JP2010241870A - Flame-retardant phosphorus-containing epoxy resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant phosphorus-containing epoxy resin composition that is excellent in heat resistance, moisture resistance and flame retardancy without causing deterioration in adhesive properties while enhancing reliability at a high temperature. <P>SOLUTION: The flame-retardant phosphorus-containing epoxy resin composition comprises a phosphorus-containing epoxy resin (X) obtained by causing an epoxy resin (a) containing 50-100 wt.% of bifunctional epoxy resins bearing a sulfur atom in its skeleton to react with a phosphorous compound (b) comprising a compound of a specific structure having a cyclic phosphinic acid structure and a 1,4-dihydroxynaphthalene structure and, admixed therewith, at most 0.06 mole, based on 1 mole of (a), of a compound of a specific structure having a cyclic phosphinic acid structure and no 1,4-dihydroxynaphthalene structure, and a curing agent (Y). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition that requires flame retardancy, and is a resin composition for producing a copper-clad laminate used for electronic circuit boards, and a sealing material, molding material, and casting material used for electronic components.・ Useful as adhesives, electrical insulating paints, etc., especially as a resin composition for the production of copper-clad laminates, it is difficult to provide laminates with not only flame retardant effects but also excellent adhesion, heat resistance and moisture resistance The present invention relates to a flammable phosphorus-containing epoxy resin composition.

  Forms in which the epoxy resin is actually used include liquid to solid, varnish dissolved in a solvent, and the like. The liquid type is widely used for casting materials and adhesives, and the solid type is used for sealing materials and powder coatings. The varnish type is used as a fiber-reinforced plastic material or a solvent-type paint used by impregnating a glass substrate or carbon fiber. In particular, it is widely used for electrical and electronic material parts because of its excellent adhesion and electrical characteristics (insulation).

  Since these electrical and electronic material parts are required to have high flame resistance (UL: V-0) as represented by glass epoxy laminates and IC encapsulants, usually halogenated epoxy resins are used. Yes. For example, in glass epoxy laminates, as flame retardant FR-4 grade, epoxy resin generally substituted with bromine as the main raw material component, mixed with various epoxy resins, and curing for epoxy resin It is used in combination with an agent.

  However, the use of such halogenated epoxy resins is one of the causes of environmental problems represented by dioxins in recent years, and the adverse effect on electrical long-term reliability due to halogen dissociation in high temperature environments. For these reasons, there is a strong demand for flame retardants using other compounds that reduce the amount of halogen used or can be substituted for halogens, or other flame retardant formulations.

  Conventionally, as a technology to replace such a flame retardant formulation with halogen, various technologies using, for example, a phosphate ester compound as an additive flame retardant have been studied. The deterioration of the property and water resistance and the problem that the flame retardant bleeds out with time, particularly the decrease in adhesion in electrical laminate applications, were severe. Thus, various techniques for improving the performance of a laminated plate by reacting an epoxy resin with a specific phosphorus compound have been studied (Patent Documents 1 to 4). However, in any of these techniques, the heat resistance is limited to the FR-4 grade, and it is difficult to further improve the heat resistance. In general, the heat resistance is improved by using a polyfunctional epoxy resin such as a cresol novolac epoxy resin. However, the flame retardancy and adhesiveness are lowered. Recently, in order to cope with lead-free solder, there has been a demand for a reduction in water absorption and low elasticity of the cured product in order to increase reliability at higher temperatures. In Patent Document 5, although an epoxy resin having a naphthalene aralkyl structure and a specific phosphorus compound are reacted, both flame retardancy and heat resistance are improved, but the adhesiveness is lowered. Thus, it has been difficult to achieve both improved heat resistance and adhesion while maintaining flame retardancy with the phosphorus-containing epoxy resin composition.

JP 2001-288247 A JP 2002-249540 A JP 2001-123049 A Japanese Patent No. 3642403 JP 2008-214513 A JP 2008-150495 A JP 61-268691 A

  The problem to be solved by the present invention is to improve the reliability at high temperatures in a phosphorus-containing epoxy resin imparted with flame retardancy without using a halogen, so that heat resistance and moisture resistance are not reduced without causing a decrease in adhesiveness. It aims at providing the flame-retardant phosphorus containing epoxy resin composition which is excellent in property and a flame retardance.

  That is, the gist of the present invention is a flame-retardant phosphorus-containing epoxy resin composition containing a phosphorus-containing epoxy resin (X) and a curing agent (Y), wherein the phosphorus-containing epoxy resin (X) has a skeleton with a sulfur atom. The epoxy resin (a) containing 50 wt% to 100 wt% of the bifunctional epoxy resin contained therein and the chemical formula (2) is mixed at a ratio of 0.06 mol or less with respect to 1 mol of the chemical formula (1). A phosphorus-containing epoxy resin (X) obtained by reacting the phosphorus compounds (b), and a phosphorus content of 0.5 to all epoxy resin components in the flame-retardant phosphorus-containing epoxy resin composition It is a flame-retardant phosphorus-containing epoxy resin composition characterized by having a sulfur content of from 2% to 9% by weight.

  When the flame-retardant phosphorus-containing epoxy resin composition according to the present invention is used, it has excellent adhesion and heat resistance in addition to flame retardancy. Furthermore, it is flame retardant when the phosphorus content is from 0.5% to less than 2.0% by weight, and a cured product having high heat resistance and particularly excellent adhesion to metal can be obtained. The effect is further improved by containing the bifunctional epoxy resin contained therein as an essential component.

Hereinafter, embodiments of the present invention will be described in detail.
The epoxy resins (a) used in the present invention contain 50 wt% to 100 wt% of a bifunctional epoxy resin having a sulfur atom in the skeleton as an essential component. If it is less than 50% by weight, not only the heat resistance cannot be improved, but also the flame retardancy is lowered, and a composition that can be used in a high heat resistance application cannot be obtained.

  The bifunctional epoxy resins having a sulfur atom in the skeleton may have any structure as long as it is a bifunctional epoxy resin containing a sulfur atom, but a sulfur atom-containing bisphenol type epoxy resin is particularly preferable. Specifically, bisphenol S type epoxy resin such as Epototo TX-0908 (Substituted bisphenol S type epoxy resin manufactured by Toto Kasei Co., Ltd.) or Epototo YSLV-120TE (Dimethyldihydroxy-ditertiary butyl diphenyl sulfide type epoxy manufactured by Toto Kasei Co., Ltd.) Resin) and Epototo YSLV-50TE (Bisdiphenyl sulfide type epoxy resin manufactured by Toto Kasei Co., Ltd.) and the like, but are not limited to these, and two or more types may be used in combination. .

  In addition, bifunctional epoxy resins having no sulfur atom in the skeleton may be used in combination as the bifunctional epoxy resins, but the bifunctional epoxy resins having a sulfur atom in the skeleton are epoxy resins (a). It is necessary to make it 50% by weight or more.

  The above-mentioned bifunctional epoxy resin having a sulfur atom in the skeleton and the bifunctional epoxy resin not having a sulfur atom to be used in combination in the skeleton as necessary are necessary for improving adhesion. The amount thereof is 50% by weight or more in the epoxy resins (a), preferably 65% by weight or more, and more preferably 80% by weight or more. This is because if the amount is less than 50% by weight, the adhesiveness is drastically lowered, and only a composition having poor practicality can be obtained.

  Bifunctional epoxy resins that do not have a sulfur atom in the skeleton that can be used with a bifunctional epoxy resin that has a sulfur atom in the skeleton include hydroquinone type epoxy resins, bisphenol type epoxy resins, biphenol type epoxy resins, and naphthalenediol type epoxy resins. Etc. Specifically, Epototo YDC-1312, Epototo ZX-1027 (manufactured by Toto Kasei Co., Ltd., hydroquinone type epoxy resin), Epototo ZX-1251 (Toto Kasei Co., Ltd., biphenol type epoxy resin), Epototo YD-127, Epototo YD -128, Epototo YD-8125, Epototo YD-825GS, Epototo YD-011, Epototo YD-900, Epototo YD-901 (manufactured by Tohto Kasei Co., Ltd., bisphenol A type epoxy resin), Epototo YDF-170, Epototo YDF-8170 Epototo YDF-870GS, Epototo YDF-2001 (Toto Kasei Co., Ltd., bisphenol F type epoxy resin), Epototo ZX-1201 (Toto Kasei Co., Ltd., bisphenol fluorene type epoxy) Fat), Epotohto ZX-1355, Epotohto ZX-1711 (manufactured by Tohto Kasei Co., Ltd., and not but like is limited to naphthalene diol type epoxy resin), or may be used in combination of two or more kinds. From the viewpoint of flame retardancy, epoxy resins having no alkyl substituent are preferred, and among these, naphthalenediol type epoxy resins, biphenyl type epoxy resins, and bisphenol F type epoxy resins are more preferred.

  If bifunctional epoxy resins having a sulfur atom in the skeleton are used in an amount of 50% by weight or more, heat resistance and adhesiveness can be sufficiently satisfied. However, in order to improve flame retardancy, heat resistance and adhesiveness, An epoxy resin other than a bifunctional epoxy resin having a skeleton in the skeleton may be contained in an amount of less than 50% by weight. However, aliphatic epoxy resins are not preferable from the viewpoint of flame retardancy, and bifunctional epoxy resins are preferable from the viewpoint of improving adhesiveness. However, from the viewpoint of improving heat resistance, the number of average functional groups is 2.1 or more. Functional epoxy resins are preferred.

  Examples of the polyfunctional epoxy resins having an average functional group number of 2.1 or more include phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aralkyl type epoxy resins. Specific examples include Epototo YDPN-638 (manufactured by Toto Kasei Co., Ltd., phenol novolac type epoxy resin), Epototo YDCN-701, Epototo YDCN-702, Epototo YDCN-703, Epototo YDCN-704 (manufactured by Toto Kasei Co., Ltd., Ortho Cresol novolac type epoxy resin), Epototo ESN-175 (manufactured by Toto Kasei Co., Ltd., β-naphthol aralkyl type epoxy resin), Epototo ESN-475V, Epototo ESN-485 (manufactured by Toto Kasei Co., Ltd., α-naphthol aralkyl type epoxy resin) ), Epototo ESN-355, Epototo ESN-375 (manufactured by Toto Kasei Co., Ltd., dinaphthol aralkyl type epoxy resin), EPPN-501H, EPPN-502 (Nippon Kayaku Co., Ltd., polyfunctional epoxy tree) Fat), NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin) and the like, but are not limited thereto, and two or more kinds may be used in combination. From the viewpoint of flame retardancy, epoxy resins having no alkyl substituent are preferred, and among these, phenol novolac type epoxy resins and naphthol aralkyl type epoxy resins are more preferred.

  Patent Document 1 discloses a phosphorus-containing epoxy resin obtained from an epoxy resin containing a maximum of 45% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton, but has sufficient heat resistance because it is less than 50% by weight. It wasn't. Patent Document 5 discloses a phosphorus-containing epoxy resin obtained with a naphthol aralkyl type epoxy resin, but has sufficient heat resistance, but does not use bifunctional epoxy resins having a sulfur atom in the skeleton. The sex was slightly inferior.

  The phosphorus compound (b) used in the present invention is a phosphorus compound in which the compound represented by the chemical formula (2) is mixed at a ratio of 0.06 mol or less with respect to 1 mol of the compound represented by the chemical formula (1). It is essential to be a kind.

  Typical examples of the compound represented by the chemical formula (1) are 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1,4-naphthoquinone which are the compounds represented by the chemical formula (2). It is a phosphorus compound obtained by reaction with.

  As the phosphorus compounds (b), a compound represented by the chemical formula (1) synthesized in advance and a compound represented by the chemical formula (2) may be mixed and used, or the epoxy resins (a) and Before the reaction, 1,4-naphthoquinone may be reacted in the range of 0.94 mol to 1.00 mol with respect to 1 mol of the compound represented by the chemical formula (2). When the compound represented by the chemical formula (2) is reacted with 1,4-naphthoquinone before the reaction with the epoxy resins (a), 1,4-naphthoquinone is added to 1 mol of the compound represented by the chemical formula (2). It is preferable to use less than 1.00 mol. In this case, the reaction between the compound represented by the chemical formula (2) and 1,4-naphthoquinone proceeds as theoretically, and the compound represented by the chemical formula (1) is obtained. In the resulting phosphorus-containing epoxy resin (X) The raw material 1,4-naphthoquinone does not remain. When 1,4-naphthoquinone is used in an amount of 1.00 mol or more with respect to 1 mol of the compound represented by the chemical formula (2), 1,4-naphthoquinone as a raw material remains in the obtained phosphorus-containing epoxy resin (X) and is cured. This is not preferable because the moisture resistance of the product deteriorates.

  When the compound represented by the chemical formula (2) exceeds 0.06 mol, the phosphorous content can be easily adjusted, which is effective in improving the flame retardancy and decreasing the viscosity, but represented by the monofunctional chemical formula (2). The reaction between the compound and the epoxy group occurs frequently and the number of epoxy groups decreases, resulting in a decrease in the adhesiveness of the cured product, a decrease in heat resistance, and a decrease in moisture resistance, resulting in remarkable electrical insulation reliability in high heat resistance applications. descend. When the compound represented by the chemical formula (2) is not used, it is necessary to produce the compound represented by the chemical formula (1) in advance. The production of this compound requires many steps, and the productivity is poor and industrially disadvantageous. Furthermore, in the reaction with the epoxy resins (b), when the phosphorus content in the final phosphorus-containing epoxy composition is set high, the molecular weight of the resulting phosphorus-containing epoxy resin increases, and the resin viscosity increases too much, Not only does the impregnation with glass cloth worsen and it is industrially disadvantageous, but the physical properties of the resulting laminate, especially the soldering heat resistance, deteriorates and the elastic modulus tends to increase, making the laminate hard and brittle. It is easy to become inconvenient. Therefore, the molar ratio of the compound represented by the chemical formula (2) to 1 mole of the compound represented by the chemical formula (1) is 0.06 mol or less, and preferably 0.01 to 0.05 mol. .

  Patent Document 4 suggests a phosphorus-containing epoxy resin obtained with a bisphenol S-type epoxy resin, but there is no disclosure in Examples, and no consideration is given to the remaining compound represented by the chemical formula (2). In the examples, bisphenol A and bisphenol F are exemplified, but the compound represented by the chemical formula (2) is reacted at 0.92 mol with respect to 1 mol of the compound represented by the chemical formula (1). Since a large amount of the compound represented by the chemical formula (2) remains, the heat resistance is slightly inferior, and there is a problem in electrical insulation reliability in high heat resistance applications.

  In the reaction of the epoxy resins (a) and phosphorus compounds (b) used in the present invention, bifunctional or higher functional phenol compounds other than the phosphorus compounds (b) may be used. Examples of the bifunctional or higher functional phenol compounds include bisphenol A, bisphenol S, bisphenol F, naphthalene diol, biphenol, phenol novolac resin, cresol novolac resin, glyoxal tetraphenol resin, bisphenol A novolac resin, phenol aralkyl resin, and naphthol aralkyl resin. And biphenol aralkyl resin. In particular, from the viewpoint of flame retardancy, a phenol compound having no alkyl substituent is preferable, and among these, bisphenol S, naphthalenediol, and biphenol are particularly preferable. The purpose of using bifunctional or higher functional phenol compounds is to adjust the phosphorus content, sulfur content, softening point and epoxy equivalent when reacting the epoxy resins (a) and the phosphorus compounds (b), This is for adjusting the elastic modulus of the laminate.

  In addition, the reaction between the epoxy resins (a) and phosphorus compounds (b) used in the present invention and the bifunctional or higher functional phenol compounds used as necessary can be carried out by a known method. The temperature can be 100 to 200 ° C., more preferably 120 to 180 ° C. with stirring. The reaction time can be determined by measuring the epoxy equivalent. The epoxy equivalent can be measured by the method of JIS K-7236. The epoxy equivalent increases as the phosphorus compounds (b) react with the epoxy resins (a) and the phenolic compounds, and the end point of the reaction can be determined by comparison with the theoretical epoxy equivalent.

  Further, when the reaction rate is slow, productivity can be improved by using a catalyst as necessary. Specifically, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, ethyltriphenylphosphonium Various catalysts such as phosphonium salts such as bromide and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used.

  It is essential that the phosphorus content with respect to all the epoxy resin components in the flame-retardant phosphorus-containing epoxy resin composition of the present invention is 0.5% by weight to less than 2.0% by weight. If it is less than 0.5% by weight, sufficient flame retardancy cannot be imparted. If it is 2.0% by weight or more, the moisture resistance of the cured product is lowered due to the influence of the phosphorus component in the phosphorus-containing epoxy resin, and the reliability in the high heat resistance application is remarkably lowered.

  From the necessity of adjusting the phosphorus content to the total epoxy resin component in the flame-retardant phosphorus-containing epoxy resin composition from 0.5 wt% to 2.0 wt%, to 100 parts by weight of the phosphorus-containing epoxy resin (X) Thus, 0 to 50 parts by weight of the phosphorus-free epoxy resin can be blended. When trying to mix 50 parts by weight or more, it is necessary to increase the phosphorus content of the phosphorus-containing epoxy resin (X) so as not to impair the flame retardancy. In this case, the heat resistance of the flame-retardant phosphorus-containing epoxy resin composition is increased. It will drop significantly. As the phosphorus-free epoxy resin, an aliphatic epoxy resin is not preferable from the viewpoint of flame retardancy, and from the viewpoint of heat resistance, it is preferably a polyfunctional epoxy resin having an average functional group number of 2.1 or more. Are preferred. In particular, when a polyfunctional epoxy resin having an average functional group number of 2.1 or more is used as a phosphorus-free epoxy resin, the flame-retardant phosphorus of the present invention can be used without impairing heat resistance and flame retardancy as long as it is 50 parts by weight or less. A contained epoxy resin composition can be obtained. More preferably, the amount of the phosphorus-free epoxy resin is 0 to 25 parts by weight with respect to 100 parts by weight of the phosphorus-containing epoxy resin (X).

  The phosphorus content of the phosphorus-containing epoxy resin (X) of the present invention may be in the range of 0.5 wt% to 3.5 wt%, preferably 0.8 wt% to 3.0 wt%, more preferably Is 1.2 wt% to 2.7 wt%, more preferably 1.5 wt% to 2.3 wt%. If the phosphorus content is less than 0.5% by weight, it is difficult to ensure flame retardancy. If it exceeds 3.5% by weight, the resin viscosity becomes extremely high and synthesis becomes difficult, and the molecular weight of the resin increases, which adversely affects the heat resistance and further impairs impregnation into glass cloth, which is industrially disadvantageous. In addition, the physical properties of the resulting cured product, particularly moisture resistance and solder heat resistance, are deteriorated. Moreover, in the case where no epoxy resin other than the phosphorus-containing epoxy resin (X) is used, it is essential that the phosphorus content of the phosphorus-containing epoxy resin (X) is 0.5 wt% to less than 2.0 wt%. Become.

  It is essential that the sulfur content with respect to all epoxy resin components in the flame-retardant phosphorus-containing epoxy resin composition of the present invention is 2% by weight to 9% by weight. If it is less than 2% by weight, sufficient heat resistance cannot be imparted. If it exceeds 9% by weight, the physical properties of the cured product obtained under the influence of the sulfur component in the phosphorus-containing epoxy resin, particularly moisture resistance and soldering heat resistance will deteriorate, and the reliability in high heat resistance applications will be significantly reduced. Preferably they are 3 weight%-8 weight%, More preferably, they are 4 weight%-7 weight%. Moreover, when not using epoxy resins other than phosphorus containing epoxy resin (X), it becomes essential that the sulfur content rate of phosphorus containing epoxy resin (X) shall be 2 to 9 weight%.

  The epoxy equivalent of the phosphorus-containing epoxy resin (X) of the present invention is preferably 200 g / eq to 900 g / eq, more preferably 250 g / eq to 800 g / eq, and still more preferably 300 g / eq to 600 g / eq. When the epoxy equivalent is less than 200 g / eq, the adhesiveness is inferior, and when it exceeds 900 g / eq, the heat resistance is adversely affected, so it is desirable to adjust to 200 g / eq to 900 g / eq.

  Examples of the curing agent (Y) of the present invention include phenol novolak resins, alkylphenol novolak resins, aralkylphenol novolak resins, triazine ring-containing phenol novolak resins, biphenylaralkylphenol resins, aralkylnaphthalenediol resins, trisphenylmethane, and tetrakisphenylethane. Polyhydric phenols, hydrazides such as adipic acid dihydrazide, sebacic acid dihydrazide, imidazole compounds and salts thereof, dicyandiamide, aminobenzoic acid esters, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, metaxylenediamine, isophoronediamine, etc. Aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone, and diaminoethylbenzene Mines, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, etc. Examples thereof include, but are not limited to, known and usual curing agents such as acid anhydrides. These curing agents may be used alone or in combination of two or more. The amount of these curing agents used is preferably in the range of 0.3 equivalents to 1.5 equivalents, more preferably 0.4 equivalents to 1.2 equivalents, relative to 1 equivalent of epoxy group in the epoxy resin used.

  In addition, the flame-retardant phosphorus-containing epoxy resin composition of the present invention may contain phosphines, imidazole compounds, quaternary phosphonium salts, tertiary amines, quaternary ammonium salts, boron trifluoride complexes, 3- Use together with a curing accelerator such as (3,4-dichlorodiphenyl) -1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea. You can also. These curing accelerators depend on the epoxy resin used together, the type of epoxy resin curing agent used, the molding method, the curing temperature, and the required characteristics, but in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the epoxy resin. Is preferable, and 0.1 to 10 parts by weight is more preferable.

  The flame retardant phosphorus-containing epoxy resin composition of the present invention may be blended with other thermosetting resins and thermoplastic resins other than the epoxy resin as long as the characteristics are not impaired. For example, phenol resin, acrylic resin, petroleum resin, indene resin, indene coumarone resin, phenoxy resin, cyanate resin, polyurethane, polyester, polyamide, polyimide, polyamideimide, polyetherimide, bismaleimide triazine resin, polyethersulfone, polysulfone, Examples include polyether ether ketone, polyphenylene sulfide, and polyvinyl formal, but are not limited thereto.

  The flame-retardant phosphorus-containing epoxy resin composition of the present invention can contain an inorganic filler and an organic filler as necessary. Examples of fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, Examples thereof include glass fiber, carbon fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, and aramid fiber. These fillers are preferably 1% by weight to 95% by weight based on the total amount of the epoxy resin.

  The flame-retardant phosphorus-containing epoxy resin composition of the present invention further comprises a silane coupling agent, an antioxidant, a mold release agent, an antifoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant, and a pigment as necessary. Various additives such as can be blended. These additives are preferably in the range of 0.01% by weight to 20% by weight in the total amount of the epoxy resin composition.

  The flame-retardant phosphorus-containing epoxy resin composition of the present invention is an essential component of a phosphorus-containing epoxy resin (X), a curing agent (Y), a curing accelerator, various fillers, and various additives as required by known methods. It can be obtained by blending an agent or the like and mixing them uniformly.

  The flame-retardant phosphorus-containing epoxy resin composition of the present invention can be easily molded into a cured product by molding and curing by a known method. The molding method and the curing method can be the same methods as known epoxy resin compositions.

  The flame retardant phosphorus-containing epoxy resin cured product of the present invention can take the form of a sealing material, an adhesive layer, a molded product, a laminate, a film and the like.

  As a result of evaluating the characteristics of the laminate obtained using the flame-retardant phosphorus-containing epoxy resin composition of the present invention, the cured product has high heat resistance, low water absorption, and high reliability at high temperatures. It is possible to obtain The flame-retardant phosphorus-containing epoxy resin composition and its cured product are a resin composition for producing a copper-clad laminate used for an electronic circuit board and a sealing material, a molding material, a casting material, and an adhesive used for an electronic component. It was found to be useful as a film material, an electrical insulating paint material, and the like.

  Hereinafter, the present invention will be specifically described based on synthesis examples, examples, and comparative examples, but the technical scope of the present invention is not limited only to the examples. In addition, unless otherwise indicated, the compounding part number of each component in a synthesis example, an Example, and a comparative example shows a weight part.

In the present invention, the following analysis method was used.
Epoxy equivalent: The method described in JIS K-7236. Specifically, the sample was dissolved in 10 mL of chloroform, 20 mL of acetic anhydride and 10 mL of 20% tetraethylammonium bromide solution were added, and titrated with a 0.1 mol / L perchloric acid acetic acid standard solution using a potentiometric titrator.

  Softening point: Ring and ball method described in JIS K-7234. That is, the sample was melted and degassed, poured into a ring, and measured with a glycerin bath.

  Phosphorus content: Nitric acid-perchloric acid decomposition method. That is, sulfuric acid, nitric acid, and perchloric acid are added to the sample and thermally decomposed to convert all phosphorus to normal phosphoric acid, and then a 0.25% ammonium vanadate solution and a 5% ammonium molybdate solution in a sulfuric acid acidic solution. The color development of the resulting phosphorus-banad molybdate complex was allowed to react, the absorbance at a wavelength of 420 nm was measured, and the phosphorus content was determined by a calibration curve.

  Sulfur content: A method in accordance with the oxygen combustion flask method described in JIS K-6233-1. That is, the sample was completely decomposed in a combustion flask and supplemented and absorbed as sulfate ions in the solution, and then measured by ion chromatography.

  Copper foil peeling strength: The method as described in JIS C-6481 5.7. That is, peeling was performed at a speed of 50 mm / min between the copper foil and the insulating plate in the direction perpendicular to the measurement.

  Interlaminar peel strength: A method according to JIS C-6481 5.7. That is, the measurement was performed by peeling between one prepreg and the remaining three sheets at a speed of 50 mm / min in the perpendicular direction.

  Flame retardancy: Measured according to UL (Underwriters Laboratories) standard, UL94 vertical test method, V-0, V-1, V-2, NG (no flame retardancy) of the standard of the standard Judgment was made at 4 levels (flame retardance was worse as later).

  Glass transition temperature: TMA method. In other words, TMA / SS120U manufactured by SII Nano Technology Co., Ltd. was used for the analyzer, and the temperature was measured at 10 ° C./min by thermomechanical analysis (TMA).

  Linear thermal expansion coefficient: TMA method. That is, it is obtained as a displacement from 50 ° C. to 150 ° C. measured with a temperature rise rate of 10 ° C./min by thermomechanical analysis (TMA) using TMA / SS120U manufactured by SII Nano Technology Co., Ltd. as an analyzer. It was.

  Water absorption: A method according to JIS C-6481 5.13. That is, using a test piece cut to 50 mm × 50 mm, the dry weight after drying for 24 hours in an oven at 50 ° C. is measured, and subsequently the weight after boiling at 100 ° C. for 2 hours is measured. The moisture absorption rate was measured on the basis of the increase in.

  Solder heat resistance: A method in accordance with JIS C-6481 5.5. That is, using a test piece cut to 25 mm × 25 mm, the test piece after boiling at 100 ° C. for 2 hours was immersed in a solder bath at 288 ° C. for 20 seconds at n = 5, and no swelling or peeling occurred at all 5 points. The result was marked with ◯, and the result of even one was marked with x.

Synthesis example 1
In a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing device, HCA (manufactured by Sanko Co., Ltd., phosphorus content: 14. 2 wt.%) 64.0 g and 150 g of toluene were charged, and heated under stirring in a nitrogen atmosphere to be completely dissolved. Thereafter, 45.9 g of 1,4-naphthoquinone (manufactured by Kawasaki Kasei Kogyo Co., Ltd., 3% water-containing product) as quinones was added in portions while paying attention to temperature rise by reaction heat. The molar ratio of 1,4-naphthoquinone to HCA at this time was 1,4-naphthoquinone / HCA = 0.95. After heating reaction, Epototo TX-0908 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 219 g / eq) 317.1 g as a bifunctional epoxy resin having a sulfur atom in the skeleton, and a polyfunctional having an average functional group number of 2.1 or more Epototo YDPN-638 (manufactured by Toto Kasei Co., Ltd., phenol novolac type epoxy resin, epoxy equivalent: 176 g / eq) as an epoxy resin was charged 74.4 g, stirred while introducing nitrogen gas, and heated to 130 ° C. Toluene was removed out of the system. Thereafter, 0.11 g of triphenylphosphine (made by Hokuko Chemical Co., Ltd., product name: TPP) is added as a catalyst and reacted for 4 hours while keeping the reaction temperature at 160 ° C. to 165 ° C. Obtained. The obtained phosphorus-containing epoxy resin A had an epoxy equivalent of 392 g / eq, a phosphorus content of 1.8% by weight, a sulfur content of 5.2% by weight, and a softening point of 83 ° C.

Synthesis example 2
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction device, 45.5 g of HCA (as described above) and 110 g of toluene as a phosphorus compound represented by the chemical formula (2) were charged. The solution was completely dissolved by heating with stirring under a nitrogen atmosphere. Thereafter, 33.6 g of 1,4-naphthoquinone (described above) as quinones was added in portions while paying attention to the temperature rise by reaction heat. The molar ratio of 1,4-naphthoquinone to HCA at this time was 1,4-naphthoquinone / HCA = 0.98. After the heating reaction, 420.7 g of Epototo TX-0908 (described above) as a bifunctional epoxy resin having a sulfur atom in the skeleton was added, stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene. Removed. Thereafter, 0.08 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain a phosphorus-containing epoxy resin B. The obtained phosphorus-containing epoxy resin B had an epoxy equivalent of 338 g / eq, a phosphorus content of 1.3% by weight, a sulfur content of 7.0% by weight, and a softening point of 76 ° C.

Synthesis example 3
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction device, 64.5 g of HCA (as described above) and 150 g of toluene as a phosphorus compound represented by the chemical formula (2) were charged. The solution was completely dissolved by heating with stirring under a nitrogen atmosphere. Thereafter, 47.2 g of 1,4-naphthoquinone (described above) as quinones was added in portions while paying attention to the temperature rise by reaction heat. The molar ratio of 1,4-naphthoquinone to HCA at this time was 1,4-naphthoquinone / HCA = 0.97. After the heating reaction, 350.0 g of Epototo TX-0908 (described above) as a bifunctional epoxy resin having a sulfur atom in the skeleton was added, stirred while introducing nitrogen gas, heated to 130 ° C., and toluene was removed from the system. Removed. Thereafter, 0.11 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain a phosphorus-containing epoxy resin C. The obtained phosphorus-containing epoxy resin C had an epoxy equivalent of 751 g / eq, a phosphorus content of 2.0% by weight, a sulfur content of 6.3% by weight, and a softening point of 120 ° C.

Synthesis example 4
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction device, 75.0 g of HCA (as described above) and 175 g of toluene as a phosphorus compound represented by the chemical formula (2) were charged. The solution was completely dissolved by heating with stirring under a nitrogen atmosphere. Thereafter, 55.9 g of 1,4-naphthoquinone (described above) as quinones was added in portions while paying attention to temperature rise by reaction heat. The molar ratio of 1,4-naphthoquinone to HCA at this time was 1,4-naphthoquinone / HCA = 0.99. After the heating reaction, 320.0 g of Epototo TX-0908 (described above) as a bifunctional epoxy resin having a sulfur atom in the skeleton, and Epotot ESN-485 (Toto Kasei Co., Ltd.) as a polyfunctional epoxy resin having an average functional group number of 2.1 or more Company-made α-naphthol aralkyl type epoxy resin, epoxy equivalent: 269 g / eq) 30.0 g and 4,4′-biphenol (manufactured by Nippon Steel Chemical Co., Ltd., hydroxyl group equivalent: 93 g / eq) 18.0 g was charged, stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene out of the system. Thereafter, 0.15 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain phosphorus-containing epoxy resin D. The obtained phosphorus-containing epoxy resin D had an epoxy equivalent of 723 g / eq, a phosphorus content of 2.1 wt%, a sulfur content of 5.3 wt%, and a softening point of 125 ° C.

Synthesis example 5
2,4-bisphenol S-type epoxy resin as a bifunctional epoxy resin having a sulfur atom in its skeleton in a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device (patented) 340.0 g of epoxy equivalent: 220 g / eq) synthesized in advance by the method described in Example 1 of Reference 6, and 9,10-dihydro-9-oxa-10- (2) as the phosphorus compound represented by the chemical formula (1) , 7-dihydroxynaphthyl) -10-phosphaphenanthrene-10-oxide (previously synthesized by the method described in Example 1 of Patent Document 7, hereinafter abbreviated as HCA-NQ), 64.8 g, chemical formula (2) 1.1 g of HCA (described above) as a phosphorus compound represented by formula 4,4′-bisphenol S (manufactured by Nikka Chemical Co., Ltd., B S-P (T), hydroxyl equivalent: 125 g / eq) were charged 25.0 g, was heated with stirring to 130 ° C. under a nitrogen atmosphere. The phosphorus compound shown by Chemical formula (2) was 0.03 mol with respect to 1 mol of phosphorus compounds shown by Chemical formula (1) at this time. Thereafter, 0.09 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain a phosphorus-containing epoxy resin E. The obtained phosphorus-containing epoxy resin E had an epoxy equivalent of 441 g / eq, a phosphorus content of 1.2 wt%, a sulfur content of 7.8 wt%, and a softening point of 104 ° C.

Synthesis Example 6
Epototo YSLV-50TE (Epoxy manufactured by Tohto Kasei Co., Ltd.) as a bifunctional epoxy resin having a sulfur atom in its skeleton in a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introducing device Equivalent: 172 g / eq) 400.0 g, HCA-NQ (described above) 62.0 g as the phosphorus compound represented by the chemical formula (1), 40.0 g of 4,4′-biphenol (described above) as the bifunctional or higher phenol compound The mixture was charged and heated to 130 ° C. with stirring under a nitrogen atmosphere. At this time, the phosphorus compound represented by the chemical formula (2) was not used. Thereafter, 0.1 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain a phosphorus-containing epoxy resin F. The obtained phosphorus-containing epoxy resin F had an epoxy equivalent of 333 g / eq, a phosphorus content of 1.0% by weight, a sulfur content of 7.7% by weight, and a softening point of 96 ° C.

Synthesis example 7
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction device, 75.0 g of HCA (as described above) and 175 g of toluene as a phosphorus compound represented by the chemical formula (2) were charged. The solution was completely dissolved by heating with stirring under a nitrogen atmosphere. Thereafter, 55.9 g of 1,4-naphthoquinone (described above) as quinones was added in portions while paying attention to temperature rise by reaction heat. The molar ratio of 1,4-naphthoquinone to HCA at this time was 1,4-naphthoquinone / HCA = 0.99. After heating reaction, 180.0 g of Epototo TX-0908 (described above) as a bifunctional epoxy resin having a sulfur atom in the skeleton, and Epotot ZX-1711 (2,5-naphthalenediol, manufactured by Tohto Kasei Co., Ltd.) as a bifunctional epoxy resin Type epoxy resin, epoxy equivalent: 146 g / eq) 175.0 g was charged, stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene out of the system. Thereafter, 0.13 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain a phosphorus-containing epoxy resin G. The obtained phosphorus-containing epoxy resin G had an epoxy equivalent of 371 g / eq, a phosphorus content of 2.2 wt%, a sulfur content of 3.0 wt%, and a softening point of 110 ° C.

Synthesis example 8
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing device, 103.6 g of HCA (previously described) and 240 g of toluene as a phosphorus compound represented by the chemical formula (2) were charged. The solution was completely dissolved by heating with stirring under a nitrogen atmosphere. Thereafter, 53.4 g of 1,4-naphthoquinone (described above) as quinones was added in portions while paying attention to the temperature rise by reaction heat. The molar ratio of 1,4-naphthoquinone to HCA at this time was 1,4-naphthoquinone / HCA = 0.68. After heating reaction, 226.4 g of Epototo TX-0908 (described above) as a bifunctional epoxy resin having a sulfur atom in the skeleton, and Epotot YDPN-638 (described above) 117 as a polyfunctional epoxy resin having an average functional group number of 2.1 or more. .3 g was charged, stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene out of the system. Thereafter, 0.16 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain a phosphorus-containing epoxy resin H. The obtained phosphorus-containing epoxy resin H had an epoxy equivalent of 563 g / eq, a phosphorus content of 2.9% by weight, a sulfur content of 3.7% by weight, and a softening point of 110 ° C.

Synthesis Example 9
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing device, 70.0 g of HCA (as described above) and 160 g of toluene as a phosphorus compound represented by the chemical formula (2) were charged. The solution was completely dissolved by heating with stirring under a nitrogen atmosphere. Thereafter, 46.4 g of 1,4-naphthoquinone (described above) as quinones was added in portions while paying attention to the temperature rise by reaction heat. The molar ratio of 1,4-naphthoquinone to HCA at this time was 1,4-naphthoquinone / HCA = 0.88. After the heating reaction, 172.8 g of Epototo TX-0908 (described above) as a bifunctional epoxy resin having a sulfur atom in the skeleton, and Epototo YD-128 (produced by Toto Kasei Co., Ltd., bisphenol A type epoxy resin as a bifunctional epoxy resin, Epoxy equivalent: 187 g / eq) 211.2 g was charged, stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene out of the system. Thereafter, 0.11 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain a phosphorus-containing epoxy resin I. Epoxy equivalent of the obtained phosphorus-containing epoxy resin I was 384 g / eq, phosphorus content was 2.0% by weight, sulfur content was 3.0% by weight, and softening point was 70 ° C.

Synthesis Example 10
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing device, 70.0 g of HCA (as described above) and 160 g of toluene as a phosphorus compound represented by the chemical formula (2) were charged. The solution was completely dissolved by heating with stirring under a nitrogen atmosphere. Thereafter, 46.4 g of 1,4-naphthoquinone (described above) as quinones was added in portions while paying attention to the temperature rise by reaction heat. The molar ratio of 1,4-naphthoquinone to HCA at this time was 1,4-naphthoquinone / HCA = 0.88. After heating reaction, 300.0 g of Epototo YSLV-50TE (described above) is charged as a bifunctional epoxy resin having a sulfur atom in the skeleton, stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene. Removed. Thereafter, 0.12 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain a phosphorus-containing epoxy resin J. The obtained phosphorus-containing epoxy resin J had an epoxy equivalent of 370 g / eq, a phosphorus content of 2.4% by weight, a sulfur content of 7.1% by weight, and a softening point of 106 ° C.

Synthesis Example 11
Epototo TX-0908 (previously described) 315.8 g as a bifunctional epoxy resin having a sulfur atom in the skeleton in a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introducing device, As the phosphorus compound represented by the chemical formula (1), 181.8 g of HCA-NQ (described above) was charged and heated to 130 ° C. with stirring in a nitrogen atmosphere. At this time, the phosphorus compound represented by the chemical formula (2) was not used. Thereafter, 0.18 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 170 ° C. to 190 ° C. to obtain a phosphorus-containing epoxy resin K. The obtained phosphorus-containing epoxy resin K had an epoxy equivalent of 1,080 g / eq, a phosphorus content of 3.0% by weight, a sulfur content of 5.2% by weight, and a softening point of 140 ° C. or higher and could not be measured.

Synthesis Example 12
In a four-necked glass separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction device, 332.0 g of Epototo YSLV-50TE (described above) as a bifunctional epoxy resin having a sulfur atom in the skeleton, While charging 96.3 g of 4,4′-bisphenol S (described above) as a bifunctional or higher functional phenol compound and 71.3 g of HCA-NQ (described above) as a phosphorus compound represented by the chemical formula (1), stirring in a nitrogen atmosphere Heated to 130 ° C. At this time, the phosphorus compound represented by the chemical formula (2) was not used. Thereafter, 0.17 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 170 ° C. to 190 ° C. to obtain a phosphorus-containing epoxy resin L. The obtained phosphorus-containing epoxy resin L had an epoxy equivalent of 651 g / eq, a phosphorus content of 1.2% by weight, a sulfur content of 9.1% by weight, and a softening point of 140 ° C. or higher and could not be measured.

Synthesis Example 13
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing device, 90.0 g of HCA (described above) and 210 g of toluene as a phosphorus compound represented by the chemical formula (2) were charged. The solution was completely dissolved by heating with stirring under a nitrogen atmosphere. Thereafter, 67.0 g of 1,4-naphthoquinone (described above) as quinones was added in portions while paying attention to the temperature rise due to reaction heat. The molar ratio of 1,4-naphthoquinone to HCA at this time was 1,4-naphthoquinone / HCA = 0.99. After the heating reaction, 324.6 g of Epototo YD-128 (described above) was charged as a bifunctional epoxy resin, stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene out of the system. At this time, a bifunctional epoxy resin having a sulfur atom in the skeleton was not used. Thereafter, 0.16 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain a phosphorus-containing epoxy resin M. The obtained phosphorus-containing epoxy resin M had an epoxy equivalent of 529 g / eq, a phosphorus content of 2.7 wt%, a sulfur content of 0 wt%, and a softening point of 104 ° C.

Examples 1-7 and Comparative Examples 1-6
A phosphorus-containing epoxy resin (X), a curing agent (Y), other epoxy resins, a curing accelerator, and the like were blended according to the blending formulation shown in Table 1. Phosphorus-containing epoxy resin and other epoxy resins are dissolved in methyl ethyl ketone, and dicyandiamide (DICY, active hydrogen equivalent: 21.0 g / eq) is used as a curing agent (Y) previously dissolved in methyl cellosolve and dimethylformamide. 2-Ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2E4MZ) was added as an agent to prepare a resin varnish so that the nonvolatile content was 50% by weight. Thereafter, the obtained resin varnish was used to impregnate a glass cloth as a base material (WEA 116E 106S 136, thickness 100 μm, manufactured by Nitto Boseki Co., Ltd.), and the impregnated glass cloth was subjected to 8 in a hot air circulation oven at 150 ° C. Drying was performed for a minute to obtain a prepreg. Subsequently, the obtained four prepregs and copper foil (Mitsui Metal Mining Co., Ltd., 3EC-III, thickness 35 μm) are stacked, and heated and heated under conditions of 130 ° C. × 15 minutes and 190 ° C. × 2.0 MPa × 70 minutes. Pressure was applied to obtain a 0.6 mm thick laminate. About each obtained laminated board, each physical property of copper foil peeling strength, delamination strength, a flame retardance, a glass transition temperature, a linear thermal expansion coefficient, a water absorption rate, and solder heat resistance was tested. The results are shown in Table 2.

  Example 1, Example 2, Example 3, Example 4, Example 7, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 6 have chemical formulas before reaction with epoxy resins (a) ( 2) Using the phosphorus-containing epoxy resin (X) reacted with the phosphorus compound (b) obtained by reacting the compound represented by 2) and 1,4-naphthoquinone, Example 5 was synthesized in advance. Using the phosphorus-containing epoxy resin (X) reacted with the compound represented by the chemical formula (1) and the compound represented by the chemical formula (2) as the phosphorus compounds (b), Example 6, Comparative Example 4 and Comparative Example 5 used a phosphorus-containing epoxy resin (X) reacted using only a phosphorus compound represented by the chemical formula (1) synthesized in advance. Moreover, Example 3, Example 4, Example 5, Example 7, Comparative Example 3, and Comparative Example 6 also used a phosphorus-free epoxy resin other than the phosphorus-containing epoxy resin (X).

  Comparative Example 1 uses 66% by weight of bifunctional epoxy resins having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin, but the compound of chemical formula (2) is used with respect to 1 mol of the compound of chemical formula (1). Since the compound has a molar ratio of 0.46 and more than 0.06 mol of the compound of the chemical formula (2), the water absorption is as high as 1.7%, the moisture resistance is poor, and the solder heat resistance is also poor. In addition, although the polyfunctional epoxy resin is frequently used, it cannot be said that the glass transition temperature is 155 ° C. and the heat resistance is not so high. The delamination strength does not reach 1.0 kN / m, and the laminate is not practical. Comparative Example 2 uses only 45% by weight and less than 50% by weight of bifunctional epoxy resins having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin, and in 1 mol of the compound of chemical formula (1). On the other hand, since the molar ratio of the compound of the chemical formula (2) is 0.14 and the compound of the chemical formula (2) is used in an amount of more than 0.06 mol, flame retardancy is not obtained even when the phosphorus content is 2% by weight. Low heat resistance and high water absorption. Comparative Example 3 uses 100% by weight of a bifunctional epoxy tree having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin, but the compound of the chemical formula (2) with respect to 1 mol of the compound of the chemical formula (1). The molar ratio of 0.14 and the compound of the chemical formula (2) are used in an amount of more than 0.06 mol, so that the delamination strength does not reach 1.0 kN / m and the solder heat resistance is poor. Comparative Example 4 uses 100% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin, and does not use the compound of chemical formula (2), but the phosphorus content is 3 Since it is as high as 0.0% by weight, the softening point of the epoxy resin is considerably high at 140 ° C. or more and the impregnation property into the glass cloth is deteriorated. Therefore, the delamination strength does not reach 1.0 kN / m and the solder heat resistance is poor. In Comparative Example 5, when the phosphorus-containing epoxy resin was synthesized, 100% by weight of the bifunctional epoxy resin having a sulfur atom in the skeleton was used, and the phosphorus compound of the chemical formula (2) was not used. Since it is as high as 9.1% by weight, the water absorption is as high as 2.2% by weight and the moisture resistance is poor. Furthermore, since the softening point of the resin is considerably higher than 140 ° C. and the impregnation property into the glass cloth is deteriorated, the delamination strength does not reach 1.0 kN / m and the solder heat resistance is poor. In Comparative Example 6, since a bifunctional epoxy resin having a sulfur atom in the skeleton is not used when synthesizing the phosphorus-containing epoxy resin, the glass transition temperature is 138 ° C. and the heat resistance is not high, and the phosphorus content is 2. If it is 07% by weight, there is no flame retardancy, and the laminate is not practical.

  In contrast, in Example 1, when synthesizing a phosphorus-containing epoxy resin, 81% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton and a polyfunctional epoxy resin having an average functional group number of 2.1 or more are used. 19% by weight, and the molar ratio of the compound of the chemical formula (2) is 0.05 and the compound of the chemical formula (2) is less than 0.06 mol with respect to 1 mol of the compound of the chemical formula (1). It is low at 1.0% and has good moisture resistance, and even when the phosphorus content is 1.8% by weight and less than 2% by weight, flame retardancy is good. Furthermore, the glass transition temperature is as high as 165 ° C., the solder heat resistance is good, and the delamination strength is 1.1 kN / m, which is a sufficiently practical laminate. Example 2 uses 100% by weight of bifunctional epoxy resins having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin, and the amount of the compound of the chemical formula (2) is 1 mol of the compound of the chemical formula (1). Since the molar ratio is 0.02 and the compound of the chemical formula (2) is less than 0.06 mol, the phosphorus content is 1.3% by weight and the sulfur content is 7% by weight, It is a good laminate. Since no polyfunctional epoxy resins having an average functional group number of 2.1 or more are used at all, the flame retardancy is V-0, but the time to extinguishment is slightly longer than in Examples 1 and 4, and the glass transition Although the temperature is 161 ° C., which is slightly worse than that of Example 1 or Example 4, it is a laminated plate that can be used for heat-resistant applications. Example 3 uses 100% by weight of bifunctional epoxy resins having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin, and the amount of the compound of the chemical formula (2) is 1 mol of the compound of the chemical formula (1). Since the molar ratio is 0.03 and the compound of the chemical formula (2) is less than 0.06 mol and the sulfur content is 4.2% by weight, even if the phosphorus content is 1.3% by weight and less than 2% by weight It is a laminated board with good flame retardancy, moisture resistance, heat resistance, and adhesion. Example 4 uses 91% by weight of bifunctional epoxy resins having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin and 9% by weight of polyfunctional epoxy resins having an average number of functional groups of 2.1 or more. The molar ratio of the compound of the chemical formula (2) is 0.01 and the compound of the chemical formula (2) is less than 0.06 mol with respect to 1 mol of the compound of the chemical formula (1), and the sulfur content is 4.2% by weight. Therefore, even if the phosphorus content is 1.7% by weight and less than 2% by weight, the flame retardancy is good, and further, the laminate has good moisture resistance, heat resistance and adhesion. Example 5 uses 100% by weight of bifunctional epoxy resins having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin, and the amount of the compound of the chemical formula (2) is 1 mol of the compound of the chemical formula (1). Since the molar ratio is 0.03 and the compound of the chemical formula (2) is less than 0.06 mol and the sulfur content is 5.9% by weight, even if the phosphorus content is 0.9% by weight and less than 1% by weight It is a laminated board with good flame retardancy, moisture resistance, heat resistance, and adhesion. Example 6 uses 100% by weight of bifunctional epoxy resins having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin, and without using the phosphorus compound of chemical formula (2), the phosphorus of chemical formula (1). Since only the compound is used and the phosphorus content is 1.0% by weight and the sulfur content is 7.7% by weight, the laminate has good moisture resistance and adhesion. Since no polyfunctional epoxy resins having an average functional group number of 2.1 or more are used at all, the flame retardancy is V-0, but the time to extinguishment is slightly longer than in Examples 1 and 4, and the glass transition Although the temperature is 160 ° C., which is slightly worse than that of Example 1 or Example 4, it is a laminate that can be used for heat-resistant applications. Example 7 uses 51% by weight of bifunctional epoxy resins having a sulfur atom in the skeleton and 49% by weight of bifunctional epoxy resin not having a sulfur atom in the skeleton when synthesizing a phosphorus-containing epoxy resin, The molar ratio of the phosphorus compound of the chemical formula (2) is 0.01 and the phosphorus compound of the chemical formula (2) is less than 0.06 mol with respect to 1 mol of the phosphorus compound of the chemical formula (1), and the sulfur content is 2.4 weight. Therefore, even if the phosphorus content is 1.8% by weight and less than 2% by weight, the flame retardancy is good, and further, the laminate has good moisture resistance, heat resistance and adhesion.

  Thus, the compound represented by the chemical formula (2) is made 0.06 mol or less with respect to 1 mol of the compound represented by the chemical formula (1), and 50 weights of the bifunctional epoxy resins having a sulfur atom in the skeleton. The phosphorus-containing epoxy resin synthesized using at least 5% is an essential component, the phosphorus content of the epoxy resin is reduced from 0.5 wt% to less than 2.0 wt%, and the sulfur content is increased from 2 wt% to 9 wt% In these examples, in addition to flame retardancy, the adhesive strength, heat resistance, and moisture resistance are also excellent. In particular, by adjusting the phosphorus content of the epoxy resin from 0.5 wt% to less than 2.0 wt% and adjusting the sulfur content from 2 wt% to 9 wt%, the water absorption rate can be maintained while maintaining heat resistance. Reduced and improved solder heat resistance. In addition, as in Example 5 and Example 6, since the flame retardancy can be satisfied even if the phosphorus content is 1% by weight or less, a laminate having good moisture resistance is obtained. Furthermore, it is also possible to use a phosphorus-free epoxy resin together as in Example 3, Example 4, Example 5, and Example 7, and in particular, polyfunctional epoxy resins having an average functional group number of 2.1 or more. By using in combination, an epoxy resin composition having high heat resistance and excellent adhesion and flame retardancy can be obtained.

  The present invention is particularly suitable for electrical insulation materials such as copper clad laminates used for electronic circuit boards, and is suitable for sealing materials, molding materials, casting materials, adhesives, and film materials used for electronic components. In addition, it is also effective as a material for electrical insulating paints.

Claims (9)

A flame-retardant phosphorus-containing epoxy resin composition containing a phosphorus-containing epoxy resin (X) and a curing agent (Y), wherein the phosphorus-containing epoxy resin (X) has a sulfur atom in the skeleton. Compounds (b) in which the chemical formula (2) is mixed in an amount of 0.06 mol or less per 1 mol of the chemical formula (1) Is a phosphorus-containing epoxy resin (X) obtained by reacting as an essential component, and the phosphorus content relative to all epoxy resin components in the flame-retardant phosphorus-containing epoxy resin composition is from 0.5% by weight A flame-retardant phosphorus-containing epoxy resin composition characterized by being less than 2.0% by weight and having a sulfur content of 2 to 9% by weight.

  The phosphorus-containing epoxy resin (X) according to claim 1 contains 50% to 95% by weight of bifunctional epoxy resins having a sulfur atom in the skeleton, and a polyfunctional epoxy having an average functional group number of 2.1 or more. The flame-retardant phosphorus-containing epoxy resin composition according to claim 1, obtained by epoxy resins (a) containing 5 to 20% by weight of resins as essential components.   The phosphorus-containing epoxy resin (X) according to claim 1 or 2 contains from 50 wt% to 95 wt% of bifunctional epoxy resins having a sulfur atom in the skeleton, and from 5 wt% of a phenol novolac type epoxy resin. The flame-retardant phosphorus-containing epoxy resin composition according to claim 1 or 2 obtained by an epoxy resin (a) containing less than 20% by weight.   The phosphorus-containing epoxy resin (X) according to claim 1 or 2 contains 50 wt% to 95 wt% of a bifunctional epoxy resin having a sulfur atom in the skeleton, and 5 wt% to 20 wt% of an aralkyl type epoxy resin. The flame-retardant phosphorus-containing epoxy resin composition according to claim 1 or 2, which is obtained by an epoxy resin (a) containing less than% by weight.   The flame-retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 4, comprising 50 parts by weight or less of a phosphorus-free epoxy resin as an essential component with respect to 100 parts by weight of the phosphorus-containing epoxy resin (X). object.   A prepreg, an insulating adhesive sheet, and an epoxy resin laminate using the flame-retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 5.   An epoxy resin encapsulant comprising the flame-retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 5.   An epoxy resin casting material comprising the flame-retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 5.   A flame-retardant phosphorus-containing epoxy resin cured product obtained by curing the flame-retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 5.