
3. The thermosetting property of 1 or 2 above, wherein the compound (B) containing an imidazole structure in the molecular structure and having a modified secondary amine moiety is a compound represented by the following general formula (II) or general formula (III): Resin composition.

（式中、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は各々独立に、水素原子、炭素数１〜２０のアルキル基又はフェニル基であり、Ａはアルキレン基又はフェニレン基である。）

(Wherein R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and A is an alkylene group or a phenylene group.)

（式中、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は各々独立に、水素原子、炭素数１〜２０のアルキル基又はフェニル基であり、Ｂは単結合、アルキレン基、アルキリデン基、エーテル基又はスルフォニル基である。）

Wherein R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and B is a single bond, an alkylene group, an alkylidene group or an ether group. Or a sulfonyl group.)

4.1 The compound (c) having at least two epoxy groups in one molecule is a compound represented by any one of the following general formula (IV), general formula (V), and general formula (VI) The thermosetting resin composition in any one of 1-3.

（式中、ｓは１以上の数である。）

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

（式中、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は各々独立に、水素原子、又はメチル基である。）

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

（式中、ｔは１以上の数である。）

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

5. The thermosetting resin composition according to any one of 2 to 4 above, wherein the inorganic filler (C) has an average particle size of 5 μm or less.
6). The thermosetting resin composition according to any one of 2 to 4 above, wherein the inorganic filler (C) is fused silica.
7). The thermosetting resin composition according to any one of 2 to 6 above, wherein the inorganic filler (C) is surface-treated with a silane compound having a functional group.
8). 8. The thermosetting resin composition according to 7 above, wherein the silane compound having a functional group is a trimethoxysilane compound represented by the following formula (VII).

9. A prepreg that has been B-staged after impregnating or coating the thermosetting resin composition according to any one of 1 to 8 above in a base material.
10. A laminate formed using the prepreg described in 9 above.

  The thermosetting resin composition, prepreg and laminate of the present invention have excellent low thermal expansion and heat resistance, and are suitably used for the production of electronic components and the like corresponding to the next generation.

Hereinafter, the present invention will be described in detail.
First, the thermosetting resin composition of the present invention includes a siloxane resin (a) having a hydroxyl group at the terminal represented by the following general formula (I), a compound (b) having at least two cyanate groups in one molecule, and The compound (c) having at least two epoxy groups in one molecule is composed of 10 to 50 parts by weight of component (a) to 100 parts by weight of component (a) to (c), and 40 to 40 parts of component (b). 80 parts by mass, (c) component 10 to 50 parts by mass in the presence of an organometallic salt (d) in at least one solvent selected from toluene, xylene and mesitylene at 80 to 120 ° C., (b) A compatibilizing resin (A) having a component reaction rate of 30 to 70 mol%, and a compound (B) containing an imidazole structure in the molecular structure and having a modified secondary amine moiety. To do.

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

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

  The siloxane resin of component (a) used for the production of the compatibilizing resin (A) of the present invention is not particularly limited as long as it is a siloxane resin containing a hydroxyl group having a structure represented by the above general formula (I). For example, trade names X-22-1821 (hydroxyl value: 35 KOHmg / g), trade names X-22-1822 (hydroxyl value: 20 KOHmg / g) manufactured by Shin-Etsu Chemical Co., Ltd., which are both phenolic hydroxyl groups, Toray -Trade name BY16-752A (hydroxyl value: 30 KOHmg / g) manufactured by Dow Corning Co., Ltd., and trade name X-22-160AS (hydroxyl value: manufactured by Shin-Etsu Chemical Co., Ltd.) where both ends are alcoholic hydroxyl groups. 112 KOH mg / g), trade name KF-6001 (hydroxyl value: 62 KOH mg / g), trade name KF-6002 (hydroxyl value: 35 KOH mg / g), trade name KF-6003 (hydroxyl value: 20 KOH mg / g), trade name X -22-4015 (hydroxyl value: 27 KOHmg / g). These can be obtained from Shin-Etsu Chemical Co., Ltd. or Toray Dow Corning Co., Ltd.

  Examples of the compound having at least two cyanate groups in one molecule of the component (b) used for the production of the compatibilizing resin (A) include novolak type cyanate resin, bisphenol A type cyanate resin, and bisphenol E type cyanate. Resins, bisphenol F-type cyanate resins, tetramethylbisphenol F-type cyanate resins and the like can be mentioned, and one kind or a mixture of two or more kinds can be used. Of these, bisphenol A type cyanate resins and novolak type cyanate resins represented by the following general formula (VIII) are particularly preferred from the viewpoints of dielectric properties, heat resistance, flame retardancy, low thermal expansion, and low cost.

  H in the above general formula (VIII) is the average number of repeats of the novolak-type cyanate resin and is not particularly limited, but is preferably 0.1 to 30 as an average value. If it is smaller than this, it may be easy to crystallize and it may be difficult to handle. Moreover, when larger than this, hardened | cured material may become weak.

Examples of the compound having at least two epoxy groups in one molecule of the component (c) used for the production of the compatibilizing resin (A) include bisphenol A, bisphenol F, biphenyl, novolac, Examples include functional phenol-based, naphthalene-based, alicyclic and alcohol-based glycidyl ethers, glycidylamine-based and glycidyl ester-based compounds (resins), and use a mixture of two or more of these compounds. You can also.
Among these, naphthalene type epoxy resin, naphthol aralkyl type epoxy resin, dihydroxynaphthalene aralkyl type epoxy resin, naphthol aralkyl cresol and naphthol aralkyl / cresol are used in terms of high rigidity, dielectric properties, heat resistance, flame resistance, moisture resistance and low thermal expansion. Naphthalene ring-containing epoxy resins such as polymerized epoxy resins, biphenyl-type epoxy resins, biphenyl aralkyl-type epoxy resins and the like are preferred, and from the viewpoint of solubility in aromatic organic solvents, general formula (IV) A naphthol aralkyl / cresol copolymer type epoxy resin represented by the formula (II), a biphenyl type epoxy resin represented by the general formula (V), and a biphenyl aralkyl type epoxy resin represented by the general formula (VI) are more preferable.

（式中、ｓは１以上の数である。）

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

（式中、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は各々独立に、水素原子、又はメチル基である。）

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

（式中、ｔは１以上の数である。）

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

  The organometallic salt of component (d) used in the production of the compatibilizing resin (A) serves as a reaction catalyst, and examples thereof include zinc naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate. .

  In the production of the compatibilizing resin (A), the amount of the component (a) used is 10 to 50 parts by mass, preferably 10 to 40 per 100 parts by mass of the total amount of the components (a) to (c). Part by mass, more preferably 10 to 30 parts by mass. The amount of component (b) used is 40 to 80 parts by mass, preferably 45 to 80 parts by mass, and more preferably 50 to 80 parts by mass. The amount of component (c) used is 10 to 50 parts by mass, preferably 10 to 40 parts by mass, and more preferably 10 to 30 parts by mass. A compound having a cyanate group as the component (b), which is previously uniformly dissolved in a solvent selected from toluene, xylene and mesitylene, and subjected to iminocarbonate reaction and triazine cyclization reaction at a reaction temperature of 80 to 120 ° C. The pre-reaction is carried out so that the reaction rate (disappearance rate) is 30 to 70 mol%.

In the production of the compatibilizing resin (A), an aromatic solvent selected from toluene, xylene and mesitylene is used as the reaction solvent. A small amount of other solvent may be used if necessary, but the progress of the desired reaction may be delayed, and heat resistance and the like may be reduced. 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.
When the reaction rate of the component (b) by the pre-reaction is less than 30 mol%, the resulting resin is not compatibilized, the resin is separated and clouded, and a B-stage coated fabric cannot be produced. When the reaction rate exceeds 70 mol%, the resulting thermosetting resin is insolubilized in the solvent, and the A-stage varnish (thermosetting resin composition) cannot be produced, or the gel time of the prepreg becomes too short. Formability may be reduced during pressing.

  The iminocarbonation reaction is a reaction in which an iminocarbonate bond (-O- (C = secondary amine) -O-) is generated by the addition reaction of a hydroxyl group and a cyanate group, and the triazine cyclization reaction is This is a reaction in which a cyanate group is trimerized to form a triazine ring. In addition, a three-dimensional network structure is formed by a reaction in which this cyanate group is trimerized to form a triazine ring. At this time, a compound having at least two epoxy groups in one molecule as component (c) is three-dimensional. A compatibilized resin in which the components (a), (b), and (c) are uniformly dispersed is produced by uniformly dispersing in the network structure.

  In this pre-reaction, when the amount of the component (a) used per 100 parts by mass of the total amount of the components (a) to (c) is less than 10 parts by mass, the low thermal expansion in the surface direction of the obtained substrate is obtained. When the amount of component (a) used exceeds 50 parts by mass, heat resistance and chemical resistance may be reduced. When the amount of the component (b) used is less than 40 parts by mass, the compatibility of the obtained resin may be reduced, and when the amount of the component (b) used exceeds 80 parts by mass, The low thermal expansion property in the surface direction may decrease. When the amount of the component (c) used is less than 10 parts by mass, the moisture resistance and heat resistance may be reduced. When the amount of the component (c) used exceeds 50 parts by mass, the copper foil adhesion and dielectric properties are reduced. May decrease.

  The amount of component (d) used in the reaction catalyst is preferably 0.0001 to 0.004 parts by mass with respect to 100 parts by mass of the total amount of components (a) to (c). By setting it to 0.0001 parts by mass or more, a desired reaction rate can be achieved without requiring a long time for the reaction. Moreover, by setting it as 0.004 mass part or less, reaction rate is not too fast and end point management becomes difficult. Here, the reaction rate of the compound having the cyanate group of the component (b) is compared with the peak area of the compound having the cyanate group of the component (b) at the start of the reaction by the GPC measurement and the peak area after the reaction for a predetermined time. The peak area disappearance rate is obtained.

  Next, the compound (B) in which the molecular structure contains an imidazole structure and the secondary amine moiety is modified [hereinafter also referred to as imidazole compound (B)] is an imidazole compound in which the secondary amine moiety is modified. Without limitation, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ') -Ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4 Examples include imidazole compounds such as '-methylimidazolyl- (1')]-ethyl-s-triazine, and particularly compounds represented by the following general formula (II) or general formula (III) are storage stable. From the viewpoint of low coefficient of thermal expansion.

（式中、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は各々独立に、水素原子、炭素数１〜２０のアルキル基又はフェニル基であり、Ａはアルキレン基又はフェニレン基である。）

(Wherein R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and A is an alkylene group or a phenylene group.)

（式中、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は各々独立に、水素原子、炭素数１〜２０のアルキル基又はフェニル基であり、Ｂは単結合、アルキレン基、アルキリデン基、エーテル基又はスルフォニル基である。）

Wherein R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and B is a single bond, an alkylene group, an alkylidene group or an ether group. Or a sulfonyl group.)

  0.05-3 mass parts is preferable with respect to 100 mass parts of compatibilizing resin (A), and, as for the usage-amount of an imidazole compound (B), 0.07-2 mass parts is more preferable, 0.1-1. 5 parts by mass is particularly preferred. The effect of reducing the coefficient of thermal expansion is obtained by setting it to 0.05 parts by mass or more, and the storage stability is not lowered by setting it to 3 parts by mass or less.

It is preferable that an inorganic filler (C) is further added to the thermosetting resin composition of the present invention. Examples of the inorganic filler (C) include fused silica, crushed silica, mica, talc, short glass fiber or fine powder and hollow glass, calcium carbonate, quartz powder, metal hydrate, and the like. From the viewpoints of low thermal expansion coefficient and high elasticity, fused silica is particularly preferable.
Further, as the inorganic filler (C), metal hydrates such as aluminum hydroxide and magnesium hydroxide are preferable from the viewpoint of heat resistance and flame retardancy, and among the metal hydrates, high heat resistance and flame retardancy are preferred. The thermal decomposition temperature of a metal hydrate having a thermal decomposition temperature of 300 ° C. or higher, such as boehmite type aluminum hydroxide (AlOOH) or gibbsite type aluminum hydroxide (Al (OH) ₃ ), is obtained by heat treatment. Is more preferably a compound adjusted to 300 ° C. or higher, magnesium hydroxide, etc., especially boehmite type aluminum hydroxide (AlOOH) which is inexpensive and has a particularly high thermal decomposition temperature of 350 ° C. or higher and high chemical resistance. preferable.

It is preferable that the usage-amount of an inorganic filler (C) shall be 10-300 mass parts with respect to 100 mass parts of solid content conversion of the total amount of compatibilizing resin (A) and imidazole compound (B), and 100- It is more preferable to set it as 250 mass parts, and it is especially preferable to set it as 150-250 mass parts. By setting it to 10 parts by mass or more, the rigidity of the base material, moisture heat resistance, and flame retardancy can be obtained, and by setting it to 300 parts by mass or less, chemical resistance such as moldability and plating solution resistance decreases. There is nothing.
The average particle size of the inorganic filler (C) is preferably 5 μm or less, more preferably 2 μm or less, and particularly preferably 1 μm or less, from the viewpoint of ensuring insulation reliability.

The inorganic filler (C) used in the present invention is preferably one that has been surface-treated with a silane compound having a functional group.
The silane compound having a functional group used for the inorganic filler (C) is not particularly limited as long as it is a silane compound having a functional group and an alkoxyl group, but vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, N- 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, etc. N- phenyl-3-aminopropyltrimethoxysilane, and the like. Among these, N-phenyl-3-aminopropyltrimethoxysilane represented by the general formula (VII) is particularly preferable.

  Examples of surface treatment methods for the inorganic filler (C) include inorganic organic fillers such as ketone organic solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and alcohol organic solvents such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether. After adding and mixing, the above-mentioned trimethoxysilane compound is added and reacted (surface treatment) at 60 to 120 ° C. with stirring for about 0.5 to 5 hours. The surface treatment can also be obtained commercially from Admatechs, for example, trade names SC-2050KNK and SC-2050HNK manufactured by Admatechs.

  The thermosetting resin composition of the present invention preferably contains a curing accelerator for improving heat resistance, flame retardancy, copper foil adhesion, etc., and examples of the curing accelerator include zinc naphthenate. And organic metal salts such as cobalt naphthenate, tin octylate and cobalt octylate, imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts. By blending these curing accelerators, heat resistance, flame retardancy, copper foil adhesion, and the like can be improved.

In the thermosetting resin composition of the present invention, other flame retardants and flame retardant aids can be optionally used in combination. However, halogen-containing flame retardants containing bromine and chlorine and metal hydroxides having a thermal decomposition temperature of less than 300 ° C. are not suitable for the purpose of the present invention.
Examples of flame retardants and flame retardant aids include phosphoric flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, phosphazenes, red phosphorus, antimony trioxide, and molybdic acid. Examples include inorganic flame retardant aids such as zinc.
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 mass with respect to 100 parts by mass of the compatibilizing resin (A). By setting it to 5 parts by mass or more, flame retardancy and drilling workability are improved, and by setting it to 20 parts by mass or less, the gel time of the varnish becomes too short and the moldability is improved when a laminate is formed by pressing. There is no decline.

The thermosetting resin composition of the present invention can optionally contain a known thermoplastic resin, elastomer, and organic filler.
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.
Examples of the elastomer include polybutadiene, ABS resin, 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, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

  In the present invention, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like can be arbitrarily added to the resin composition, and there is no particular limitation. 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 above-described thermosetting resin composition of the present invention on a base material and then forming a B-stage. 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 used for the prepreg, 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 substrate is not particularly limited. For example, a substrate having a thickness of about 0.03 to 0.5 mm can be used, and the substrate is surface-treated with a silane coupling agent or the like, or mechanically opened. Is suitable from the viewpoints of heat resistance, moisture resistance and processability.
After the prepreg of the present invention is impregnated or coated on the base material so that the amount of the thermosetting resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, It can be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).

The laminate of the present invention is formed using the prepreg of the present invention, and can be formed by laminate molding using the prepreg described above.
That is, the laminated board of this invention can be manufactured by laminating | molding the above-mentioned prepreg, for example by the structure which laminated | stacked 1-20 sheets, and arrange | positioned metal foil, such as copper and aluminum, on the single side | surface or both surfaces. 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 multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and a temperature of 100 to 250 ° C. and a pressure of 2 It can be molded in a range of ˜100 kg / cm ² (0.2 to 10 MPa) and 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.
In addition, the copper clad laminated board obtained in the following examples and comparative examples was measured by the following method and evaluated.

(1) Glass transition temperature (Tg)
A 5 mm square evaluation board from which the copper foil was removed by immersing the copper clad laminate in a copper etching solution was prepared, and the thermal expansion characteristics in the surface direction of the evaluation board were measured using a TMA test apparatus (manufactured by DuPont, TMA2940). Evaluation was made by observation.

(2) Linear thermal expansion coefficient A 5-mm square evaluation board | substrate which removed the copper foil by immersing a copper clad laminated board in a copper etching liquid was produced, and the evaluation board | substrate of the evaluation board | substrate was used using the TMA test apparatus (the Du Pont company make, TMA2940). The linear thermal expansion coefficient of 30 to 100 ° C. in the plane direction was measured.

Production Example 1: Production of compatibilizing resin (A-1) A bisphenol A-type cyanate resin (manufactured by Lonza Japan Co., Ltd.) was added to a reaction vessel having a volume of 3 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. Trade name: Primaset BADCy): 600.0 g, a siloxane resin having a hydroxyl group at the end represented by the following formula (IX) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name: X-22-1821, hydroxyl equivalent: 1,600): 200.0 g Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin; trade name YX-4000, epoxy equivalent; 186): 200.0 g and toluene: 1000.0 g were charged.
Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing resin (A-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 [that is, the reaction rate of the component (b)] was 68%. Moreover, the peak of the product of the thermosetting resin which appears in the vicinity of about 10.9 minutes and 8.0-10.0 minutes was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid was taken out and subjected to FT-IR measurement. A peak around 1700 cm ⁻¹ due to the imino carbonate group, a strong peak near 1560 cm ⁻¹ due to the triazine ring, and a strong peak near 1380 cm ⁻¹ can be confirmed, and the compatibilizing resin (A-1) is produced. I confirmed.

（式中のｐは平均して３５〜４０である。）

(P in the formula is 35-40 on average.)

Production Example 2: Production of compatibilizing resin (A-2) A novolak-type cyanate resin (manufactured by Lonza Japan Co., Ltd.) was placed 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. Product name Primaset PT-15, mass average molecular weight 500 to 1,000): 800.0 g, a siloxane resin having a hydroxyl group at the end represented by the following formula (X) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KF-6003, hydroxyl group equivalent); 2800): 100.0 g, naphthol aralkyl-cresol copolymerization type epoxy resin (manufactured by Nippon Kayaku Co., Ltd .; trade name NC-7000L, epoxy equivalent: 230): 100.0 g and toluene: 1000.0 g were charged. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing resin (A-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 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 novolak-type cyanate resin, the disappearance rate of the peak area [reaction rate of the component (b)] was 43%. Moreover, the peak of the product of the thermosetting resin which appears in the vicinity of about 10.9 minutes and 8.0-10.0 minutes was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. A peak around 1700 cm ⁻¹ due to the imino carbonate group, a strong peak near 1560 cm ⁻¹ due to the triazine ring, and a strong peak near 1380 cm ⁻¹ can be confirmed, and the compatibilizing resin (A-2) is produced. I confirmed.

（式中のｑは平均して７０〜７５である。）

(Q in the formula is 70 to 75 on average.)

Production Example 3: Production of compatibilizing resin (A-3) Dicyclopentadiene-type cyanate resin (Lonza Japan Co., Ltd.) 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. Product name: Primaset DT-4000, weight average molecular weight: 500 to 1,000): 400.0 g, siloxane resin having a hydroxyl group at the end represented by the following general formula (XI) (manufactured by Shin-Etsu Chemical Co., Ltd .; product name X-22 160AS, hydroxyl equivalent: 500): 100.0 g, biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd .; trade name NC-3000H, epoxy equivalent: 280): 500.0 g, mesitylene: 1000.0 g were charged. Next, the temperature was raised to 120 ° C. while stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.30 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing resin (A-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 novolak-type cyanate resin, which is a synthetic raw material that appears in the vicinity of about 12.0 minutes, is shown at the start of the reaction. As compared with the peak area of the novolak-type cyanate resin, the disappearance rate of the peak area [reaction rate of the component (b)] was 43%. Moreover, the peak of the product of the thermosetting resin which appears in the vicinity of about 10.9 minutes and 8.0-10.0 minutes was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. imino carbonates due to group 1700 cm ^-1 vicinity of the peak also, around 1560 cm ^-1 due to the triazine ring, and confirmed strong peak at around 1380 cm ^-1, compatibilizing resin (a-3) is prepared I confirmed.

（式中のｒは平均して１０〜１５である。）

(In the formula, r is 10 to 15 on average.)

Production Example 4: Production of compatibilizing resin (A-4) A bisphenol A-type cyanate resin (manufactured by Lonza Japan Co., Ltd.) was placed in a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heat-coolable volume of 3 liters. Trade name Primaset BADCy): 400.0 g, a siloxane resin having a hydroxyl group at the end shown in the above general formula (IX) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl equivalent: 1,600): 500. 0 g, naphthalene type epoxy resin (Dainippon Ink Chemical Co., Ltd .; trade name: Epiklon HP-4032, epoxy equivalent: 150): 100.0 g and toluene: 1000.0 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, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of compatibilizing resin (A-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 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 [reaction rate of component (b)] was 55%. Moreover, the peak of the product of the thermosetting resin which appears in the vicinity of about 10.9 minutes and 8.0-10.0 minutes was confirmed. Further, the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing weight ratio of 1: 1) to cause reprecipitation, whereby the purified solid content was taken out and subjected to FT-IR measurement. A peak around 1700 cm ⁻¹ due to the imino carbonate group, a strong peak near 1560 cm ⁻¹ due to the triazine ring, and a strong peak near 1380 cm ⁻¹ can be confirmed, and the compatibilizing resin (A-4) is produced. I confirmed.

Production Example 5: Production of fused silica (C-1) surface-treated (wet treatment) with a silane compound having a functional group Reaction with a volume of 3 liters capable of being heated and cooled with a thermometer, a stirrer and a reflux condenser In a container, fused silica (manufactured by Admatechs; trade name SO-25R): 700.0 g and propylene glycol monomethyl ether: 1000.0 g are blended and stirred with N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu). Chemical company make; brand 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 solution of fused silica (C-1) that was wet-treated was obtained.

Comparative Production Example 1: Production of Resin (R-1: Reaction Rate of Component (b) 18%) Bisphenol A was added to a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heat-coolable volume of 3 liters. Type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset BADCy): 600.0 g and a siloxane resin having a hydroxyl group at the end shown in the above general formula (IX) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl group) Equivalent; 1,600): 200.0 g, Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin; trade name YX-4000, epoxy equivalent; 186): 200.0 g and toluene: 1000.0 g were charged. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 1 ° C. for 1 hour. Then, it cooled to room temperature and obtained the solution of resin (R-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 [reaction rate of component (b)] was 18%. In addition, a precipitate was formed in the solution by crystallization the next day.

Comparative Production Example 2: Production of Resin (R-2: Reaction Rate of Component (b) 76%) Bisphenol A was added to a 3 liter reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and capable of heating and cooling. Type cyanate resin (manufactured by Lonza Japan Co., Ltd .; trade name Primaset BADCy): 600.0 g and a siloxane resin having a hydroxyl group at the end shown in the above general formula (IX) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl group) Equivalent; 1,600): 200.0 g, Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; trade name YX-4000, epoxy equivalent 186) 200 g and toluene: 1000.0 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, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 120 The reaction was carried out at 6 ° C. for 6 hours. Then, it cooled to room temperature and obtained the solution of resin (R-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 [reaction rate of the component (b)] was 76%.

Comparative Production Example 3: Production of Resin (R-3: Reaction Rate of Component (b) 53%, (c) No Component) Thermometer, Stirrer, Heating and Cooling Volume with Reflux Cooling Tube In a reaction vessel, bisphenol A type cyanate resin (manufactured by Lonza Japan; trade name Primaset BADCy): 600.0 g and a siloxane resin having a hydroxyl group at the end shown in the general formula (IX) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X -22-1821, hydroxyl equivalent: 1,600): 200.0 g and toluene: 800.0 g. Next, the temperature was raised to 120 ° C. with stirring, and after confirming that the resin solids had dissolved and became a uniform solution, 0.01 g of an 8% by mass mineral spirit solution of zinc naphthenate was added, and about 110 The reaction was carried out at 4 ° C. for 4 hours. Then, it cooled to room temperature and obtained the solution of resin (R-3) which does not contain an epoxy resin. 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 [reaction rate of the component (b)] was 53%.

Examples 1-6, Comparative Examples 1-4
Component (A) compatibilized resin obtained in Production Examples 1 to 4, or resin obtained in Comparative Production Examples 1 to 3, commercially available (B) component imidazole compound, Production Example 5 or Commercial Ingredients (C) inorganic filler and curing accelerator were mixed with methyl ethyl ketone as a diluting solvent and mixed at the blending ratios (parts by mass) shown in Tables 1 and 2 to obtain a resin component. A 60% by weight uniform varnish was obtained.
Next, the obtained 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 mass%.
Four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 25 kg / cm ² (2.5 MPa) and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate.
Using the copper-clad laminate thus obtained, the glass transition temperature and the thermal expansion coefficient were measured and evaluated by the above methods. The evaluation results are shown in Tables 1 and 2.

  In Tables 1 and 2, the (B) component, the (C) component, the curing accelerator, and the epoxy resin used in Comparative Example 3 are as follows.

(B) Component: Imidazole compound (B-1) Epoxy mask imidazole: Mitsubishi Chemical Corporation product name: P-200Z50, imidazole compound modified with secondary amine represented by formula (III))
(B-2) 1-cyanoethyl-2-phenylimidazole (trade name: 2PZ-CN, manufactured by Shikoku Chemicals Co., Ltd.)
(B-3) 2-ethyl-4-methylimidazole (trade name: 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., without modification of amine functional group),
(C) component: inorganic filler (C-1): fused silica surface-treated (wet treatment) with a silane compound having a functional group according to Production Example 5,
(C-2): Fused silica surface-treated with 1.0% by mass of N-phenyl-3-aminopropyltrimethoxysilane based on fused silica (manufactured by Admatech; trade name SC-2050KNK, diluent solvent; methyl isobutyl) Ketone)
(C-3): Fused silica surface-treated with 1.0% by mass of N-phenyl-3-aminopropyltrimethoxysilane based on fused silica (manufactured by Admatech; trade name SC-2050HNK, diluent solvent: cyclohexanone)
(C-4): Boehmite type aluminum hydroxide (AlOOH, manufactured by Kawai Lime; trade name BMT-3L, thermal decomposition temperature: 400 ° C.)
Curing accelerator: 8% by mass mineral spirit solution of zinc naphthenate Epoxy resin used in Comparative Example 3: Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin; trade name YX-4000, epoxy equivalent; 186)

In Table 2, Comparative Examples 1 to 3 could not evaluate the performance of the laminate for the following reasons.
Comparative Example 1: A thermosetting resin precipitated and a varnish could not be produced.
Comparative Example 2: The moldability was poor and a laminate could not be produced.
Comparative Example 3: When the prepreg was formed from the varnish, the resin was separated, and the prepreg and the laminate could not be produced.

  As is apparent from Table 1, the examples of the present invention achieve an excellent glass transition temperature (Tg) and a low coefficient of thermal expansion. On the other hand, as is clear from Table 2, the glass transition temperature (Tg) in Comparative Example 4 is the same as that in Example 1, but the coefficient of thermal expansion is 1.5 ppm / ° C. higher than that in Example 1, and the functional group It can be seen that it is essential to use an imidazole modified with a secondary amine having the above in order to reduce the coefficient of thermal expansion.

  A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition of the present invention and a laminate produced by laminating the prepreg have a high glass transition temperature (Tg) and low thermal expansion. It is useful as a printed wiring board for electronic equipment that exhibits a high rate.

Claims (10)

A siloxane resin having a hydroxyl group at the terminal represented by the following general formula (I) (a), a compound (b) having at least two cyanate groups in one molecule, and a compound having at least two epoxy groups in one molecule (C) per 100 parts by mass of the total amount of components (a) to (c), (a) component 10 to 50 parts by mass, (b) component 40 to 80 parts by mass, (c) component 10 to 50 parts by mass As a phase in which the reaction is carried out at 80 to 120 ° C. in at least one solvent selected from toluene, xylene and mesitylene in the presence of the organometallic salt (d), and the reaction rate of the component (b) is 30 to 70 mol%. A thermosetting resin composition comprising: a resin containing resin (A); and a compound (B) containing a imidazole structure in the molecular structure and having a modified secondary amine moiety.

(In the formula, each R ₁ is independently an alkylene group or alkyleneoxy group having 1 to 5 carbon atoms, Ar ₁ is each independently a single bond, an arylene group or an alkylene group having 1 to 5 carbon atoms, and m is 5 to 5) It is an integer of 100.)   Furthermore, the thermosetting resin composition of Claim 1 containing an inorganic filler (C). The compound (B) containing a imidazole structure in the molecular structure and having a modified secondary amine moiety is a compound represented by the following general formula (II) or general formula (III): Thermosetting resin composition.

(Wherein R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and A is an alkylene group or a phenylene group.)

Wherein R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a phenyl group, and B is a single bond, an alkylene group, an alkylidene group or an ether group. Or a sulfonyl group.) The compound (c) having at least two epoxy groups in one molecule is a compound represented by any one of the following general formula (IV), general formula (V), and general formula (VI): The thermosetting resin composition in any one of -3.

(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.)

(In the formula, t is a number of 1 or more.)   The thermosetting resin composition according to any one of claims 2 to 4, wherein the inorganic filler (C) has an average particle size of 5 µm or less.   The thermosetting resin composition according to any one of claims 2 to 5, wherein the inorganic filler (C) is fused silica.   The thermosetting resin composition according to any one of claims 2 to 6, wherein the inorganic filler (C) is surface-treated with a silane compound having a functional group. The thermosetting resin composition according to claim 7, wherein the silane compound having a functional group is a trimethoxysilane compound represented by the following formula (VII).

  A prepreg that is B-staged after impregnating or coating the base material with the thermosetting resin composition according to claim 1.   A laminate formed using the prepreg according to claim 9.