JP2013108067A - Method for producing compatibilized resin, compatibilized resin, thermosetting resin composition, prepreg and laminated plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a compatibilized resin, capable of providing a thermosetting resin composition which is excellent in all of low thermal expandability, copper foil adhesion, heat resistance, flame retardancy, copper-clad heat resistance (T-300), dielectric characteristic, and drill workability, a compatibilized resin produced by the method, a thermosetting resin composition, and a prepreg and a laminated plate using the same.SOLUTION: The method for producing a compatibilized resin includes: reacting a cyanate compound, a siloxane resin having hydroxyl at the terminal, and a cyloxane resin having epoxy at the terminal at a specific reaction rate. The compatibilized resin is produced by the method. The thermosetting resin composition contains the compatibilized resin (A) and molten silica (B) surface-treated with a trimethoxysilane compound. The prepreg and laminated plate use the composition.

Description

  The present invention relates to a compatibilized resin from which a thermosetting resin composition excellent in low thermal expansion, copper foil adhesion, heat resistance, flame retardancy, heat resistance with copper (T-300), dielectric properties, and drill workability is obtained. The manufacturing method, compatibilizing resin, thermosetting resin composition, prepreg and laminate.

  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

  In other words, due to recent demands for higher density and higher reliability, laminated board materials require high copper foil adhesion, heat resistance, good low thermal expansion, etc. As for the adhesiveness, the copper foil peel strength 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 of the laminated plate material increases, the base material tends to be thinner, and the warp of the base material during heat treatment needs to be small. In order to reduce warpage, it is effective that the surface direction of the substrate has a low thermal expansion, and the linear expansion coefficient is preferably 7 ppm / ° C. or less, more preferably 5 ppm / ° C. or less. Further, as the density is increased, the base material is in a direction that requires more reliability, and the inner wall roughness of the drill hole during drilling is required to be small. The evaluation of the inner wall roughness of the drill hole is evaluated by the penetration property of the plated copper, and the maximum plating penetration length is desirably 20 μm or less, and more desirably 15 μm or less. Furthermore, the demand for high-speed response continues to increase, and it is desirable that the relative dielectric constant of the base material is 4.7 or less and the dielectric loss tangent is 0.010 or less.

As described above, the thermosetting resin composition used as the insulating resin is required to have a high level of properties because of the demand for higher density and high reliability of the laminated board material, and the resin composition satisfying all these characteristics is required. Development is underway.
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.

Cyanate compound, which is a thermosetting resin, is a resin with excellent dielectric properties and flame retardancy, but when used as it is in an epoxy curable thermosetting resin, it does not have sufficient heat resistance and toughness. Further, low thermal expansion is desired as a thermosetting resin corresponding to the generation.
For this reason, 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 document 1, 2, and 3). However, since these exhibit low thermal expansibility, the amount of inorganic filler used is large, and when 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

  In view of the current situation, the object of the present invention is to solve the above-mentioned problems when using a cyanate compound that is a thermosetting resin, low thermal expansion, copper foil adhesion, heat resistance, flame resistance, and heat resistance with copper. (T-300), a method for producing a compatibilizing resin capable of producing a thermosetting resin composition excellent in all of dielectric properties and drill workability, a compatibilizing resin produced by the production method, and thermosetting It is providing a resin composition, a prepreg using this, and a laminated board.

As a result of diligent research to solve the above-mentioned problems, the present invention is a compatibilized resin (A) obtained by reacting a cyanate compound, a siloxane resin having a hydroxyl group at the terminal, and a siloxane resin having an epoxy group with a specific reaction rate. ) And a resin composition containing fused silica (B) surface-treated with a trimethoxysilane compound, it is found that an excellent thermosetting resin composition having the above-mentioned characteristics can be obtained, and the present invention It came to complete. The present invention has been completed based on such findings.
That is, the present invention provides the following method for producing a compatibilizing resin, compatibilizing resin, 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 an epoxy group at the terminal represented by the following general formula (II) A siloxane resin (c) having a component (a) 5 to 15 parts by mass, component (b) 40 to 90 parts by mass, and component (c) 5 per 100 parts by mass of the total amount of components (a) to (c). In the presence of the organic metal salt (d), the reaction is carried out at 80 to 120 ° C. in a solvent selected from toluene, xylene and mesitylene, and the reaction rate of the component (b) is 30 to 70 mol%. A method for producing a compatibilizing resin having an imino carbonate structure and a triazine structure.

（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.)

（式中Ｒ₂は、各々独立に炭素数１〜５のアルキレン基であり，ｎは５〜１００の整数である。）

(In the formula, each R ₂ is independently an alkylene group having 1 to 5 carbon atoms, and n is an integer of 5 to 100.)

2. A thermosetting resin comprising a compatibilizing resin (A) produced by the method of 1 and a fused silica (B) surface-treated with a trimethoxysilane compound represented by the following formula (III): Composition.

3. A prepreg that has been B-staged after impregnating or coating the thermosetting resin composition of 2 in a substrate.
4). A laminate formed by using the prepreg of 3 above.
5. 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 an epoxy group at the terminal represented by the following general formula (II) A siloxane resin (c) having a component (a) 5 to 15 parts by mass, component (b) 40 to 90 parts by mass, and component (c) 5 per 100 parts by mass of the total amount of components (a) to (c). In the presence of the organic metal salt (d), the reaction is carried out at 80 to 120 ° C. in a solvent selected from toluene, xylene and mesitylene, and the reaction rate of the component (b) is 30 to 70 mol%. A compatibilizing resin having an imino carbonate structure and a triazine structure.

（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.)

（式中Ｒ₂は、各々独立に炭素数１〜５のアルキレン基であり，ｎは５〜１００の整数である。）

(In the formula, each R ₂ is independently an alkylene group having 1 to 5 carbon atoms, and n is an integer of 5 to 100.)

  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 low thermal expansion, copper foil adhesion, heat resistance. , Flame retardant, heat resistance with copper (T-300), dielectric properties, drilling workability, no environmental problems, and excellent product safety It is.

Hereinafter, the present invention will be described in detail.
First, the method for producing a compatibilizing resin of the present invention includes a siloxane resin (a) having a hydroxyl group at a terminal represented by the following general formula (I), a compound (b) having at least two cyanate groups in one molecule, and The siloxane resin (c) having an epoxy group at the terminal represented by the following general formula (II) is used in an amount of (a) 5 to 15 parts by mass per 100 parts by mass of the total components (a) to (c). 40) to 90 parts by mass of component (c) and 5 to 55 parts by mass of component (c), in the presence of the organometallic salt (d), in the solvent selected from toluene, xylene and mesitylene at 80 to 120 ° C. In this method, a triazine ring formation reaction is performed, and the reaction rate of the component (b) is 30 to 70 mol%.

（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.)

（式中Ｒ₂は、各々独立に炭素数１〜５のアルキレン基であり，ｎは５〜１００の整数である）

(In the formula, each R ₂ is independently an alkylene group having 1 to 5 carbon atoms, and n is an integer of 5 to 100)

  The siloxane resin of component (a) used for the production of the compatibilizing resin 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).

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

  H in the above general formula (X) 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.

  The component (c) used for the production of the compatibilizing resin is not particularly limited as long as it is a siloxane resin having an epoxy group at the terminal represented by the general formula (II). For example, the product name KF-105 (epoxy equivalent: 490), brand name X-22-163A (epoxy equivalent: 950), brand name X-22-163B (made by Shin-Etsu Chemical Co., Ltd.) whose both ends are epoxy groups Epoxy equivalent: 1760), trade name X-22-163C (epoxy equivalent: 2790), and the like. These are commercially available from Shin-Etsu Chemical Co., Ltd. and Toray Dow Corning Co., Ltd.

In the method for producing the compatibilized resin, the raw material composition is (a) 5 to 15 parts by mass, (b) 40 to 90 parts by mass, (c) per 100 parts by mass of the total amount of the components (a) to (c). As component 5 to 55 parts by mass, the reaction is carried out at 80 to 120 ° C. in a solvent selected from toluene, xylene and mesitylene in the presence of organometallic salt (d), and the reaction rate of component (b) is 30 to 70 mol%. And
The organometallic salt of component (d) serves as a reaction catalyst, and examples thereof 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.

That is, in the method for producing a compatibilizing resin of the present invention, components (a) to (c) are uniformly dissolved in a solvent selected in advance from toluene, xylene and mesitylene, and converted to imino carbonate at a reaction temperature of 80 to 120 ° C. The reaction and the triazine cyclization reaction are performed, and a pre-reaction is performed so that the reaction rate of the compound (b) having a cyanate group is 30 to 70 mol%.
Here, 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 desired reaction does not proceed with the other solvent, and heat resistance and the like are lowered. 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.

  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. Further, the three-dimensional network structure proceeds by a reaction in which the cyanate group is trimerized to form a triazine ring. At this time, the siloxane resin (c) having an epoxy group at the terminal represented by the general formula (II) is 3 A compatibilized resin in which the components (a), (b), and (c) are uniformly dispersed is produced by uniformly dispersing in the dimensional network structure.

  The raw material composition in the production of the compatibilized resin is (a) component 5 to 15 parts by mass, (b) component 40 to 90 parts by mass, and (c) component 5 per 100 parts by mass of the total amount of components (a) to (c). It is preferable to set it as (a) component 10-15 mass part, (b) component 50-80 mass part, and (c) component 10-35 mass part. Here, when the component (a) is less than 5 parts by mass, the low thermal expansion property in the surface direction of the obtained substrate may be lowered, and when the component (a) exceeds 15 parts by mass, Chemical resistance may decrease. When the component (b) is less than 40 parts by mass, the compatibility of the obtained resin may be reduced, and when the component (b) exceeds 90 parts by mass, the low thermal expansion property in the surface direction of the obtained substrate is obtained. May decrease. When the component (c) is less than 5 parts by mass, the moisture resistance and heat resistance may be reduced, and when the component (c) is more than 55 parts by mass, the copper foil adhesion and dielectric properties may be reduced.

  The amount of the organic metal salt (d) used is preferably 0.0001 to 0.004 parts by mass with respect to 100 parts by mass of the total amount of the 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 (b) having a cyanate group 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 reaction for a predetermined time by GPC measurement. It is calculated from the disappearance rate.

The reaction temperature of such a pre-reaction is 80 to 120 ° C, preferably 100 to 110 ° C. If the reaction temperature is less than 80 ° C., the production time (reaction time) may be too long, and if it exceeds 120 ° C., a side reaction of the epoxy resin occurs, which may cause gelation.
The reaction rate of the pre-reaction is such that the reaction rate (disappearance rate) of the compound (b) having a cyanate group is 30 to 70 mol%, preferably 40 to 68 mol%. If the reaction rate is less than 30 mol%, the resulting resin is not compatibilized, the resin separates and becomes cloudy, and the B-stage coated fabric is not manufactured. 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 thermosetting resin composition of the present invention contains a compatibilizing resin (A) produced by the above method and a fused silica (B) surface-treated with a trimethoxysilane compound represented by the following formula (III) It is characterized by doing.

  The surface-treated fused silica of the component (B) can be obtained by surface-treating the fused silica using the trimethoxysilane compound represented by the above formula (III). (B) component, for example, after adding fused silica to a ketone organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or alcohol organic solvent such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and the like, The trimethoxysilane compound represented by the formula (III) is added and subjected to surface treatment (wet treatment) at 60 to 120 ° C. with stirring for about 0.5 to 5 hours. The fused silica is also commercially available from Admatechs and others, for example, trade names SC-2050KNK and SC-2050HNK manufactured by Admatechs.

  The amount of component (B) fused silica used is preferably 10 to 300 parts by weight, more preferably 100 to 250 parts by weight, with respect to 100 parts by weight of component (A) in terms of solid content. It is especially preferable to set it as -250 mass parts. By being 10 parts by mass or more, the rigidity of the base material, moisture heat resistance, and flame resistance are not insufficient, and by being 300 parts by mass or less, resistance to moldability, plating solution resistance, etc. There is no deterioration in chemical properties.

  In the thermosetting resin composition of the present invention, an inorganic filler (C) other than the component (B) may be used. Examples of the inorganic filler (C) include crushed silica, mica, talc, short glass fiber or fine powder, hollow glass, calcium carbonate, quartz powder, and metal hydrate. 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, such as boehmite type aluminum hydroxide (AlOOH), or gibbsite type aluminum hydroxide, because both high heat resistance and flame retardancy are compatible. More preferred is a compound in which the thermal decomposition temperature of (Al (OH) 3) is adjusted to 300 ° C. or higher by heat treatment, magnesium hydroxide, etc., particularly inexpensive, a particularly high thermal decomposition temperature of 350 ° C. or higher, and a high resistance to resistance. Boehmite type aluminum hydroxide (AlOOH) having chemical properties is particularly preferable.

  The amount of the inorganic filler (C) used is preferably 0 to 200 parts by weight, more preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the component (A) in terms of solid content. It is especially preferable to set it as 150 mass parts. If it is 10 parts by mass or more, the flame retardancy will not be insufficient, and if it is 200 parts by mass or less, chemical resistance such as plating solution resistance and moldability will not be reduced.

  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. By using a curing accelerator, heat resistance, flame retardancy, copper foil adhesion, etc. are not insufficient.

In the thermosetting resin composition of the present invention, an inorganic flame retardant aid (D) other than the components (B) and (C) can be arbitrarily used. 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 inorganic flame retardant aids (D) include triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric ester compounds, phosphazenes, phosphorous flame retardants such as red phosphorus, antimony trioxide, 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. It is preferable that the usage-amount of zinc molybdate shall be 5-20 mass parts with respect to 100 mass parts of 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, flame retardant, 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 the flame retardant include the inorganic filler (C).
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 the resin composition is not particularly limited. 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 in a base material and then forming a B-stage. Hereinafter, the prepreg of the present invention will be described in detail.
That is, 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) Copper foil adhesion (copper foil peel strength)
A 1 cm wide copper foil was formed by immersing the copper clad laminate in a copper etching solution to produce an evaluation substrate, and the adhesion (peel strength) of the copper foil was measured using a tensile tester.

(2) 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.

(3) Solder heat resistance A 5 cm square evaluation board from which the copper foil has been removed by immersing a copper clad laminate in a copper etching solution is prepared and 121 ° C. using a pressure cooker test apparatus manufactured by Hirayama Seisakusho. After performing the pressure-cooker treatment for up to 4 hours under the condition of 2 atm, the evaluation substrate was immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the solder heat resistance was evaluated by observing the appearance.

(4) 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 was used using the TMA test apparatus (made by DuPont, TMA2940). The linear thermal expansion coefficient of 30 to 100 ° C. in the plane direction was measured.

(5) Flame retardance A test piece cut out to a length of 127 mm and a width of 12.7 mm was prepared from an evaluation substrate obtained by removing a copper foil by immersing a copper clad laminate in a copper etching solution, and a UL94 test method ( Evaluation was made according to V method.

(6) Heat resistance with copper (T-300)
A 5 mm square evaluation board was produced from the copper clad laminate, and evaluation was performed by measuring the time until the evaluation board swells at 300 ° C. using a TMA test apparatus (manufactured by DuPont, TMA2940).

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

(8) Drill workability Using a drill with a diameter of 0.105 mm (Union Tool MV J676), the number of rotations: 160,000 rpm, feed rate: 0.8 m / min, the number of stacked sheets: 6000 hits, 6000 hits Thus, an evaluation substrate was produced, and the inner wall roughness of the drill hole was evaluated. The inner wall roughness was evaluated by performing electroless copper plating (plating thickness: 15 μm) and measuring the maximum value of the plating penetration length into the hole wall.

Production Example 1: Production of Compatibilized 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 stirring device, and a reflux condenser. Brand name Primaset BADCy): 800.0 g, siloxane resin represented by the following formula (IV) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl group equivalent; 1600): 50.0 g, the following formula (V) 150.0 g (trade name X-22-163B, epoxy equivalent; 1760): 150.0 g and toluene: 1500.0 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-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 the component (b)] was 68%. Moreover, the peak of the product of the thermosetting resin which appears at about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. peak around 1700 cm ^-1 due to the imino carbonate group also, around 1560 cm ^-1 due to the triazine ring, and 1380cm intense peaks can be confirmed at around ^-1, compatibilizing resin (a-1) is produced It was confirmed.

（式中のｐは平均値として３５〜４０の数である。）

(P in the formula is a number of 35 to 40 as an average value.)

（式中のｑは平均値として３８〜４３の数である。）

(Q in the formula is an average value of 38 to 43.)

Production Example 2: Production of compatibilizing resin (A-2) A novolak-type cyanate resin (manufactured by Lonza Japan Co., Ltd.) Name Primaset PT-15, mass average molecular weight 500-1,000): 800.0 g and a siloxane resin represented by the following formula (VI) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name KF-6003, hydroxyl group equivalent; 2800): 100 0.0 g, a siloxane resin represented by the above formula (V) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-163B, epoxy equivalent: 1760): 100.0 g and toluene: 1500.0 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-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 35%. Moreover, the peak of the product of the thermosetting resin which appears at about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, 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. peak around 1700 cm ^-1 due to the imino carbonate group also, around 1560 cm ^-1 due to the triazine ring, and confirmed strong peak at around 1380 cm ^-1, compatibilizing resin (a-2) is prepared It was confirmed.

（式中のｒは平均値として７０〜７５の数である。）

(R in the formula is a number of 70 to 75 as an average value.)

Production Example 3: Production of Compatibilized 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. Trade name: Primaset DT-4000, mass average molecular weight: 500 to 1,000): 400.0 g, siloxane resin represented by the following formula (VII) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name: X-22-160AS, hydroxyl group equivalent: 500) : 50.0 g, a siloxane resin represented by the above formula (V) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-163B, epoxy equivalent: 1760) 550.0 g and mesitylene: 1500.0 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 dicyclopentadiene-type cyanate resin, the disappearance rate of the peak area [reaction rate of the component (b)] was 53%. Moreover, the peak of the product of the thermosetting resin which appears at about 10.9 minutes vicinity and 8.0-10.0 vicinity was confirmed. Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. peak around 1700 cm ^-1 due to the imino carbonate group 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 It was confirmed.

（式中のｓは平均値として１０〜１５の数である。）

(S in the formula is an average value of 10 to 15)

Production Example 4: Production of compatibilizing resin (A-4) A bisphenol A type cyanate resin (manufactured by Lonza Japan Co., Ltd.) 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. Trade name Primaset BADCy): 400.0 g, siloxane resin represented by the above formula (IV) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl equivalent: 1600): 150.0 g, in the following formula (VIII) The following siloxane resin (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-163C, epoxy equivalent; 2790): 450.0 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-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 at 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 carbonate group peak near 1700 cm ^-1 due to the addition, the vicinity of 1560 cm ^-1 attributable to the triazine ring, and 1380 cm ^-1 can strong peaks confirmed the vicinity, compatibilizing resin (a-4) is prepared It was confirmed.

（式中のｑは平均値として７０〜７５の数である。）

(Q in the formula is an average value of 70 to 75.)

Production Example 5: Production of fused silica (B-1) surface-treated with a trimethoxysilane compound In a 3 liter reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and capable of heating and cooling, fused silica ( Admatechs Co., Ltd .; trade name SO-25R): 700.0 g and propylene glycol monomethyl ether: 1000.0 g were mixed and stirred with N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .; product) 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 wet-processed fused silica (B-1) solution was obtained.

Comparative production example 1: Production of (resin (A-5): reaction rate of component (b) 22%) In a reaction vessel having a volume of 3 liters capable of being heated and cooled with a thermometer, a stirrer and a reflux condenser, Bisphenol A type cyanate resin (manufactured by Lonza Japan; trade name Primaset BADCy): 600.0 g and a siloxane resin represented by the above formula (IV) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821, hydroxyl equivalent: 1600) ): 200.0 g, a siloxane resin represented by the above formula (V) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-163B, epoxy equivalent: 1760): 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 (A-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 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 22%. In addition, a precipitate was formed in the solution by crystallization the next day.

Comparative Production Example 2: Production of (resin (A-6): 79% reaction rate of component (b)) In a reaction vessel having a volume of 3 liters capable of being heated and cooled with a thermometer, a stirrer and a reflux condenser, Bisphenol A type cyanate resin (manufactured by Lonza Japan; trade name Primaset BADCy): 600.0 g, siloxane resin represented by the above formula (IV) (manufactured by Shin-Etsu Chemical; trade name X-22-1821, hydroxyl equivalent: 1600) : 200.0 g, a siloxane resin represented by the above formula (V) (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-163B, epoxy equivalent: 1760): 200.0 g and toluene: 1500.0 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 (A-6).
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 79%.

Comparative Production Example 3: Production of (Resin (A-7): (b) Component Reaction Rate 53%, (c) No Component) Heating and Cooling Volume 2 with Thermometer, Stirrer, Reflux Cooling Tube 2 In a reaction vessel of 1 liter, bisphenol A type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset BADCy): 600.0 g, siloxane resin represented by the above formula (IV) (Shin-Etsu Chemical Co., Ltd .; trade name X-22-1821) , Hydroxyl equivalent: 1600): 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 (A-7).
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 1-5
Component (A) compatibilized resin obtained in Production Examples 1 to 4, or resin obtained in Comparative Production Examples 1 to 3, Production Example 5 or commercially available (B) component, and if necessary (C ) Component, component (D), and curing accelerator were mixed in the mixing ratio (parts by mass) shown in Tables 1 and 2 using methyl ethyl ketone as a diluent solvent, and the resin content was uniform at 60% by mass. 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, copper foil adhesion (copper foil peel strength), glass transition temperature, solder heat resistance, linear expansion coefficient, flame resistance, heat resistance with copper (T-300) ), Relative dielectric constant (1 GHz), dielectric loss tangent (1 GHz) and drill workability were measured and evaluated by the methods described above. The evaluation results are shown in Tables 1 and 2.

  In Tables 1 and 2, commercially available (B) component, optionally used (C) component, (D) component, curing accelerator, epoxy resin and fused silica used in Comparative Examples are as follows: Street.

Component (B) Fused silica (B-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)
Fused silica (B-3): Fused silica surface-treated with 1.0% by mass of N-phenyl-3-aminopropyltrimethoxysilane with respect to fused silica (manufactured by Admatech; trade name SC-2050HNK, diluent solvent; Cyclohexanone)
Fused silica (B-4): Fused silica (manufactured by Admatech; trade name SO-25R)
Fused silica (B-5): 1.0% by mass of fused silica represented by the following formula (IX) and surface-treated with γ-glycidoxypropyltrimethoxysilane (manufactured by Admatech; trade name SC1030- MJA, diluent solvent; methyl ethyl ketone)

(C) Inorganic filler (AlOOH): Boehmite type aluminum hydroxide (manufactured by Kawai Lime Co., Ltd .; trade name BMT-3L, thermal decomposition temperature: 400 ° C.)
(D) Inorganic flame retardant aid (KG-1100): Inorganic flame retardant aid having zinc molybdate supported on talc (manufactured by Sherwin Williams; trade name Chemguard 1100)
Curing accelerator: 8 mass% mineral spirit solution of zinc naphthenate Epoxy group-containing siloxane resin used in Comparative Example 3 (manufactured by Shin-Etsu Chemical Co., Ltd .; trade name X-22-163B, epoxy equivalent: 1760)

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 are copper foil peel strength, crow transition temperature (Tg), solder heat resistance, low thermal expansion, flame resistance, heat resistance with copper (T-300), Excellent low dielectric properties, low dielectric loss tangent, and drillability.
On the other hand, as is clear from Table 2, the comparative examples are copper foil peel strength, crow transition temperature (Tg), solder heat resistance, low thermal expansion, flame retardancy, heat resistance with copper (T-300), low None of them satisfy all of the dielectric characteristics, low dielectric loss tangent, and drillability, and are inferior to any of the characteristics.

The thermosetting resin composition of the present invention is not only excellent in solder heat resistance and flame retardancy, but also described in the background art, copper foil adhesion (copper foil peel strength), heat resistance with copper (T-300), All the characteristics of drill workability, relative permittivity, and dielectric loss tangent have reached the level required for high density and high reliability in recent years.
Therefore, by using the thermosetting resin composition of the present invention, high density and high reliability of the wiring board required today are achieved, and the thermosetting resin composition of the present invention is manufactured for electronic devices and the like. Can be widely used.

Claims (5)

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 an epoxy group at the terminal represented by the following general formula (II) A siloxane resin (c) having a component (a) 5 to 15 parts by mass, component (b) 40 to 90 parts by mass, and component (c) 5 per 100 parts by mass of the total amount of components (a) to (c). In the presence of the organic metal salt (d), the reaction is carried out at 80 to 120 ° C. in a solvent selected from toluene, xylene and mesitylene, and the reaction rate of the component (b) is 30 to 70 mol%. A method for producing a compatibilizing resin having an imino carbonate structure and a triazine structure.

(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.)

(In the formula, each R ₂ is independently an alkylene group having 1 to 5 carbon atoms, and n is an integer of 5 to 100) The heat | fever characterized by including the compatible resin (A) manufactured by the method of Claim 1, and the fused silica (B) surface-treated by the trimethoxysilane compound shown by following formula (III) Curable resin composition.

  A prepreg that has been B-staged after impregnating or coating the thermosetting resin composition according to claim 2 in a substrate.   A laminate formed using the prepreg according to claim 3. 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 an epoxy group at the terminal represented by the following general formula (II) A siloxane resin (c) having a component (a) 5 to 15 parts by mass, component (b) 40 to 90 parts by mass, and component (c) 5 per 100 parts by mass of the total amount of components (a) to (c). In the presence of the organic metal salt (d), the reaction is carried out at 80 to 120 ° C. in a solvent selected from toluene, xylene and mesitylene, and the reaction rate of the component (b) is 30 to 70 mol%. A compatibilizing resin having an imino carbonate structure and a triazine structure.

(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.)

(In the formula, each R ₂ is independently an alkylene group having 1 to 5 carbon atoms, and n is an integer of 5 to 100)