JP2007138127A - Phosphorus-containing guanamine resin, thermosetting resin composition using the same, and prepreg and laminated plate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin having good solubility in an organic solvent when forming a thermosetting resin composition, providing the thermosetting resin composition having all excellent metal foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance when attached to copper, low dielectric characteristics and low dielectric loss tangent; and to provide the thermosetting resin composition using the resin, and a prepreg and a laminated plate using the composition. <P>SOLUTION: The phosphorus-containing guanamine resin is a reaction product of (a) a 6-substituted guanamine compound, with an aromatic compound having (b) an acid anhydride group including maleic anhydride and (c) at least one P-H bond in one molecule. The thermosetting resin composition contains the phosphorus-containing guanamine resin and an epoxy resin. The prepreg and the laminated plate are obtained by using the composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a thermosetting resin having good solubility in an organic solvent, excellent in metal foil adhesion, heat resistance, moisture resistance, flame retardancy, etc., and providing a thermosetting resin composition suitable for electronic parts and the like. The present invention relates to a thermosetting resin composition using the same, and a prepreg and a laminate 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 their solubility in organic solvents is insufficient, making it difficult to produce thermosetting resin compositions. There was also a problem that storage stability was insufficient. In addition, copper-clad laminates and interlayer insulation materials using these thermosetting resins have a problem of contaminating various chemicals such as plating solutions when manufacturing electronic parts and the like.

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 22)
However, although these resin compositions have improved solubility in organic solvents, they have a low thermal decomposition temperature and lack the heat resistance to lead-free solder and the heat resistance with copper required in recent years. 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.

In addition, a method for producing an etherified methylolguanamine resin by reacting a prepolymerization agent such as urea or melamine with etherified methylolguanamine has been disclosed (see, for example, Patent Document 23). However, this etherified methylolguanamine resin also has problems such as heat resistance, adhesiveness, and workability as described above.
In addition, phosphorus compounds are widely studied as halogen-free flame retardants to 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 Patent Publication No. 06-008342 Japanese Patent Publication No. 06-039581 Japanese Patent Publication No. 06-102701 Japanese Patent Publication No. 07-051659 Japanese Patent Publication No. 03-000410 Japanese Patent Publication No. 03-001343 Japanese Patent Publication No. 04-054613 Japanese Examined Patent Publication No. Sho 62-017655 Japanese Patent Publication No. 62-035417 Japanese Patent Publication No. 63-060788 Japanese Patent No. 002611404 Japanese Patent No. 002832672 Japanese Patent No. 002893845 Japanese Patent No. 002899637 Japanese Patent No. 003588456 Japanese Patent No. 003106211 Japanese Patent No.003113268 Japanese Patent No. 002674179 Japanese Patent No. 002680355 Japanese Patent No. 002719793 Japanese Patent No. 003287475 Japanese Patent No. 003356901 Japanese Examined Patent Publication No. 62-61051

  In view of the current situation, the object of the present invention is to have good solubility in an organic solvent during the preparation of a thermosetting resin composition, adhesion to metal foil, heat resistance, moisture resistance, flame resistance, heat resistance with copper, low By providing a thermosetting resin that provides a thermosetting resin composition excellent in all of dielectric properties and low dielectric loss tangent, a thermosetting resin composition using the same, and a prepreg and a laminate using the thermosetting resin composition is there.

  As a result of intensive studies to achieve the above object, the inventors of the present invention comprise a reaction product of a specific guanamine compound, a carboxylic acid anhydride containing maleic anhydride, and an aromatic compound having a P—H bond. It has been found that a resin or a resin comprising a reaction product containing an N-substituted maleimide compound as a reaction component 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 thermosetting resin, thermosetting resin composition, prepreg and laminate.
1. (A) a 6-substituted guanamine compound represented by the following general formula (1), (b) a carboxylic acid anhydride containing maleic anhydride, and (c) an aromatic compound having at least one PH bond in one molecule. A phosphorus-containing guanamine resin characterized by being a reaction product of

(In the formula (1), R ₁ represents a phenyl group, a phenyl group having a substituent, an alkyl group having 1 to 5 carbon atoms, or a benzyloxy group.)
2. (D) The phosphorus-containing guanamine resin according to 1 above, which is a reaction product having an N-substituted maleimide compound represented by the following general formula (2) as a reaction component.

(In formula (2), R ₂ represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a phenyl group having a substituent.)
3. (A) A thermosetting resin composition comprising the above-mentioned 1 or 2 phosphorus-containing guanamine resin and (B) an epoxy resin having at least two epoxy groups in one molecule.
4). A prepreg obtained by impregnating or coating the thermosetting resin composition of 3 above on a base material and then forming a B-stage.
5. A laminate obtained by laminating one or more prepregs of the above 4 and heating and pressing.
6). 6. The laminate of 5 above, which is a metal-clad laminate obtained by stacking a metal foil on at least one of the stacked prepregs and then heating and pressing.

The phosphorus-containing guanamine resin of the present invention has good solubility in an organic solvent during preparation of a thermosetting resin composition, 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.

The present invention will be described in detail below.
First, the thermosetting guanamine resin of the present invention comprises (a) a 6-substituted guanamine compound represented by the following general formula (1), (b) a carboxylic acid anhydride containing maleic anhydride, and (c) at least 1 in one molecule. It is a reaction product of an aromatic compound having one P—H bond.

(In the formula (1), R ₁ represents a phenyl group, a phenyl group having a substituent, an alkyl group having 1 to 5 carbon atoms, or a benzyloxy group.)
The 6-substituted guanamine compound represented by the general formula (1) in (a) is, for example, benzoguanamine,
Examples include acetoguanamine and substituted melamine derivatives. Among them, benzoguanamine and acetoguanamine are more preferable from the viewpoint of high reaction rate during reaction and higher heat resistance, and benzoguanamine is particularly preferable from the viewpoint of low toxicity. .

The component (b) contains maleic anhydride as an essential component and, if necessary, other carboxylic acid anhydrides are used in combination.
Examples of the carboxylic anhydride used in combination include aliphatic carboxylic anhydrides such as succinic anhydride and tetrahydrophthalic anhydride, and aromatic carboxylic anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride. Etc. Of these, succinic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride, which have a high reaction rate and can achieve higher heat resistance, are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred because of their excellent solubility. Succinic anhydride is particularly preferable from the viewpoint of flammability.
The proportion of maleic anhydride in component (b) is preferably 10 mol% or more.

  Examples of the aromatic compound having at least one P—H bond in one molecule of (c) include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine, and diphenylphosphine. Among them, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenyl, which have a high reaction rate at the time of reaction and can have higher heat resistance. Phosphine is more preferred, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is particularly preferred from the viewpoint of low toxicity and low cost.

In the phosphorus-containing guanamine resin of the present invention, (a) the anhydride carboxyl group equivalent (b ¹ ) of the carboxylic anhydride containing maleic anhydride (b) relative to the equivalent (a ¹ ) of the —NH ₂ group of the 6-substituted guanamine compound The ratio (b ¹ / a ¹ ) is preferably in the range of 0.5 to 1.2. When the ratio (b ¹ / a ¹ ) is 0.5 or more, good solubility in an organic solvent used for a 6-substituted guanamine compound can be obtained when producing a phosphorus-containing guanamine resin. The heat resistance excellent in the thermosetting resin can be obtained by setting the ratio (b ¹ / a ¹ ) to 1.2 or less without causing it.

  Moreover, the phosphorus containing guanamine resin of this invention uses the N-substituted maleimide compound shown to (d) following General formula (2) as a reaction component further as needed.

In the above formula (2), R ₂ represents a phenyl group having an alkyl group, a phenyl group or a substituent having 1 to 5 carbon atoms.
Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the phenyl group having a substituent include a hydroxyphenyl group and a carboxyphenyl group.

  Accordingly, examples of the N-substituted maleimide compound represented by (d) the general formula (2) include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide and the like. It is done. Among these, N-methylmaleimide, N-phenylmaleimide, and N-hydroxyphenylmaleimide, which have a high reaction rate at the time of reaction and can be further improved in heat resistance, are preferred, and N-phenylmaleimide, N- Hydroxyphenylmaleimide is more preferable, and N-phenylmaleimide is particularly preferable because it is inexpensive. Further, if necessary, a bifunctional maleimide resin such as bis (4-maleimidophenyl) methane may be used in combination. By using the bifunctional maleimide resin in combination, the glass transition temperature (Tg) of the thermosetting resin can be further improved.

In the phosphorus-containing guanamine resin of the present invention, when the component (d) is used, (b) a carboxylic acid anhydride containing maleic anhydride with respect to the equivalent (a ¹ ) of the —NH ₂ group of the 6-substituted guanamine compound The ratio [(b ¹ + d ¹ ) / a ¹ ] of the total amount of the anhydride carboxyl group equivalent (b ¹ ) and the C = C group equivalent (d ¹ ) of the (d) N-substituted maleimide compound is 0.5 to 1. A range of 2 is preferable. By setting the ratio [(b ¹ + d ¹ ) / a ¹ ] to 0.5 or more, good solubility in an organic solvent used for a 6-substituted guanamine compound can be obtained when producing a phosphorus-containing guanamine resin. Therefore, gelation does not occur, and excellent heat resistance of the thermosetting resin can be obtained by setting the ratio [(b ¹ + d ¹ ) / a ¹ ] to 1.2 or less.

Further, in the phosphorus-containing guanamine resin of the present invention, (b) at least one P—H bond is contained in one molecule with respect to the anhydride carboxyl group equivalent (b ¹ ) of the carboxylic anhydride containing maleic anhydride. The ratio (c ¹ / b ¹ ) of the P—H bonding group equivalent (c ¹ ) of the aromatic compound is preferably in the range of 0.1 to 1.2. When the ratio (c ¹ / b ¹ ) is 0.1 or more, excellent flame retardancy is obtained, and when it is 1.2 or less, excellent heat resistance is obtained.

The phosphorus-containing guanamine resin of the present invention comprises (a) a 6-substituted guanamine compound represented by the general formula (1), (b) a carboxylic anhydride containing maleic anhydride, and (c) at least one P in one molecule. It is a reaction product of an aromatic compound having a -H bond and an N-substituted maleimide compound represented by (d) general formula (2) used as necessary. That is, it is produced by reacting compound (b) and, if necessary, compound (d) with all / or a part of the terminal amino group of compound (a), and further reacting compound (c).
Specifically, for example, a mixture of a 6-substituted guanamine compound represented by the general formula (1) and an organic solvent is mixed with maleic anhydride and, if necessary, an N-substituted maleimide compound represented by the general formula (2) in small amounts. Added and allowed to react at 70 ° C. or higher for 0.5 to 10 hours, and further added with an aromatic compound having at least one PH bond in one molecule and reacted at 70 ° C. or higher for 0.5 to 10 hours. By doing so, the phosphorus-containing guanamine resin of the present invention is obtained.

Examples of organic solvents optionally used in this reaction include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohol solvents such as methyl cellosolve and propylene glycol monomethyl ether, ether solvents such as tetrahydrofuran, Aromatic solvents such as toluene, xylene and mesitylene, and N atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone can be used, and one or a mixture of two or more can be used. Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility and low toxicity, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone from the viewpoint of suppressing side reactions. Is more preferable, and cyclohexanone is particularly preferable from the viewpoint of reactivity (synthesis yield).
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, phosphorus-based catalysts such as triphenylphosphine, and the like. Can be mixed and used.

The thermosetting resin composition of the present invention comprises (A) the above phosphorus-containing guanamine resin and (B) an epoxy resin having at least two epoxy groups in one molecule.
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 Glycidyl ethers, glycidyl amines, glycidyl esters, etc., such as those of nobles, novolacs, polyfunctional phenols, naphthalenes, alicyclics and alcohols, etc., one or a combination of these being used can do. 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.

In the thermosetting resin composition of the present invention, an epoxy resin curing agent may be used. Examples of the curing agent include maleic anhydride, maleic anhydride copolymer and other acid anhydrides, 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 be used in combination with 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) phosphorus-containing guanamine resin is 1 to 99 parts by mass per 100 parts by mass of (A) phosphorus-containing guanamine resin and (B) epoxy resin. It is preferable to set it to 20 to 99 parts by mass, and particularly preferable to set to 20 to 90 parts by mass. (A) Excellent flame retardancy, adhesiveness and flexibility are obtained by setting the amount of phosphorus-containing guanamine resin to 1 part by mass or more, and excellent heat resistance is obtained by setting it to 99 parts by mass or less. It is done.

Moreover, the thermosetting resin composition of this invention can use together 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 standpoint 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 the organic solvent 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 Examples thereof include formamide dimethylacetamide, N-methylpyrrolidone and the like, and two or more kinds of organic solvents can be mixed and 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 formed by impregnating or coating the thermosetting resin composition of the present invention 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 stacking one or more of the prepregs of the present invention, and heating and pressing. A laminated board can be manufactured by laminating 1 to 20 sheets of the prepreg of the present invention and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material applications. 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 the temperature is 100 to 250 ° C. 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 in any way.
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 2 atm, 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 phosphorus-containing guanamine resin (1-1) 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, benzoguanamine: 187.00 g Cyclohexanone: 562.00 g was added, then maleic anhydride: 196.00 g was added, and the mixture was heated to 140 ° C. and dissolved uniformly. After dissolution, reflux dehydration reaction was performed at 160 ° C. for 8 hours. Next, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide: 215.00 g was added, and the reaction was further performed at 160 ° C. for 5 hours to obtain a solution of phosphorus-containing guanamine resin (1-1). Got.

Production Example 2 Production of Phosphorus-Containing Guanamin Resin (1-2) 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 Cyclohexanone: 655.00 g was added, N-phenylmaleimide: 173.00 g and maleic anhydride: 98.00 g were added, and the mixture was heated to 140 ° C. and dissolved uniformly. After dissolution, reflux dehydration reaction was performed at 160 ° C. for 8 hours. Subsequently, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide: 215.00 g was added, and the reaction was further performed at 160 ° C. for 5 hours to obtain a solution of phosphorus-containing guanamine resin (1-2). Got.

Production Example 3 Production of Phosphorus-Containing Guanamine Resin (1-3) 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 Cyclohexanone: 564.00 g was added, succinic anhydride: 100.00 g and maleic anhydride: 98.00 g were added, and the mixture was heated to 140 ° C. and uniformly dissolved. After dissolution, reflux dehydration reaction was performed at 160 ° C. for 8 hours. Subsequently, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide: 215.00 g was added, and the reaction was further performed at 160 ° C. for 5 hours to obtain a solution of phosphorus-containing guanamine resin (1-2). Got.

Production Example 4: Production of Phosphorus-Containing Guanamin Resin (1-4) In a reaction vessel with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser and a heat-coolable volume of 2 liters, benzoguanamine: 187.00 g Cyclohexanone: 533.00 g was added, then maleic anhydride: 196.00 g was added, and the mixture was heated to 140 ° C. and dissolved uniformly. After dissolution, reflux dehydration reaction was performed at 160 ° C. for 8 hours. Then, 186.00 g of diphenylphosphine was added, and the reaction was further performed at 160 ° C. for 5 hours to obtain a solution of phosphorus-containing guanamine resin (1-4).

Example 1
30 parts by mass of the phosphorus-containing guanamine resin (1-1) obtained in Production Example 1 as the component (A), and a cresol novolac type epoxy resin (trade name: Epicron N, manufactured by Dainippon Ink & Chemicals, Inc.) as the component (B) -673) 30 parts by mass, cresol novolac type phenolic resin (manufactured by Dainippon Ink and Chemicals, trade name: KA-1165) as an epoxy curing agent, 30 parts by mass, 50 parts by mass of aluminum hydroxide as a flame retardant, A uniform varnish having a resin content of 70% by mass was obtained by mixing using methyl ethyl ketone. Next, the varnish was impregnated and coated on 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 conducted except that 30 parts by mass of the phosphorus-containing guanamine resin (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 conducted except that 30 parts by mass of the phosphorus-containing guanamine resin (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 30 parts by mass of the phosphorus-containing guanamine resin (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 conducted except that 30 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 conducted except that 30 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.

Comparative Example 1
The same procedure as in Example 1 was performed except that 30 parts by mass of benzoguanamine as the component (A) and 10 parts by mass of triphenyl phosphate as the flame retardant were further used. Table 2 shows the measurement and evaluation results of the performance of the obtained copper-clad laminate.

Comparative Example 2
(A) It was the same as that of Comparative Example 1 except that 30 parts by mass of a condensate of benzoguanamine and formaldehyde (trade name: FP-100B, manufactured by Nippon Shokubai Co., Ltd.) was used as the component. 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 30 parts by mass of hexamethoxymethylolated melamine resin (trade name: C-300, manufactured by Mitsui Cyanamid Co., Ltd.) 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, there is no 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 thermosetting resin composition containing the phosphorus-containing guanamine resin of the present invention on a base material, and a laminate produced by laminating the prepreg, have a copper foil adhesive property. It has excellent 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 equipment.

Claims (6)

(A) a 6-substituted guanamine compound represented by the following general formula (1), (b) a carboxylic acid anhydride containing maleic anhydride, and (c) an aromatic compound having at least one PH bond in one molecule. A phosphorus-containing guanamine resin characterized by being a reaction product of

(In the formula (1), R ₁ represents a phenyl group, a phenyl group having a substituent, an alkyl group having 1 to 5 carbon atoms, or a benzyloxy group.) The phosphorus-containing guanamine resin according to claim 1, which is a reaction product having (d) an N-substituted maleimide compound represented by the following general formula (2) as a reaction component.

(In formula (2), R ₂ represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a phenyl group having a substituent.)   (A) A thermosetting resin composition comprising the phosphorus-containing guanamine resin according to claim 1 or 2 and (B) an epoxy resin having at least two epoxy groups in one molecule.   A prepreg obtained by impregnating or coating the base material with the thermosetting resin composition according to claim 3 and then forming a B-stage.   A laminate obtained by stacking one or more prepregs according to claim 4 and molding by heating and pressing.   The laminate according to claim 5, wherein the laminate is a metal-clad laminate obtained by superposing metal foil on at least one of the overlaid prepregs and then heating and pressing.