JP4923862B2 - Method for producing epoxy-modified guanamine compound solution, thermosetting resin composition, and prepreg and laminate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a guanamine compound solution which gives a thermosetting resin composition having a low toxicity and a good solubility with safe organic solvents, and excellent in all of metal foil-bonding property, heat resistance, moisture resistance, flame retardance, heat resistance with copper, a low dielectric characteristic and a low dielectric tangent, the thermosetting resin composition, and a prepreg and laminated board by using the same. <P>SOLUTION: This method for producing the epoxy-modified guanamine compound is provided by adding (d) a resin or monomer having an epoxy group in its molecular structure into the uniform solution consisting of (a) a 6-substituted guanamine compound, (b) a carboxyl group-containing acidic compound having &ge;4.05 acid dissociation constant (pKa) in an infinite dilution aqueous solution at 25&deg;C and (c) a ketone-based organic solvent without having a nitrogen atom in its molecular structure, and reacting at &ge;70&deg;C temperature. The thermosetting resin composition, and the prepreg and laminated board obtained by using the same are also provided. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention provides an epoxy-modified guanamine compound solution that has good solubility in organic solvents, excellent metal foil adhesion, heat resistance, moisture resistance, flame retardancy, and the like, and provides a thermosetting resin composition suitable for electronic parts and the like The manufacturing method of this, a thermosetting resin composition, and a prepreg and laminated board using the same.

  Thermosetting resins are widely used in fields that require high reliability, such as electronic parts, because their unique cross-linked structure exhibits high heat resistance and dimensional stability. In the interlayer insulating material, due to the recent demand for higher density, high copper foil adhesiveness for forming fine wiring and workability when drilling or punching is required.

  Moreover, due to recent environmental problems, mounting of electronic parts using lead-free solder and flame resistance using halogen-free are required, and therefore higher heat resistance and flame resistance than conventional ones are required. Furthermore, in order to improve the safety of the product and the working environment, there is a demand for a thermosetting resin composition that is composed only of low-toxic components and does not generate toxic gases.

  Melamine resins and guanamine compounds, which are thermosetting resins, are resins that are excellent in adhesiveness, flame retardancy, and heat resistance, but lack solubility in organic solvents and are highly toxic, such as N, N-dimethylformamide. If a large amount of the nitrogen atom-containing organic solvent is not used, it is difficult to produce a thermosetting resin composition, and storage stability is insufficient. Moreover, the copper clad laminated board and interlayer insulation material which used these thermosetting resin compositions had a problem which contaminates various chemical | medical solutions, such as a plating solution, when manufacturing an electronic component etc.

Under the circumstances as described above, many resin compositions using a thermosetting resin obtained by condensing a melamine resin or a guanamine compound with an aldehyde such as formaldehyde have been proposed. (For example, see Patent Documents 1 to 4)
However, although these resin compositions have improved solubility in organic solvents, they have a low thermal decomposition temperature and generate toxic decomposition gas, thereby deteriorating the working environment and lead-free solders that have recently been required. Insufficient heat resistance and heat resistance with copper. Also, in fine processing and wiring formation, copper foil adhesion, flexibility, and toughness are insufficient, circuit patterns are broken or peeled off, and cracks occur when drilling or punching is performed. Such problems occur.

  Also disclosed is a method for producing an etherified methylolguanamine compound by reacting a prepolymerization agent such as urea or melamine with etherified methylolguanamine (see, for example, Patent Document 5). However, this etherified methylolguanamine compound also has problems such as heat resistance, adhesiveness, and workability as described above.

  Furthermore, phosphorus compounds have been widely studied as halogen-free flame retardants that can replace bromine-containing flame retardants. However, when using phosphoric acid or phosphoric acid ester, the amount of use is limited and sufficient flame retardancy cannot be obtained due to problems such as bleed, hydrolyzability, heat resistance and electrical reliability degradation. There's a problem. In addition, red phosphorus has problems such as safety reasons such as ignition due to impact and significant deterioration in reliability such as electric corrosion resistance.

Japanese Examined Patent Publication No. 62-046584 Japanese Patent Laid-Open No. 02-258820 Japanese Patent Laid-Open No. 03-145476 JP 2001-11672 A Japanese Examined Patent Publication No. 62-61051

  In view of the present situation, the object of the present invention is to have good solubility in organic solvents with low toxicity and safety, metal foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with copper, low dielectric properties, low It is to provide a method for producing a guanamine compound solution, a thermosetting resin composition, a prepreg and a laminate using the same, which provide a thermosetting resin composition having excellent dielectric loss tangency.

  As a result of intensive research to achieve the above object, the present inventors have determined that an epoxy solution is applied to a homogeneous solution comprising a specific guanamine compound, a carboxyl group-containing acidic compound, and a ketone organic solvent that does not contain a nitrogen atom in the molecular structure. It has been found that an epoxy-modified guanamine compound solution produced by adding a resin or a monomer and reacting it meets the above-mentioned purpose and can be advantageously used for a laminated board or the like. The present invention has been completed based on such findings.

That is, the present invention provides the following method for producing an epoxy-modified guanamine compound solution, a thermosetting resin composition, a prepreg, and a laminate.
1. (A) a 6-substituted guanamine compound represented by the following general formula (1), (b) p-hydroxybenzoic acid and / or m-hydroxybenzoic acid, and (c) an organic solvent containing no nitrogen atom in the molecular structure (D) A method for producing an epoxy-modified guanamine compound solution, which comprises adding (d) a resin or monomer having an epoxy group in the molecular structure and reacting at a temperature of 70 ° C. or higher.

[Equation (1), R ₁ is a phenyl group, a methyl group, butyl group, an allyl group, a vinyl group, a methoxy group or a benzyloxy group. ]
2. (A) A thermosetting resin composition in which an epoxy resin having at least two epoxy groups in one molecule is blended with the epoxy-modified guanamine compound solution produced by the method 1 above.
3. A prepreg obtained by impregnating or coating the thermosetting resin composition of 2 above on a base material and then forming a B-stage.
4). A laminate obtained by laminating the prepreg of 3 above.
5. 4. The laminate of 4 above, which is a metal-clad laminate obtained by heating and pressing after a metal foil is laminated on at least one of the prepregs.

Epoxy-modified guanamine compound solution obtained by the method of the present invention has good solubility in organic solvents that are low in toxicity and safe, metal foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with copper, low dielectric properties The present invention provides a thermosetting resin composition having excellent low dielectric loss tangent properties.
For this reason, the thermosetting resin composition can be used to provide a prepreg or laminate having excellent performance.

Hereinafter, the present invention will be described in detail.
First, the present invention relates to (a) a 6-substituted guanamine compound represented by the following general formula (1), (b) a carboxyl group-containing acidic compound having an acid dissociation constant (pKa) in an infinitely diluted aqueous solution of 4.05 or higher. And (c) (d) a resin or monomer having an epoxy group in the molecular structure is added to a homogeneous solution composed of an organic solvent that does not contain a nitrogen atom in the molecular structure, and reacted at a temperature of 70 ° C. or higher. A method for producing an epoxy-modified guanamine compound solution is provided.
In the present invention, the “compound” in the epoxy-modified guanamine compound solution includes those present as monomers and those present as resins having repeating units.

[Equation (1), R ₁ is a phenyl group, a methyl group, butyl group, an allyl group, a vinyl group, a methoxy group or a benzyloxy group. ]
Examples of the 6-substituted guanamine compound represented by the general formula (1) in (a) include 2,4-diamino-6-phenyl-s-triazine called benzoguanamine and 2,4-diamino called acetoguanamine. -6-methyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine, and the like. Among these, benzoguanamine having a high reaction rate and higher heat resistance, 2,4 -Diamino-6-vinyl-s-triazine is more preferred, and benzoguanamine is particularly preferred because of its low toxicity and low cost.

Examples of the carboxyl group-containing acidic compound having an acid dissociation constant (pKa) in an infinitely diluted aqueous solution of component (b) at 25 ° C. of 4.05 or more include acrylic acid, adipic acid, azelaic acid, (o−, m -, p-) anisic acid, 4-aminobutyric acid, isobutyric acid, isovaleric acid, valeric acid, glutaric acid, acetic acid, cyclohexanecarboxylic acid, 2-naphthoic acid, (o-, m-, p-) hydroxybenzoic acid , Pimelic acid, phenylacetic acid, p-fluorobenzoic acid, propionic acid, hexanoic acid, heptanoic acid, butyric acid, levulinic acid and the like.
Among them, acrylic acid, adipic acid, (o-, m-, p-) anisic acid, isobutyric acid, glutaric acid, acetic acid, cyclohexanecarboxylic acid, which have high solubility of guanamine compounds and can be further improved in heat resistance, (O-, m-, p-) hydroxybenzoic acid, phenylacetic acid, p-fluorobenzoic acid, propionic acid, hexanoic acid, heptanoic acid, butyric acid are preferred, and (o-, m-, p-) Hydroxybenzoic acid is more preferred, p-hydroxybenzoic acid is particularly preferred because it is inexpensive and has excellent copper foil adhesion.
The acid dissociation constant (pKa) in an infinitely diluted aqueous solution at 25 ° C. specified in the present invention is quoted from the Chemical Handbook (Revised 4th edition, Basic edition II, p317, published by Maruzen Co., Ltd. in 1993). It is a numerical value.

  Examples of the organic solvent that does not contain a nitrogen atom in the molecular structure as component (c) include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, and methyl isobutyl. Examples include ketone solvents such as ketone and cyclohexanone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene, and sulfur atom-containing solvents such as dimethyl sulfoxide. Can be used. Among these, cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity, and they remain as residual solvents when producing prepreg because of their high volatility. The difficult propylene glycol monomethyl ether is particularly preferred.

Examples of the resin or monomer having an epoxy group in the molecular structure of the component (d) include, for example, bisphenol A, bisphenol F, biphenyl, novolac, polyfunctional phenol, naphthalene, alicyclic, and alcohol. Examples thereof include glycidyl ether-based resins, glycidyl amine-based resins and glycidyl ester-based resins or monomers, and one or a mixture of two or more types can be used.
Among these, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion Resin, phenol novolac type epoxy resin and cresol novolac type epoxy resin are preferable, and bisphenol F type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin from the viewpoint of flame retardancy and molding processability, A cresol novolac type epoxy resin is more preferable, and a phenol novolac type epoxy resin and a bisphenol F type epoxy resin are particularly preferable because they are inexpensive.

Here, the amount of the carboxyl group-containing acidic compound to equivalents of 6-substituted guanamine compound of the -NH ₂ group in terms, carboxyl groups reactive substituents Conversion (a) of the 6-substituted guanamine compound (b) It is desirable that the ratio of equivalents of the contained acidic compound [(equivalent of 6-substituted guanamine compound) / (equivalent of carboxyl group-containing compound)] is in the range of 0.1 to 10.0. The heat resistance of the thermosetting resin composition obtained by making it 0.1 or more is reduced without causing insufficient solubility in a solvent or causing gelation by making the corresponding amount ratio 10.0 or less. There is nothing to do.

  The amount of the organic solvent not containing a nitrogen atom in the molecular structure of the component (c) is preferably 10 to 1000 parts by mass per 100 parts by mass of the sum of the components (a) and (b). It is more preferable to set it as 100-500 mass parts, and it is especially preferable to set it as 200-500 mass parts. The blending amount of the component (c) is 10 parts by mass or more per 100 parts by mass of the sum of the components (a) and (b), so that the solubility is not insufficient, and it is preferable that the amount is 1000 parts by mass or less. Reaction time.

Further, the amount of the resin or monomer having an epoxy group in the molecular structure of the component (d) is such that the equivalent of the 6-substituted guanamine compound of (a) to the equivalent of the epoxy resin or monomer of the component (d) (—NH ₂ Group conversion) and the sum of the equivalents of the carboxyl group-containing compound (converted to reactive substituents) of (b) [(total of equivalents of 6-substituted guanamine compound and equivalents of carboxyl group-containing compound) / (epoxy resin or monomer) Is preferably in the range of 0.5 to 10.0. By setting it to 10.0 or less, suitable solubility in a solvent can be obtained, and by setting it to 0.5 or more, it is avoided that gelation occurs or the heat resistance of the thermosetting resin is lowered.

The epoxy-modified guanamine compound solution of the present invention is prepared by adding the component (d) to the guanamine compound solution in which the components (a), (b) and (c) are completely dissolved at a temperature of 70 ° C. or higher. Manufactured. Specifically, after the mixture of the components (a), (b) and (c) is heated as necessary to make a uniform solution, the component (d) is added in small portions over time and dissolved. The guanamine compound solution modified with a resin or monomer having an epoxy group in the molecular structure is obtained by reacting at a temperature of 70 ° C. or higher, preferably 100 to 130 ° C. for 0.5 to 10 hours.
In the present invention, the mixture of the components (a), (b), and (c) is a uniform solution at 70 ° C., and as shown in the examples, the epoxy modification is performed without lowering the solder heat resistance and the heat resistance with copper. be able to.
In this reaction, a reaction catalyst can be optionally used as necessary. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. Can be used.

The thermosetting resin composition of the present invention comprises (A) an epoxy-modified guanamine compound solution produced by the above method and (B) an epoxy resin having at least two epoxy groups in one molecule. is there.
The epoxy resin used in the thermosetting resin composition of the present invention is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, biphenyl Resins such as glycidyl ethers, glycidylamines, and glycidyl esters, such as diols, novolacs, polyfunctional phenols, naphthalenes, alicyclics, and alcohols, and one or more of these are mixed Can be used. Among these, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion Resin, phenol novolac type epoxy resin and cresol novolac type epoxy resin are preferable, and bisphenol F type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol are preferable from the viewpoint of flame retardancy and molding processability. A novolac type epoxy resin is more preferable, and a phenol novolac type epoxy resin and a bisphenol F type epoxy resin are particularly preferable because they are inexpensive.

The thermosetting resin composition of the present invention may contain an epoxy resin curing agent. Examples of the curing agent include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, dicyanodiamide and the like. And phenol compounds such as phenol novolak and cresol novolak. Of these, phenol compounds such as phenol novolak and cresol novolak that have good heat resistance are preferred, and cresol novolak type phenol resins are particularly preferred because of their improved flame retardancy and adhesion.
Further, the thermosetting resin composition of the present invention may contain an epoxy resin curing accelerator. Examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines and quaternary. An ammonium salt etc. are mentioned.

  In the thermosetting resin composition of the present invention, the blending amount of (A) the epoxy-modified guanamine compound solution is 1 to 99 mass per 100 mass parts of the total amount of (A) the epoxy-modified guanamine compound solution and (B) the epoxy resin. Part, preferably 20 to 99 parts by weight, more preferably 20 to 90 parts by weight. (A) Excellent flame retardancy, adhesiveness and flexibility can be obtained by setting the blend amount of the epoxy-modified guanamine compound solution to 1 part by mass or more, and excellent heat resistance can be obtained by setting it to 99 parts by mass or less. can get.

Moreover, the thermosetting resin composition of this invention can mix | blend a well-known thermoplastic resin, an elastomer, a flame retardant, a filler, etc. arbitrarily.
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, polyacrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified polyacrylonitrile.

  Examples of flame retardants include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphazenes, red phosphorus and other phosphorus flame retardants, antimony trioxide, hydroxylation Examples include inorganic flame retardants such as aluminum and magnesium hydroxide. Among these flame retardants, the thermosetting resin composition of the present invention also has an advantage that the flame retardant effect is high, and therefore, a non-halogen flame retardant such as a phosphorus flame retardant or an inorganic flame retardant is environmentally friendly. It is preferable from a problem, and it is particularly preferable to use a phosphorus-based flame retardant together with an inorganic flame retardant such as aluminum hydroxide from the viewpoint of compatibility with other characteristics such as flame retardancy and heat resistance.

  Examples of fillers include silica, mica, talc, short glass fiber or inorganic powder such as fine powder and hollow glass, silicone powder, organic powder such as tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether. It is done.

  Furthermore, the thermosetting resin composition of the present invention can arbitrarily use an organic solvent, and the organic solvent is not particularly limited. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohol solvents such as methyl cellosolve, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene, dimethyl Formamide dimethylacetamide, N-methylpyrrolidone and the like can be mentioned, and two or more organic solvents can be mixed and used, but the same organic solvent used for the epoxy-modified guanamine compound solution is preferably used.

  In the present invention, it is possible to add an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like to the thermosetting resin composition. Examples of these additives include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, thioxanthones, stilbene derivatives, etc. Fluorescent 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-mentioned thermosetting resin composition on a base material and then forming a B-stage. That is, the thermosetting resin composition of the present invention can be impregnated or coated on a substrate, and semi-cured (B-staged) by heating or the like to produce the prepreg of the present invention. Hereinafter, the prepreg of the present invention will be described in detail.

As the base material used for the prepreg of the present invention, known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and tetrafluoroethylene, and mixtures thereof. These base materials have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined.
The thickness of the 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 impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. Can be heated and dried for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.

  The laminate of the present invention is obtained by laminating the above-described prepreg of the present invention. That is, a laminated board can be manufactured by laminating | molding the prepreg of this invention, for example by the structure which piled 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. The molding conditions may be, for example, a laminated plate for an electrical insulating material and a multilayer plate. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine or the like is used, and a temperature of 100 to 250 ° C. and a pressure of 0 It can be molded in a range of 2 to 10 mPa and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
The copper clad laminate obtained in the following examples was measured and evaluated for performance by the following method.

(1) Evaluation of copper foil adhesiveness (copper foil peel strength) By immersing a copper-clad laminate in a copper etching solution, an evaluation board was prepared by removing the copper foil while leaving a 1 cm wide band portion. The peel strength of the belt portion was measured using (AG-100C manufactured by Shimadzu Corporation).
(2) Measurement of glass transition temperature (Tg) A 5 mm square evaluation board from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (TMA2940 manufactured by DuPont Co., Ltd.) was used. Used and evaluated by observing the thermal expansion characteristics of the evaluation substrate.

(3) Evaluation of solder heat resistance A 5 cm square evaluation board from which the copper foil has been removed is prepared by immersing a copper clad laminate in a copper etching solution, and a pressure cooker test apparatus (manufactured by Hirayama Seisakusho Co., Ltd.) is used. Then, after performing pressure-cooker treatment for up to 4 hours under the conditions of 121 ° C. and 0.2 mPa, after immersing the evaluation board in a solder bath at a temperature of 288 ° C. for 20 seconds, the solder heat resistance can be improved by observing the appearance. evaluated.
(4) Evaluation of heat resistance with copper (T-288) An evaluation board of 5 mm square was prepared from a copper clad laminate, and the evaluation board was swollen at 288 ° C. using a TMA test apparatus (TMA2940 manufactured by DuPont). It was evaluated by measuring the time until it occurred.

(5) Evaluation of hygroscopicity (water absorption rate) A copper-clad laminate is immersed in a copper etching solution to prepare an evaluation board from which copper foil is removed, and a pressure cooker test apparatus (manufactured by Hirayama Seisakusho Co., Ltd.) is used. Then, after the pressure cooker treatment was performed for 4 hours under the conditions of 121 ° C. and 0.2 mPa, the water absorption rate of the evaluation substrate was measured.
(6) Flame Retardancy Evaluation An evaluation board cut out to a length of 127 mm and a width of 12.7 mm was prepared from an evaluation board obtained by removing a copper foil by immersing a copper-clad laminate in a copper etching solution, and tested for UL94. Evaluation was made according to the method (Method V).
(7) Measurement of relative dielectric constant and dielectric loss tangent An evaluation board from which the copper foil was removed by immersing the obtained copper-clad laminate in a copper etching solution was prepared, and a relative dielectric constant measuring apparatus (HP4291B manufactured by Hewlett-Packard Company) was produced. ) Was used to measure the dielectric constant and dielectric loss tangent at a frequency of 1 GHz.

Production Example 1: Production of epoxy-modified guanamine compound solution (1-1) In a reaction vessel having a thermometer, a stirrer, a moisture meter with a reflux condenser and a heat-coolable volume of 2 liters, benzoguanamine: 168.51 g And p-hydroxybenzoic acid: 49.74 g and propylene glycol monomethyl ether: 509.25 g were added, and the mixture was heated to 120 ° C. and dissolved uniformly. Next, bisphenol F type epoxy resin [manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 807]: 272.50 g was added little by little over 1 hour and dissolved, and then reacted at 120 ° C. for 5 hours to be epoxy modified. A guanamine compound solution (1-1) was obtained. Incidentally, the equivalent ratio of the components in this reaction, - (equivalent of p- hydroxybenzoic acid) / (equivalent of NH ₂ groups in terms of benzoguanamine) a = 2.50, and the equivalent of (-NH ₂ group in terms benzoguanamine p-hydroxybenzoic acid equivalent sum) / (epoxy resin equivalent) = 1.56. The acid dissociation constant (pKa) of p-hydroxybenzoic acid in an infinitely diluted aqueous solution at 25 ° C. is 4.58.

Production Example 2: Production of epoxy-modified guanamine compound solution (1-2) Benzguanamine: 157.76 g in a reaction vessel with a volume of 2 liters capable of being heated and cooled equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. And p-hydroxybenzoic acid: 46.57 g and propylene glycol monomethyl ether: 476.77 g were added, and the mixture was heated to 120 ° C. and dissolved uniformly. Next, phenol novolac-type epoxy resin [manufactured by Dow Chemical Co., Ltd., trade name: DEN-438]: 271.06 g was added and dissolved little by little over 1 hour, and then reacted at 120 ° C. for 2 hours for epoxy. A modified guanamine compound solution (1-2) was obtained. Incidentally, the equivalent ratio of the components in this reaction, - (equivalent of p- hydroxybenzoic acid) / (equivalent of NH ₂ groups in terms of benzoguanamine) a = 2.50, and the equivalent of (-NH ₂ group in terms benzoguanamine p-hydroxybenzoic acid equivalent sum) / (epoxy resin equivalent) = 1.56.

Production Example 3: Production of epoxy-modified guanamine compound solution (1-3) In a reaction vessel with a thermoliter, a stirrer, and a moisture meter with a reflux condenser and a heat-coolable volume of 2 liters, benzoguanamine: 74.55 g And p-hydroxybenzoic acid: 110.03 g and cyclohexanone: 430.70 g were added, and the mixture was heated to 120 ° C. and dissolved uniformly. Next, biphenyl type epoxy resin [trade name: YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.]: 384.72 g was added little by little over 1 hour and dissolved, and then reacted at 140 ° C. for 5 hours to be epoxy modified. A guanamine compound solution (1-3) was obtained. Incidentally, the equivalent ratio of the components in this reaction, - (equivalent of p- hydroxybenzoic acid) / (equivalent of NH ₂ groups in terms of benzoguanamine) a = 0.50, and the equivalent of (-NH ₂ group in terms benzoguanamine The sum of equivalents of p-hydroxybenzoic acid) / (equivalents of epoxy resin) = 1.20.

Production Example 4: Production of epoxy-modified guanamine compound solution (1-4) In a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, benzoguanamine: 168.51 g And m-hydroxybenzoic acid: 49.74 g and propylene glycol monomethyl ether: 509.25 g were added, and the mixture was heated to 120 ° C. and dissolved uniformly. Next, bisphenol F type epoxy resin [manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 807]: 272.50 g was added little by little over 1 hour and dissolved, and then reacted at 120 ° C. for 5 hours to be epoxy modified. A guanamine compound solution (1-4) was obtained. Incidentally, the equivalent ratio of the components in this reaction, - (equivalent of m- hydroxybenzoic acid) / (equivalent of NH ₂ groups in terms of benzoguanamine) a = 2.50, and the equivalent of (-NH ₂ group in terms benzoguanamine The sum of the equivalents of m-hydroxybenzoic acid) / (equivalents of epoxy resin) = 1.56. In addition, the acid dissociation constant (pKa) in the infinite dilution aqueous solution of m-hydroxybenzoic acid at 25 ° C. is 4.08.

Comparative Production Example 1: (Solution of benzoguanamine and maleic acid)
In a 2 liter reaction vessel equipped with a thermometer, a stirrer, a moisture meter with a reflux condenser, and capable of heating and cooling, a benzoguanamine: 187.00 g, maleic acid: 232.00 g, and propylene glycol monomethyl ether: 977. 67 g was added and the temperature was raised to 130 ° C., but it did not dissolve and a solution in which the guanamine compound was uniformly dissolved could not be obtained. The acid dissociation constant (pKa) in an infinitely diluted aqueous solution of maleic acid at 25 ° C. is 1.75.

Comparative Production Example 2: (Solution of benzoguanamine and 2,4-dihydroxybenzoic acid)
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, benzoguanamine: 187.00 g, 2,4-dihydroxybenzoic acid: 308.00 g, and propylene glycol Monomethyl ether: 1155.00 g was added and the temperature was raised to 130 ° C., but it did not dissolve, and a solution in which the guanamine compound was uniformly dissolved could not be obtained. The acid dissociation constant (pKa) of 2,4-dihydroxybenzoic acid in an infinitely diluted aqueous solution at 25 ° C. is 3.30.

Comparative production example 3: (Solution of benzoguanamine and benzoic acid)
In a 2 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser, a liter of benzoguanamine: 187.00 g, benzoic acid: 244.00 g, and propylene glycol monomethyl ether: 1005. 67 g was added and the temperature was raised to 130 ° C., but it did not dissolve and a solution in which the guanamine compound was uniformly dissolved could not be obtained. The acid dissociation constant (pKa) of benzoic acid in an infinitely diluted aqueous solution at 25 ° C. is 4.00.

Example 1
(A) 40 parts by mass of the epoxy-modified guanamine compound solution (1-1) obtained in Production Example 1 as the component, and a cresol novolac type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: Epicron) as the component (B) N-673) 50 parts by mass, cresol novolac type phenolic resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: KA-1165) as an epoxy curing agent, 30 parts by mass of aluminum hydroxide as a flame retardant, solvent The mixture was mixed using methyl ethyl ketone to obtain a uniform varnish having a resin content of 70% by mass. Next, the varnish was impregnated and applied to an E glass cloth having a thickness of 0.2 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 55% by mass. Four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 mPa and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate.
Using the obtained copper-clad laminate, the copper foil adhesiveness (copper foil peel strength), glass transition temperature, solder heat resistance, moisture absorption (water absorption), flame retardancy, relative dielectric constant ( 1 GHz) and dielectric loss tangent (1 GHz) were measured and evaluated, and the results are shown in Table 1.

Example 2
The same procedure as in Example 1 was performed except that 40 parts by mass of the epoxy-modified guanamine compound solution (1-2) obtained in Production Example 2 was used as the component (A). Table 1 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Example 3
The same procedure as in Example 1 was performed except that 40 parts by mass of the epoxy-modified guanamine compound solution (1-3) obtained in Production Example 3 was used as the component (A). Table 1 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Example 4
The same procedure as in Example 1 was performed except that 40 parts by mass of the epoxy-modified guanamine compound solution (1-4) obtained in Production Example 4 was used as the component (A). Table 1 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Example 5
The same procedure as in Example 1 was performed except that 50 parts by mass of a phenol novolac type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: Epicron N-770) was used as the component (B). Table 1 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Example 6
The same procedure as in Example 2 was performed except that 50 parts by mass of a phenol novolac epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: Epicron N-770) was used as the component (B). Table 1 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Comparative Example 1
The same procedure as in Example 1 was performed except that 40 parts by mass of the benzoguanamine solution obtained in Comparative Production Example 1 was used as the component (A) instead of the epoxy-modified guanamine compound solution (1-1). Table 2 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Comparative Example 2
The same procedure as in Example 1 was performed except that 40 parts by mass of the benzoguanamine solution obtained in Comparative Production Example 2 was used as the component (A). Table 2 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Comparative Example 3
The same procedure as in Comparative Example 1 was conducted except that 40 parts by mass of the benzoguanamine solution obtained in Comparative Production Example 3 was used as the component (A). Table 2 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Comparative Example 4
The same procedure as in Comparative Example 1 was conducted except that 45 parts by mass of the epoxy resin and 45 parts by mass of the curing agent were used without using the component (A). Table 2 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Comparative Example 5
(B) It was the same as that of the comparative example 4 except having made 45 parts by mass of a phenol novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron N-770). Table 2 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

As apparent from Table 1, in the examples of the present invention, the copper foil peel strength, heat resistance, moisture resistance,
Excellent flame resistance, heat resistance with copper (T-288), low dielectric properties, and low dielectric loss tangent.
On the other hand, in the comparative example, none of the copper foil peel strength, heat resistance, moisture resistance, flame resistance, heat resistance with copper (T-288), low dielectric properties, low dielectric loss tangent, Inferior in characteristics.
A prepreg obtained by impregnating or coating a base material with a thermosetting resin composition containing the epoxy-modified guanamine compound solution of the present invention, and a laminate produced by laminating the prepreg are bonded to copper foil. Excellent in heat resistance, heat resistance, moisture resistance, flame resistance, heat resistance with copper (T-288), low dielectric properties and low dielectric loss tangent, and is extremely useful as a printed wiring board for electronic devices.

Claims (5)

(A) a 6-substituted guanamine compound represented by the following general formula (1), (b) p-hydroxybenzoic acid and / or m-hydroxybenzoic acid, and (c) an organic solvent containing no nitrogen atom in the molecular structure (D) A method for producing an epoxy-modified guanamine compound solution, which comprises adding (d) a resin or monomer having an epoxy group in the molecular structure and reacting at a temperature of 70 ° C. or higher.

[Equation (1), R ₁ is a phenyl group, a methyl group, butyl group, an allyl group, a vinyl group, a methoxy group or a benzyloxy group. ]   (A) A thermosetting resin composition in which an epoxy resin having at least two epoxy groups in one molecule is blended with the epoxy-modified guanamine compound solution produced by the method according to claim 1.   A prepreg obtained by impregnating or coating the base material with the thermosetting resin composition according to claim 2 and then forming a B-stage.   A laminate obtained by laminating the prepreg according to claim 3.   The laminate according to claim 4, wherein the laminate is a metal-clad laminate obtained by heating and pressing after a metal foil is laminated on at least one of the prepregs.