TW201132668A - Method for making a phosphor-containing epoxy resin, epoxy resin composition and a cured article thereof - Google Patents

Abstract

This invention provides a method for making a phosphor-containing epoxy resin having a flame retardant property and an excellent low viscosity property, a curable resin composition containing a phosphor-containing epoxy resin made by such a method, and a curing agent, and a cured article thereof. It is a method for making a phosphor-containing epoxy resin having an epoxy equivalent of 200 to 600g/eq and a phosphor content 1 to 6 wt.% by reacting an epoxy resin (A) with an organic phosphor compound (B), the epoxy resin (A) being constituted by at least one of the epoxy resin (a1) represented by general formula (1) or epoxy resin (a2) represented by general formula (3) or epoxy resin (a3) represented by general formula (4), the organic phosphor compound (B) being constituted by organic phosphor compound (b1) represented by general formula 5 and/or organic phosphor compound (b2) represented by general formula (6), the epoxy resin (A) has a concentration of hydroxide group of 200 meq/100g or less, a total chroline content of 0.4 wt.% or less, and an α -diol content of 10 meg/100g or less; and the organic phosphor compound (B) has a ratio of organic phosphor compound (b1)/organic phosphor compound (b2) in the range by wt. of 50/50 to 100/0. GO-H2C-R1-CH2-OG (1) Wherein R1 is C6-31 hydrocarbon group having at least one aromatic ring; the C6-31 hydrocarbon group may contain an oxygen atom, a nitrogen atom, and a sulfur atom; G represents formula (2) or hydrogen; GO-R2-OG (3) Wherein R2 is C6-17 aliphatic hydrocarbon group having at least one cyclohexane ring which may be a single ring or a heterocyclic ring; the C6-17 aliphatic hydrocarbon group may contain an oxygen atom, a nitrogen atom, and a sulfer atom; G represents formula (2) or hydrogen; Wherein R3 respectively independently is C1-4 aliphatic hydrocarbon group which may contain an oxygen atom, a nitrogen atom, and a sulfur atom; R4 represents -R3-OG, or -R3-H1, or hydrogen; G represents formula (2) or hydrogen; K represents an integer of 0 or 1; Wherein R5, R6 represents hydrogen or a hydrocarbon group and may be the same or different, and may be in a straight chain, a branched chain, or in a ring; R5 and R6 may be bonded to form a ring; n represents an integer of 0 or 1; Ar represents benzene, biphenyl, naphthalene, anthracene, phenantone, d or a hydrocarbon substituent thereof; Wherein R7, R8 represents a hydrocarbon group and may be the same or different, and may be in a straight chain, a branched chain, or in a ring. R7 and R8 may be bonded to form a ring shape construction; m is an integer of 0 or 1.

Description

[Technical Field] The present invention relates to an excellent low-viscosity property, and provides a flame-retardant and excellent use as an electrical and electronic component represented by a semiconductor element. A novel 111⁄4 oxy-resin for hardened materials such as materials, laminates, composites, etc., and is suitable for use in electrical circuits such as printed circuit boards and semiconductor seals, such as epoxy resins, and products and cured products thereof. Insulating materials in the field of electronics. [Prior Art] Although epoxy resins have been used in a wide range of industrial applications, the demand for their sexual conditions has been increasing in recent years. For example, although there is a semi-conductive (four) sealing material in a representative field of a resin composition mainly composed of an epoxy resin, in recent years, as the semiconductor element has increased in bulk, in addition to making the package size large and thin, In addition to the formation, the domain method has also moved toward surface assembly, and it has been desired to develop a material having more excellent solder heat resistance.

At the same time, at the same time, due to the technical trend of high-integration and high-density assembly, in the past, the mold was transferred into a package by transfer molding, and the hybrid IC (hybrid 1C) was no longer used, and the wafer was directly attached to the circuit board. (ch ip on board ' C0B ), tape carr i package (TCP), plastic pin gHd array (PPGA), plastic ball grid array (piastic baU gHd Array, PBGA), etc., but sealed with a liquid material, which increases the assembly method. However, in general, the liquid material has a low reliability when compared with the solid material used in the transfer molding. The liquid material has a viscosity limit of 322722 7 201132668, and limits the resin, hardener, filler, etc. used. Moreover, (4) in recent years, it has no self-inflammation, and even when using a tooth-based flame retardant, even In these applications, there is also a need to improve the flammability. J ~, and in the field of materials also improve the requirements of non-toothing, but must also be low-viscosity due to the need to break the flame retardancy , therefore not It is possible to obtain materials that meet the requirements. In order to overcome these problems, it is expected to be able to achieve low viscosity, low moisture absorption, high heat and flame retardancy on epoxy resins and hardeners as main agents. On the low-viscosity epoxy resin, although the well-known double-anti-ring type ring (10) grease, (four) F-type epoxy resin, etc. are generally known, the low viscosity is insufficient, and * is difficult. In Patent Document 1, Although it is described that the & oxy-resin having an oxy-anthracene group bond can be used as an epoxy tree with excellent low-viscosity, it has to be improved in heat resistance and moisture resistance, and the flame retardancy is not considered at all. In Patent Document 2, although it is described that it has a bicyclohexyl ring = oxygen resin, the whole fiber is considered in terms of flame retardancy. In the patent document, the epoxy resin having flame retardancy is described, but it has (4) The bismuth-containing oxy-resin obtained by the difunctional epoxy resin and the phosphorus-containing saponin has a problem of low viscosity. In Patent Document 4, it is said that the Japanese special tax is And _ sex, and the fat alum oxygen tree can also be used as a scaly epoxy resin. However, the effect of the Japanese aliphatic epoxy resin is not mentioned, and the degree of the epoxy containing the dish is not considered at all. In Patent Document 5, the epoxide single epoxy is The composition of the resin, but it is necessary to use an aliphatic diluent at the same time as 322722 8 201132668, and it is not possible to use it alone. [Prior Art Document] [Patent Document] Patent Document 1: Japanese Patent Application Laid-Open No. Hei-4-359009 Patent Document 2: 曰Japanese Patent Laid-Open Publication No. JP-A No. 2001-249540 (Patent Document 5): JP-A-2001-106766 (Patent Document 5): JP-A-2001-106766 JP-A-61-268691 SUMMARY OF INVENTION (Problems to be Solved by the Invention) It is not easy to obtain a liquid epoxy resin which is inflammable in this manner. Therefore, an object of the present invention is to provide a method for producing a phosphorus-containing epoxy resin which is excellent in low viscosity and which can supply a hardenable hardenable material, and a lining-containing epoxy resin obtained by the production method. An epoxy resin composition, and a cured product thereof. (Means for Solving the Problem) In order to solve the above problems, the inventors conducted intensive studies and found that it is necessary to produce a phosphorus-containing epoxy resin which does not significantly impair the physical properties of the hardened material and has an effective flame retardancy. The method for producing the phosphorus-containing epoxy resin of the present invention is the necessary condition for the viscosity of the epoxy resin, and the method for solving the aforementioned problems is the following described in the patent application. A method for producing an epoxy resin according to the formula, wherein the epoxy resin (8) represented by the formula} or the epoxy resin (a3) represented by the cycloolefin resin 322722 9 201132668 4 represented by the formula 3 is used. At least one epoxy resin (A) formed is reacted with an organophosphorus compound (B) represented by Formula 5 and an organophosphorus compound (B) represented by Formula 6 to produce a ring In the method of the phosphorus-containing epoxy resin having an oxygen equivalent of 200 to 600 g/eq and a phosphorus ratio of 1 to 6% by weight, the epoxy group (A) has a hydroxyl group concentration of 200 meq/100 g or less and a total chlorine content of 0. 4% by weight or less, the α-diol content is 10 meq/100 g or less, and the organophosphorus compound (b)/organophosphorus compound (b2) has a weight ratio ranging from 50/50 to 100/0. , GO~H2C-Ri-CH2~OG (1) wherein R1 represents a hydrocarbon group having 6 to 31 carbon atoms which may have an aromatic ring containing an oxygen atom, a nitrogen atom or a sulfur atom, and G represents a formula 2 or a hydrogen group. any type. (2) GO—R2-〇G (3) wherein R 2 represents a monocyclic or heterocyclic ring having at least one cyclohexane ring which may contain an oxygen atom, a nitrogen atom or a sulfur atom. An aliphatic hydrocarbon group having 6 to 17 carbon atoms, and G represents any one of formula 2 or hydrogen;

-OG R4—C-fRs^OG (4)

R3—OG wherein R3 independently represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom, and R4 represents any of -R3-0G or -R3-H or hydrogen 10 322722 201132668. One, G represents any of the formula 2 or hydrogen, and k represents an integer of 〇 or i;

II (5)

P—Ar—OH R6 OH wherein R 5 and R 6 represent hydrogen or a hydrocarbon group, which may be different or the same, and may be linear, branched or cyclic, and may also be formed by combining R 5 and R 6 . a cyclic structure, η represents an integer of 〇 or 1, and Ar represents any one of benzene, biphenyl, phenyl, anthracene, phenanthrene, and the like;

(6) where R7 R8 represents hydrogen or a transport group, which may be different or identical, and may be linear, branched or cyclic, and may also form a cyclic structure by combining R7 with a shape, m represents An integer of 0 or 1. (2) An epoxy resin composition characterized by comprising (IV) a resinous epoxy resin and a curing agent as a component of the method for producing a phosphorus-containing epoxy resin as described in (1). (3) A cured product obtained by hardening the filled epoxy resin composition described in the item (2). The epoxy resin (A) of the present invention must contain a ringtone (9) represented by the phantom or an epoxy resin (a3) represented by the formula 3. The purpose of using these tree 妒 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 322722 11 201132668 _Generally, the epoxy resin and the phenol resin are reacted to synthesize a novel epoxy resin, and in the obtained epoxy resin, the residue of the epoxy resin which is a raw material cannot be avoided. Therefore, in the obtained phosphorus-containing epoxy resin, the influence of the epoxy resin (A) which becomes a raw material must also be considered. The glycidyl etherification of the alcoholic base group is inferior in reactivity, and the amount of unreacted residual hydroxyl groups is increased. Since the residual hydroxyl group in the raw material epoxy resin (A) is not related to the reaction of the phosphide, it may remain so that the purity of the terminal group of the phosphorus-containing epoxy resin is lowered, so the residual light base in the raw material epoxy resin (A) The increase in the hygroscopicity of the so-called epoxy resin composition increases the storage stability of the anhydride hardener or the microcapsule latent hardener. In addition, it is necessary to improve the purity of the residual hydroxyl group of the raw material epoxy resin because of the main factor that deteriorates the physical properties of the cured product such as the strength or heat resistance of the cured product. Therefore, the residual hydroxyl group concentration of the epoxy resin (A) is preferably 200 meq/100 g or less' and is preferably 1 〇〇 meq/l 〇〇 g or less, and more preferably 50 eq/l 〇〇 g or less. At the same time, in order to reduce the residual hydroxyl group concentration, such as adding a catalyst or the like to increase the reactivity, parallel side reactions are also increased to cause a high concentration of the total gas contained. Since the amount of total chlorine in the epoxy resin (A) of the raw material directly remains in the phosphorus-containing epoxy resin, the electrical reliability of the cured product is remarkably lowered. Therefore, it is necessary to increase the purity of the total fluorine content. The total amount of the raw material ring resin (A) is preferably 0.4% by weight or less, more preferably 2% by weight or less, and most preferably 3% by weight or less. In the case of alcoholic hydroxyl-derived glycidyl etherification, 'because it is almost 1% by weight or more of total gas volume', it is necessary to reduce the amount of gas by 322722 12 201132668 via a high-purification reaction or distillation operation or extraction operation. There are no specific rules for these methods, and the various methods currently considered can be used. At the same time, the content of the α-diol in the raw material epoxy resin (A) is also the same as that of the residual felt base, and it is irrelevant to the reaction of the phosphide, and the residue can be left as it is. Decrease, so q & in the raw material epoxy resin (A) can increase the absorption property of the phosphorus-containing epoxy resin composition directly, and become an acid anhydride hardener or microcapsule type hard agent, % The reason for the decrease in stability. Further, since the hardened material is a major factor that deteriorates the physical properties of the cured product such as a decrease in heat generation, the α-diol content of the oxygen resin (4) is required to be lowered. Therefore, the epoxy resin (Α) ck diacid table θ, good 3 s should preferably be l〇meq/100g or less, and preferably 5meq/100g, preferably, and preferably 3meq/l〇〇g or less. . In the case of the epoxy resin (a3) represented by the formula 4, if the residual hydroxyl group-functional plant alcohol content is too high, in addition to the above-mentioned reasons, the non-lipid-based % oxygen resin is The bifunctional epoxy tree ^' ^ which does not have a cyclohexane ring causes poor flame retardancy, which is not preferable. The epoxy resin (a1) represented by the formula 1 which is at least a compound reaction, and which has a structure of -0-CH2-R1-CH2-0- if it is a scented scented ring. -o-chH is used to improve the flame retardancy of scaly epoxy resins. For example, the structure of Bu (3) 2~0—the low viscosity of the epoxy resin containing phosphorus

S 脂作心2 has "(4) Bu (3) 2 structure of the structure of the epoxy tree epoxy resin material: due to low viscosity, so low-release agent in the epoxy resin, and the soil page uses a large amount of aliphatic The reactivity such as epoxy resin is dilute to ensure its flexibility. (4) If you want to ensure flame retardancy, reduce 322722 13 201132668 When the amount of epoxy resin used is less, the viscosity of the epoxy resin composition rises significantly', which is not conducive to low viscosity, so the target is not obtained. Viscosity phosphorus-containing epoxy resin composition. That is, the bifunctional epoxy resin (al) is a glycidyl halide of a bifunctional monohydric alcohol having 8 to 33 carbon atoms and having at least one aromatic ring in the structure. The group of the formula 7 represents a specific example of R1 in the formula of the bifunctional epoxy resin (ai) represented by the formula 1. Meanwhile, R1 may be an isomer of the group 7 or may have a substituent ◊, and R1 may be either a single type or a θ 2 type or more.疋

〇

322722 14 201132668

(7-8) (7-9)

(7-11) wherein j represents an integer of 0 or 1, respectively. One h2c

CH2 - CH2 - 〇 -

(7-12) In the formula, j independently represents an integer of 0 or 1.

(7-13) Among the bifunctional epoxy resins (al) represented by Formula 1,

It is preferably a glycidyl ether compound of p-xylene glycol represented by the formula S 15 322722 201132668 8 or a glycidyl etherified product of oxymethylenebiphenyl represented by the formula 9. Ηζ〇\ /Η〇''κ,2〇—o-h2c

CH2-〇—H2C—d^-—-CH2 (8) H2C-~CH'- "Ά一〇-CHa

22-O-CHj-(9)-, the bifunctional epoxy tree represented by Formula 3 reacted with an organic filler compound must contain at least one cyclohexane ring. The cyclohexane ring is used for the purpose of improving the aliphatic Ϊ ' of one (10) hexanthene, which does not ensure flame retardancy. That is, the bifunctional epoxy resin (a 2 ) has at least one ring-like ring carbon number of 6 to a glycidyl ether compound of an aliphatic primary alcohol. The b ^ 10 group represents a specific example of the formula (4) of the bifunctional epoxy resin (10) represented by Formula 3. Meanwhile, R2 may also be an isomer of the group 1() or may have a substituent. Further, 'R2' may be one of these types, or may be two or more types.

(10-1)

(10-2)

(10-3) 322722 16 201132668

(10-4)

(10-5) one h2c

(10-6)

(10-7)

17 322722 201132668

(10-13) Among the bifunctional epoxy resins (a2) represented by Formula 3, it is preferably a glycidyl ether compound of cyclohexanedimethanol represented by Formula 11 or a hydrogenated bisphenol A represented by Formula 12 Glycidyl etherate. (11) -〇~H2C—< Η>—CH2—〇—HzC—CH——CH2

多2〇^Η〇· The polyfunctional epoxy resin (a3) represented by Formula 4 which is reactive with an organophosphorus compound is a trifunctional epoxy resin or a tetrafunctional epoxy resin having a fatty chain of 1 to 4 carbon atoms. On the other hand, in the aliphatic epoxy resin having no cyclohexane ring, the aliphatic epoxy resin other than the polyfunctional epoxy resin represented by the general formula 4 cannot ensure the flame retardancy. Among the polyfunctional epoxy resins (3) represented by the formula 4, a glycidyl ether compound of trishydroxypropylpropane represented by the formula 13 is preferred. CH2—〇—CH2 - CH—CH2 0 H3C—CH Factory C—CH2~〇—CHo-CH—CH2 (13)

V CH2—0—CH2-CH—ch2 , 〇 / simultaneous 'organophosphorus compound (B) reactive with epoxy resin (A), is an organic scale compound (bi) represented by Formula 5 and represented by Formula 6 Organic dish 18 322722 201132668 compound (b2). The organic filler compound (bl) represented by Formula 5 is a compound compound having two active hydrogens, wherein R5 and R6 represent hydrogen or a hydrocarbon group, which may be different or the same, and may be a linear or branched chain. Shape or ring. At the same time, R5 and R6 can be combined to form a cyclic structure. Specific examples of R5 and R6 include mercapto, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, pentyl, isodecyl, and new. Pentyl, third amyl, 1-decylbutyl, 1-methylpentyl, octyl, decyl, decyl, undecyl, dodecyl, phenyl fluorenyl, phenyl, fluorenylphenyl, Xylyl group and the like. Meanwhile, on the group which combines R5 and R6 to form a cyclic structure, for example, a tetrakisinyl group, a cyclopentylene group, a cyclohexylene group, a cycloheptyl group, a cyclooctyl group, a fluorenyl group, and a stretching group are mentioned. Borne base, stretching biphenyl, etc. Ar is an aryl group, and specific examples thereof include a phenyl group, a tolyl group, a diphenyl group, a naphthyl group, and a biphenyl group. At the same time, η is the number of 0 or 1. These organophosphorus compounds (bl) can be easily obtained by the reaction of the organophosphorus compound (b 2) of the formula 6 with a monocyclic or polycyclic ruthenium compound (Patent Document 6). As the ideal organophosphorus compound which can be used in the present invention, 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide of the organic scale compound represented by Formula 14 (hereinafter, abbreviated as follows) The addition reaction of DOPO) with 1,4-benzoquinone is carried out by a phosphorus-containing compound represented by Formula 15 (hereinafter, abbreviated as DOPO-HQ), or an addition reaction of DOPO with 1,4-naphthoquinone The phosphorus-containing compound represented by Formula 16 (hereinafter, abbreviated as DOPO-NQ).

S 19 322722 201132668

D0P0 is commercially available under the trade name "HCA" (manufactured by Sanko Co., Ltd.), and D0P0-HQ is commercially available under the trade name "HCA-HQ" (manufactured by Sanko Co., Ltd.). The organophosphorus compound (b2) represented by Formula 6 is an organophosphorus compound having one active hydrogen, wherein R7 and R8 represent hydrogen or a hydrocarbon tomb, which may be different or identical, respectively, and may be linear or branched. Chain or ring. At the same time, R7 and R8 can also be combined to form a ring structure. Specific examples of R7 and R8 include mercapto, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, pentyl, isopentyl, and new Pentyl, .p-pentyl, 1-decylbutyl, 1-methylheptyl, octyl, decyl, decyl, decyl, dodecyl, benzyl, phenyl, tolyl, Tolyl and the like. Meanwhile, at 20 322722 201132668, R7 and R8 are bonded to form a ring-shaped structure, and examples thereof include a tetramethylene group, a -cyclopentylene group, a cyclohexylene group, a cycloheptyl group, an exocyclooctyl group, and an extensible ring.癸 base t stretches the base of borneol, stretches biphenyl and so on. At the same time, ra is the number of 0 or 1. Among these compounds, D〇p〇 represented by the formula 14 is preferred. In the organophosphorus compound used in the phosphorus-containing epoxy resin of the present invention, the organophosphorus compound (bl) represented by the formula 5 and the (bl)/(organic compound (b2) represented by the formula 6) The weight ratio of b2) is 50/50 to 100/0, preferably 65/35 to 100/0, and preferably 8〇/2〇 to 1〇〇/〇, and 90/10 to loo/ ο is better. When the weight ratio of (bl)/(b2) is less than 0/100 to 50/50, although it is easy to adjust the phosphorus content, it has the effect of improving the difficulty or the viscosity reduction, but the one-function represented by the general formula 6 is obtained. The organic compound (10) causes a large amount of reaction with the epoxy group, and a large amount of the epoxy resin having less than the i-functionality is formed to reduce the total number of epoxy groups, so that the reactivity is greatly lowered. Further, the adhesion of the obtained cured product is lowered, the heat resistance is lowered, or the moisture resistance is lowered, and the electrical insulation reliability is remarkably lowered. As long as the weight ratio of (bl) / (b2) is in the range of 5 〇 / 5 Torr to 1 〇〇 / ,, since the reactivity of the filling knife can be ensured, the physical properties of the cured product are not lowered. When a large amount of the organophosphorus compound (bl) represented by Formula 5 is used, the molecular weight can be increased to greatly improve the adhesion. When the organophosphorus compound (b2) represented by Formula 6 is used in a large amount, The adjustment of the phosphorus rate is easy, so the amount of use must be adjusted according to the characteristics of the purpose. In the range of weight ratio of (bl)/(b2) = 50/50 to 100/0, 'if the higher flame retardancy is required, as long as the use ratio of the organophosphorus compound (b2) is increased, it must be higher. In the case of the adhesion, the use ratio of the organic dish compound (bl) may be increased. 21 322722 201132668 The organic breaking compound can be used by mixing the organic disk compound (b1) represented by the general formula 5 and the organic phosphorus compound (b2) represented by the general formula 6, and can also be used with the epoxy resin (A). Before the reaction, the organophosphorus compound (b2) represented by the formula 6 is first reacted with an anthracene. In this case, when the organophosphorus compound (b2) represented by the formula 6 is 1 mol, the anthracene is preferably reacted in an amount of less than 1 mol. With respect to the organophosphorus compound (b2) 1 mol represented by Formula 6, when a brew of 1 mol or more is used, 'the raw material hydrazine is left in the obtained phosphorus-containing epoxy resin, and the cured product is resistant. The wetness is deteriorated, so it is not good. The reaction of the epoxy resin (A) and the organophosphorus compound (B) used in the present invention can be carried out by a known method. The reaction temperature was 1 Torr. 〇 to 2〇〇. 〇, and is preferably carried out at 120 ° C to 18 (with stirring in TC. The reaction time can be determined after measuring the epoxy equivalent. The measurement can be determined according to the method of JIS_K7236. The epoxy equivalent can be determined by epoxy resin (A) The reaction with the organophosphorus compound becomes larger, so the reaction end point can be determined by comparison with the theoretical epoxy equivalent. Meanwhile, if the reaction rate is slow, the catalyst can be used as necessary to improve the yield. Use of tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as vaporized tetramethylammonium, phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine, and bromine Various catalysts such as sulfonium salts such as ethyl sulphate scales, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, etc. These catalysts may be used singly or in combination of two or more. The epoxy equivalent of the phosphorus-containing epoxy resin obtained by the production method of the present invention is preferably from 200 g/eq to 600 g/eq. If the epoxy equivalent is less than 2 〇〇g/ecj, 'the adhesion will be deteriorated' If it exceeds 600g/eq, the viscosity increases, and the heat resistance of the obtained cured product is greatly impaired. Therefore, the epoxy equivalent is preferably 22 32272. 2 201132668 200g/eq to 600g/eq ' and preferably from 230g/eq to 55〇g/eq, preferably from 250g/eq to 500g/eQ. The epoxy resin-containing epoxy resin obtained by the production method of the present invention The coverage rate is preferably from 1% by weight to 64% by volume. Although in terms of flame retardancy, the scaly ratio is preferably high, but as the content of the material becomes higher, the viscosity of the phosphorus-containing epoxy resin is increased or the ring is increased. The increase in oxygen equivalent causes the heat resistance of the obtained cured product to be greatly impaired. Therefore, the phosphorus content is preferably from 1% by weight to 6% by weight, and preferably from 5% by weight to 4% by weight, and preferably by 2% by weight. More preferably, it is more preferably 3% by weight. The total gas amount of the phosphorus-containing epoxy resin obtained by the production method of the present invention is related to the low electrical reliability of the obtained cured product, and the electrical quantity of the cured product is lowered as long as the amount is increased. When the reliability is reduced, the electrical reliability of the hard material can be improved. After considering the electrical reliability of the hardened material that can be tolerated, the total chlorine content should be G. 2% by weight or less 'and the sealing material: The epoxy resin is preferably 0.09% by weight or less, and more preferably 5% by weight or less. The melting viscosity of the phosphorus-containing epoxy resin obtained in the production method is preferably l, 〇〇〇mpa·s or less and preferably 6 〇〇mPa·s or less, and 300 mPa·s. If the melt viscosity in 1〇〇t: exceeds 1,000 mPa·s, even if a hardener having a low viscosity is used, the viscosity of the epoxy resin composition can be increased, and the actual work becomes It is difficult to obtain a normal molded product. The epoxy resin other than the phosphorus-containing epoxy resin obtained by the production method of the present invention can also be blended without damaging the characteristics of the composition of the present invention. 0 322722 23 201132668 In terms of the total epoxy resin component in the epoxy resin composition of the present invention, although the phosphorus content is not particularly specified, in terms of flame retardancy, the phosphorus content is preferred, and in the case of low viscosity. It is better to have a lower phosphorus ratio. Therefore, it is preferable to carry out the two-sided performance, that is, from 5% by weight to 5% by weight, and preferably from 1% by weight to 4% by weight, more preferably from 2% by weight to 3% by weight. In the hardener of the present invention, a polyphenol resin or an acid anhydride represented by a phenol novolak resin, an amine represented by dicyandiamide or diethyldiamine ruthenium ketone can be used. (4) The curing agent for the epoxy resin is usually used as the curing agent, and the curing agent may be used alone or in combination of two or more. At the same time, the epoxy resin composition of the present invention can be used in combination with a hard = accelerator. Examples of the hardening accelerator include phosphines, quaternary phosphonium salts, quaternary ammonium salts, imidazole compounds, and boron trifluoride complexes (dioxadiphenyl)-1,1-dimethyl group. Urea, 3-(4-phenylphenyl)-tertiary amines, quaternary hybrids..., into _-good class, 3-(3, 4-dioxadi-3-phenyl~1,1- Dimethyl urea, etc. 'but not limited to such compounds such as I 1 -dimethylurea, 3-), etc., the amount of the hardening accelerator, although it can be hardened by the epoxy resin used together, the % oxygen resin used The type of the agent, the molding method, the curing temperature, and the requirements vary from one to another, but in the case of 1 part by weight relative to the epoxy resin, it is preferably in the range of 〇1 to 20 parts by weight, and is 〇·i It is preferably used in an amount of up to 1 part by weight. The &amp;oxy resin composition of the present invention can be changed in accordance with the demand. Yi Yaogu

24 322722 201132668

^ Acid A calcium oxalate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, new 4 匕 ^, 2: 〇 &lt; ★, carbon fiber, glass fiber, alumina fiber, yttrium oxide oxidation Shaomin, . ―, strontium carbide fiber, polyester fiber, cellulose fiber, aromatic fiber brewing|* fiber, etc. These fillers are preferably from 1 to 95% by weight of the epoxy resin composition. ^ The epoxy resin composition of the present invention can be further blended with a decane coupling agent, an antioxidant, a mold release agent, an antifoaming agent, and an emulsification according to requirements. Various additives such as a agent, a shake imparting agent, 』&gt;, a slip agent, a flame retardant, a pigment, etc., are added in a range of from 0.01 to 20% by weight based on the total amount of the % gas resin composition. The epoxy resin composition of the present invention can be molded and hardened in the same manner as the known epoxy resin composition to form a cured product. The molding method and the treatment can be carried out in the same manner as the known epoxy resin composition, and the inherent method of the epoxy resin composition of the present invention is not required. The cured epoxy resin of the present invention can be formed into a coating film, an adhesive layer, a molded article, a laminate, or a film. (Effects of the Invention) The results of evaluation of the molded article obtained by using the epoxy resin composition of the present invention 'when compared with the conventional low-reduced tree-remaining product, it is possible to obtain hardening which is flame retardant and has a low water absorption rate. Things. It is understood that the epoxy resin composition and the cured product thereof can be used as a resin composition for manufacturing a copper slab layer used for an electronic circuit board or a sealing material, a molding material, a new molding material, and an adhesive for use in an electronic component. , film materials, electrical insulation coating materials, etc. [Embodiment] 322722 25 201132668 (Embodiment) Hereinafter, the present invention will be specifically described in terms of synthesis examples, examples, and comparative examples, but the technology of the present invention is not limited to the scope of the embodiments. Further, the number of parts to be dispensed of each component in the examples and the comparative examples is a part by weight unless otherwise specified. Meanwhile, the following analytical methods are used in the present invention. The method described in JISK-7236. That is, after the sample was dissolved in 10 mL of chloroform, 'the acetic anhydride was added twice, and 20% of the bromination was added.

10 mL of tetraethylammonium acetate solution, titrated with 电位· im〇1/L perchlorine acetate standard solution using a potentiometric titrator'. The concentration and amount of each reagent and the titer were determined from the epoxy resin. Epoxy equivalent. Full gas f. The method described in JISK-7243-3. Namely, the sample was dissolved in 25 mL of diethylene glycol monobutyl ether, and then 25 mL of a 1,4-〇1/L potassium hydroxide 1,2-propanediol solution was added thereto, and the mixture was heated on a hot plate for 1Q minutes to cause a reaction under reflux. After cooling to room temperature, '5 mL of acetic acid liver was added, and titration was carried out with a potentiometric titrator in a solution of 0.7 mol/L silver nitrate. The concentration and amount of each reagent and the titer were determined to determine the total amount contained in the epoxy resin. Gas volume. Viscosity: The method described in JISK-7233. That is, after taking the resin in a 5 〇〇 mL cylindrical can, and placing it in a constant temperature water bath of 25 ± 〇n: for 5 hours, the temperature is constant, and then the rotator of the rotary oximeter is impregnated in the resin. Determination. Softening point: *, also described in JISK-7234. That is, the sample is filled into the specified ring by the ring and the ball is placed horizontally in the glycerin bath. The temperature rise rate of °C/_ was measured. 322722 26 201132668 Hydroxyl group concentration: 1-2% by weight of phenyl isocyanate and dibutyltin butyl succinate as a catalyst were added to the amount of hydroxyl groups contained in the epoxy resin. After the base is sufficiently reacted with the isocyanate, dibutylamine equivalent to or more than the equivalent of the phenyl isocyanate used is added to consume excess phenyl isocyanate, and finally titrated with perchloric acid, and the concentration and addition of each reagent are added. The amount of hydroxyl groups contained in the epoxy resin is determined by the amount and the titer. Phosphorus content: sulfuric acid, hydrochloric acid, and peroxyacid are added to the sample, and after heating, the whole phosphorus atom is changed to orthophosphoric acid after being wet-ashed. In the acidic solution of sulfuric acid, the metavanadate and the molybdate are reacted, and the absorbance of the resulting phosphovanadomolybdic acid complex in 420 nm is measured, and the scale is expressed by the previously prepared calibration curve. The content of the wall contained in the epoxy resin is measured. The alpha diol content: the method described in JIS K-7146. That is, the chloroform is added to the sample and dissolved, and then the original periodate solution is added. The reaction was carried out for 2 hours, and then the iodine produced by adding the potassium iodide solution was titrated with sodium sulfate, and the content of the α-diol contained in the epoxy resin was determined from the concentration and the added amount of each of the reagents and the titer. : Using a cone-and-plate type viscometer (MOEDL CV-1S, manufactured by Toa Co., Ltd.), using 5 poise cone(d): 24mm' 0 : 0.5° as a rotator, l〇〇 The measurement was carried out at a temperature of ° C. Flame retardancy: It was measured according to the UL (Underwriters Laboratories Inc.) specification UL94 vertical test method, and V-0, V-1, V-2 'NG (not difficult) based on the criteria for the specification. The grading of the flammability is 4 (the later the s 27 322722 201132668, the more difficult the flame retardancy is.) Next: According to the method in JIS C-6481 5.7, that is, in one piece of prepolymer and the remaining 3 The sheets were peeled off at a speed of 50 mm/min in the vertical direction and measured. Moisture rate: according to the method of JIS C-6481 5. 13. That is, using a test piece cut into 50 mm x 50 mm, it was measured at 5 〇. (: dry weight after drying in an oven for 24 hours, and then measured and stored in The weight has been adjusted to 85 χ: /85% RH in the treatment tank after 72 hours, and the moisture absorption rate is measured according to the increase in dry weight. The heat quality: according to the method of IPC-TM-650 ' 2.4.24. Use the TMA device to measure the del ami nation time at TMA襄

The test piece was maintained at a constant temperature of 260 ° C. For example, when the test piece was peeled off until the time of occurrence of the displacement was 1 minute or longer, it was represented by 〇, and if it was less than 10 minutes, it was represented by X. At the same time, the TMA device is using SII

TMA/Ssl2〇u manufactured by Nanotechnology Co., Ltd. Gas ion: After the hardened material is pulverized, the sample is passed through a 2 mm mesh hole, and the sample having a particle size of 1 mm of the mesh is not subjected to a pressure cooker test at 150 Torr for 20 hours, and then the extracted water is measured by an ion chromatograph. The gas ion' can be obtained by converting it to the concentration in the hardened material. (Example 1) Epotohto TX-〇 as a difunctional aromatic epoxy resin (al) of the general formula 1 was placed in a four-neck glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser. 929 (made by Toho Chemical Co., Ltd., terephthalic acid diglycidyl ether resin, epoxy equivalent · 144 g / eq, total gas 28 322722 201132668 Quantity: 0.11% by weight, viscosity: 50 mPa · S, hydroxyl concentration: 39 meq/iM α diol content: 2.3 meq/100 g) 547.4 g, organic scalloped D0P0-HQ (manufactured by Sanko Co., Ltd., trade name: jjca-HQ, base fire 5 162 g/eq, phosphorus content) : 9.5 wt%) 252 · 6 g, covered with a Mantle heater - heated to 13 Torr while stirring. 〇, ♦ ° 13 (TC is added as a catalyst triphenyl phosphine (Beixing Chemical Co., Ltd. product name: TPP) 0 · 25g, the reaction temperature is maintained at 16 〇. (: 165 to 4 months after the reaction, A phosphorus-containing epoxy resin (E__1) of 795 g was obtained. The properties of the obtained epoxy resin (E-1) were as shown in Table 1. Scale (Example 2)

In a four-glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser, an EPQtQhtoTX-〇929 (as described above) containing a difunctional aromatic epoxy resin (al) of the formula i was prepared. 〇2.5g, a deletion of a second-line organic dish compound, (9, 10-dihydro-9-oxa-ίο-phosphinophene is a 10-oxide 1,4-naphthoquinone adduct, hydroxyl equivalent: 187g/ q, human phosphorus lining. 8_ 1 heavy 垔%) 197. 5g, with a coated electric resistance heater heated to the side of the side, when it reaches 13 (rc, add J + base + methyl mic as a catalyst) (Miyako Kasei Co., Ltd., product name: 2E4MZ) 〇· 〇5g 'The reaction temperature is maintained at 160 ° C to 165 ° C. After the anti-goose hour, the epoxy resin (E-2) 795 g is obtained. The properties of the obtained scaly bis-resin (E-2) are shown in the table. The money (Example 3) s * Four-glass separation with a mixing 2, a thermometer, a nitrogen gas guide, and a condenser In the flask, the difunctional aromatic system of the formula i is 322722 29 201132668 Epotohto Π-0934 of epoxy resin (al) (oxygen methylene biphenyl diglycidyl ether manufactured by Tosho Kasei Co., Ltd.) Resin, epoxy equivalent: 184 g / eq, total chlorine: 0.11% by weight, viscosity: 200 mPa · s, base concentration: 63 meq / 100 g 'α diol content: 2. 5meq / 100g) 608. 7g, as organic The D0P0-NQ (as described above) of the compound was filled with 116. 3g and D0P0 (manufactured by Sanko Co., Ltd., trade name: HCA, phosphorus content: 14.2% by weight) 75.0 g, while the coated electric resistance heater was stirred. Heating to 130eC, when reaching 130 ° C, adding triphenylphosphine (as described above) as a catalyst, I. Ig, maintaining the reaction temperature at 160 ° C to 165 ° C for 4 hours, can be obtained phosphorus Epoxy resin (E-3) 795 g. The properties of the obtained phosphorus-containing epoxy resin (E-3) are shown in Table 1. (Example 4) Equipped with a stirrer, a thermometer, a nitrogen gas introduction device, and a condenser tube In a four-neck glass separation flask, 182. Og and 420 g of toluene as an organic phosphorus compound were charged, and the mixture was heated while stirring under a nitrogen atmosphere to completely dissolve it. 1,4-naphthoquinone (manufactured by Kawasaki Kasei Co., Ltd., 3% aqueous product) 56. 7 g was input in batches. At this time, the molar ratio of 1,4-naphthoquinone to D0P0 was 1,4-naphthoquinone/DOPO=0.41. After heating, the difunctional aromatic system was added as the general formula 1. Epotohto TX-0917C of epoxy resin (al), manufactured by Tohto Kasei Co., Ltd., R1 of Formula 1 is a compound of Formula 7-12, epoxy equivalent: 173 g/eq, total chlorine: 0·10% by weight, viscosity: 46mPa · s,

Hydroxyl group concentration: 72 meq/100 g, α diol content: 2. 8 meq/100 g) 563. 0 g, while stirring while introducing nitrogen gas, heating to 13 (TC 30 322722 201132668 can remove toluene outside the reaction system. Then After adding the tetraphenylphosphine (as described above) as a catalyst to 0.24 g of 'reaction temperature maintained at 160 ° C to 165 ° C for 4 hours, 790 g of a phosphorus-containing epoxy resin (E-4) was obtained. The properties of the phosphorus-containing epoxy resin (E-4) are shown in Table 1. (Example 5) A four-neck glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser was charged. Epotohto ZX-1658C, which is a difunctional aliphatic epoxy resin (a2) of the formula 3, manufactured by Tohto Kasei Co., Ltd., cyclohexanediketanol diglycidyl ether resin, epoxy equivalent: 14 〇g/etl, all Chlorine content: 0. 075 wt%, viscosity: 45 mPa · s, hydroxyl concentration: I9meq / 100g 'αdiol content: 2. 8meq/100g) 547. 4g, D0P0-HQ as an organic dish compound (as mentioned above) 252. The coated heater is heated to 130 ° C while stirring, and maintains the temperature when it reaches 130 ° C. Then, triphenylphosphine (as described above) 〇·25g was added as a catalyst, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours, and then the epoxy resin (E-5) was obtained. ) 795g. The properties of the obtained phosphorus-containing epoxy resin (E-5) are shown in Table 1. (Example 6) HBPADGE (Maruzen Oil) as a difunctional aliphatic oxygen resin (a2) of the formula 3 was charged in a four-neck glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser. Chemical Co., Ltd., hydrogenated bisphenol A type diglycidyl ether resin, epoxy equivalent: 21 Og/eq, total chlorine content: 〇· 14% by weight, viscosity: 780 mPa · s, hydroxyl concentration: 66 meq/l 〇〇g , ααdiol content: 4. 6meqn〇Og) 632. 0g, D_-HQ (as mentioned above) 168.0g as an organic compound 382722201132668, heated to 13G by a coated electric resistance heater C, when the temperature reached i(1), the temperature was maintained for i hours, and then tris-phosphine (as described above) as a catalyst, 17 g, was added to maintain the reaction and the field production at (10). After reacting for 0 hours from 0 to WC, the trait of (4) ring = lipid (E-_5g. The resulting inclusion (4)) is shown in Table i J. (Example 7) Epotohto ZX- which is a polyfunctional aliphatic epoxy resin (a3) of the general formula 4 was placed in a four-neck glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser. 1542C Dongdu Chemical Co., Ltd., system, trimethyl methacrylate polyglycidyl hydrazine resin, epoxy equivalent: total chlorine: 0. 072 wt% 'viscosity: 80 mPa · s, base concentration: 195 meq/100 g' α Alcohol content: i.4meqM00g) 570.0g' as the organic phosphorus compound D0P0 (as mentioned above) 50.0g and D0P0-HQ (as before) 180. 0g' with the coated resistance heater while disturbing while heating to When it reaches 130 ° C, triphenylphosphine (as described above) is added as a catalyst. The reaction temperature is maintained at 丨 (9) and the reaction is continued for 15 hours. After the reaction for 4 hours, a phosphorus-containing epoxy resin can be obtained (E- 7) 795g. The properties of the obtained phosphorus-containing epoxy resin (E-7) are shown in Table 1. 32 322722 201132668 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example ^ 7 Epoxy resin (E-1) (E-2) (E-3) (E-4) (E-5) (E-6) (E-7) Quality of epoxy resin used al al al al al a2 a2 a3 Hydroxyloxy group concentration (meq/l〇〇g) 39 39 Ί 63 72 19 66 195 Total gas (% by weight) 0.11 0.11 0.11 0.10 0. 07 0.14 0.07 α diol content (meq/lOOg) 2.3 2.3 2.5 2.8 2.8 4.6 1.4 Use of epoxy resin (A : al, a2, a3) The weight ratio of phosphorus compound (bl) / compound (b2) is 100/0 100/0 61/39 55/45 100/0 100/0 78/22 Epoxy equivalent (q/eq) 362 261 350 393 348 386 232 Phosphorus content (% by weight) 3.0 2.0 2.5 3.2 3.0 1.7 3.0 Total gas (% by weight) 0.07 0. 06 0.07 0.07 0.04 0.10 0.04 Melt viscosity (mPa. s /100°C) 800 250 660 350 490 650 410 (Comparative Example 1) Epotohto PG as epoxy resin was placed in a four-piece glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser. 207GSC Dongdu Chemical Co., Ltd. made 'polypropylene glycol Glycidyl ether resin, epoxy equivalent: 319 g / eq, total chlorine: 0 · 10% by weight, viscosity: 45 mPa · s, hydroxyl concentration: 88 meq / 100 g, alpha diol content: 2 · 0meQ / 100g) 632. Og, D0P0-HQ (as described above) as an organic phosphorus compound (168. 0g), heated to 13 () ° C while stirring with a sheathed electric resistance heater, and added to the three stupid base as a catalyst when reaching 130 ° C The phosphine (as described above) was 0.17 g and the reaction temperature was maintained at 16 Torr. After reacting for 4 hours in 165 Torr, 795 g of a phosphorus-containing epoxy resin (E-8) was obtained. The properties of the obtained phosphorus-containing epoxy resin (Ε-8) are shown in Table 2. (Comparative Example 2) Ep〇t〇ht〇33 322722 201132668 Dingyi-0917 as an epoxy resin was placed in a four-port glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser. The above) 757.98, as an organophosphorus compound 1) (^〇- (i.e., as described above) 42. lg' is heated to 130 C with a sheathed electric resistance heater while stirring, and three as a catalyst when it reaches 130 C Phenylphosphine (as described above) 0. 05g, the reaction temperature is maintained at 丨(9). After reacting for 4 hours in i65〇c, 795 g of phosphorus-containing epoxy resin (E-9) is obtained. The properties of the resin (E-9) are shown in Table 2. (Comparative Example 3) A four-neck glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser was charged as an epoxy resin. Ep〇t〇ht〇TX-0917C as described above) 480. Og, as an organophosphorus compound D〇p〇 (as mentioned above) 220.0g and D0P0-HQC as described above) i〇〇.〇g, coated The electric resistance heater was heated to 13 Torr while stirring. (: When the 130 〇c is reached, the diphenylphosphine (as described above) 〇·32g is added as a catalyst, and the reaction temperature is maintained at 165 C for 4 hours, and a phosphorus-containing epoxy resin (E) is obtained. -10) 795 g. The properties of the obtained phosphorus-containing epoxy resin (E_1〇) are shown in Table 2. (Comparative Example 4) Four-piece glass separation type equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser The Og, as an organic phosphorus compound, D〇p〇_HQ (as described above) 295. Og, coated The electric resistance heater was heated to 130 ° C while stirring, and when it reached 130 t, triphenylphosphine (as described above) was added as a catalyst. 0. 30 g', the reaction temperature was maintained at 16 Torr, and it was reacted for 4 hours in 165 〇c. The composition of epoxy resin (E-11) 795g was obtained. The properties of the obtained filled epoxy tree 322722 34 201132668 grease (E-ll) are shown in Table 2. (Comparative Example 5) equipped with a stirrer And the phosphatase (as described above) 137. 6g And the 1,4-naphthoquinone (as described above) 31.3 g of hydrazine was added in batches while being heated in a nitrogen atmosphere. In this case, 莫, the molar ratio of 4-naphthoquinone to D0P0 is 1,4-naphthoquinone/DOP〇=〇·13. After heating, Epotohto ZX-1659C, which is an epoxy resin, was put into the company. , hydrogenated bisphenol A type diglycidyl ether resin, epoxy equivalent: 215 g / eq, total gas amount: 0. 45 wt%, viscosity: 1,500 mPa · s, hydroxyl concentration: 230 meq / 100 g 'α diol content: Llmeq/100g) 632. Og, while stirring while introducing nitrogen gas, the toluene can be removed from the reaction system when heated to i3〇°c. Then, triphenylphosphine (as described above) 〇·17g was added as a catalyst, and the reaction temperature was maintained at 16 (TC to 165 Torr for 4 hours, and then 790 g of a phosphorus-containing epoxy resin (E-12) was obtained. The properties of the epoxy resin (E-12) containing the dish are shown in Table 2. (Comparative Example 6) In a four-piece glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser, Epotohto ZX-1542 (manufactured by Tohto Kasei Co., Ltd., trimethylolpropane polyglycolate, epoxy resin equivalent: 122 g/eq' total gas amount: 〇. 〇65 wt%, degree 80gPa · s 'base concentration: 262meq/100g, α diol contains θ I 5meq/100g) 570· Og, as an organophosphorus compound d〇P〇 (as described in 322722 35 201132668) 50. 0g and D0P0- HQ (as mentioned above) 180. 0g, heated to 130 ° C with a sheathed resistance heater while stirring, and when it reaches 130 ° C, a tris-phosphine (as described above) 〇 23g is added as a catalyst to react After the temperature was maintained at 160 ° C to 165 ° C for 4 hours, 795 g of a phosphorus-containing epoxy resin (E-13) was obtained. The properties of the resin (E-13) are shown in Table 2. (Comparative Example 7) A four-neck glass separation flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser was charged as an epoxy resin. Epotohto YDF-170 (made by Tohto Kasei Co., Ltd., bisphenol F type diglycidyl ether resin 'epoxy equivalent: 168 g/eq, total gas amount: 0.15 wt%, viscosity: 3, OOOmPa · s) 547. 4g, 252. 6g of D0P0-HQ (as described above) as an organic phosphorus compound, heated to 130 ° C while stirring with a sheathed electric resistance heater. When added to 130 ° C, triphenylphosphine was added as a catalyst (as mentioned above). 〇 25g, after the reaction temperature is maintained at 160 ° C to 165 ° C for 4 hours, 795 g of phosphorus-containing epoxy resin (E-14) can be obtained. The resulting phosphorus-containing epoxy resin (E-14) The properties are shown in Table 2. [Table 2] Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example 1 2 3 4 5 6 7 Phosphorus-containing epoxy resin (E-8) (E-9) (E-10) (E-11) (E-12) (E-13) (E-14) Quality of epoxy resin used - al al al a2 a3 - Hydroxyloxy group concentration (meq/lOOg) 88 72 72 63 230 262 - full gas (heavy Amount %) 0.1 0.1 0.1 0.11 0.45 0.07 0.15 α diol content Oneq/lOOg) 2 2.8 2.8 2.5 11 1.4 _ With or without epoxy resin (A : al, a2, a3) Nothing with or without phosphorus compounds (bl ) / phosphorus compound (b2) weight ratio 100/0 100/0 31/69 100/0 43/57 39/61 100/0 quality of epoxy resin epoxy equivalent (q/eq) 630 196 705 880 392 206 490 Disc content (% by weight) 2 0.5 5.2 3.5 2.4 3 3 ~U(_wt%) 0.07 0.1 0.07 0.07 0.33 0.04 0.1 Solubility (mPa . s/100°C) 125 1&gt; 550 1,300&quot; 800 200 26,800 36 322722 201132668 (Examples 8 to 1 〇, Comparative Examples 8 to u) The epoxy resin containing a dish, a hardener hardening accelerator, etc. are prepared according to the blending prescriptions of ",, and Table 3. After dissolving the so-called epoxy resin with methyl ethyl ketone, the dicyandiamide (10) Y, which has been pre-sieved as a hardening agent in methyl ketone, dimethyl ketoamine, active hydrogen equivalent: 21 () g / eq) and 2-ethyl-4-methyl sulphur (as described above) as a hardening accelerator, and a resin composition varnish having a nonvolatile content of 50% by weight was prepared. Then, the obtained resin varnish was impregnated with a glass cloth (glass cl〇th (manufactured by Nitto Bose Co., Ltd., WEA116E 106S 136, thickness 100//111), and the impregnated glass cloth was 150 ° C. The hot air circulating oven was dried for 8 minutes to obtain a prepolymer. Next, four prepolymers were superposed, and heated and pressed under conditions of 13 〇ΐχ 15 minutes and 170 ° C x 2.0 MPa for 70 minutes to obtain a laminate having a thickness of 0.55 mm. For each of the obtained laminated sheets, physical properties of flame retardancy, adhesion, and moisture absorption rate were tested. The results are shown in Table 4. [Table 3] Example 8 Example 9 Example 10 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 (E-1) 100 filled with (E-2) 100 epoxy tree (E-5) 100 fat (E-8) ______ 100 (E-9) One 100 (E-10) - One _100 (E-11) 100 Hardener dicyandiamide 3.6 4.8 3,6 2 6. 4 1.8 1.4 Hardening accelerator 2E4MZ 0.2 0.2 0.2 0.2 0.2 0.2 *--- 0.2 Note: 2E4MZ is 2-ethyl-4-methyl-methyl 0 sitting s 37 322722 201132668

[Table 4] Example 8 Example 9 Example 10 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Flame retardancy ^ V-0 V-0 V-1 NG NG V-0 V-0 Subsequent (kN /m) 2.2 2 2 2 0.6 0.9 2.8 Moisture absorption rate (% by weight) H 1.2 1 1.3 2.5 2.1 1.8 1.2 Heat resistance 〇〇〇〇〇 XX Since Comparative Example 8 is an aliphatic phosphorus-containing epoxy resin, although It is good in subsequent properties, but it is poor in flame retardancy and poor in moisture absorption resistance. Although Comparative Example 9 is a phosphorus-containing epoxy resin of the general formula 1, the phosphorus content is 〇. 5 wt% is low, and the flame retardancy is not good, and since the ring oxime equivalent is less than 96 g/eq, And the adhesion is not good. Although Comparative Example 1 is a phosphorus-containing epoxy resin of the general formula 1, the epoxy equivalent is 7 〇 5 g / eq, which is too large, and the heat resistance is not good, and the phosphorus compound (bl) / phosphorus compound due to the raw material The weight ratio of (1) and 2) is 31/69, which is lower than 50/50, and the adhesion is not good, and the hygroscopicity is also poor. Although Comparative Example 11 is a filled epoxy resin of Formula 1, it has a large epoxy equivalent of 880 g/eq and a melt viscosity of 1,300 mPa·s is also large, although the adhesion is good, but the heat resistance is not good. On the other hand, in all of the examples, sufficient flame retardancy was ensured and the adhesion was good at the same time, and moisture absorption resistance and heat resistance were also good. (Examples 11 to 14, Comparative Examples 12 to 14) A phosphorus-containing epoxy resin, a hardener, a hardening accelerator, and the like were formulated in accordance with the blending prescription shown in Table 5. Using diethyldiaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayahard AA, active hydrogen equivalent: 63 g/eq 'viscosity: 2,500 mPa · s) as a hardener, heated to 50 on one side After stirring at ° C, an epoxy resin composition can be obtained. The obtained 322722 38 201132668 epoxy resin composition was defoamed and then injected into a mold to form a cured product having a thickness of 2 mm at 15 (TC &gt;&lt; 120 minutes. After hardening under the temperature of the clock). The obtained cured test piece was tested for physical properties of chloride ion, flame retardancy, and moisture absorption rate. The results are shown in Table 6. Meanwhile, in Comparative Example 12, Epotohto ZX-1059 (manufactured by Tohto Kasei Co., Ltd., A mixture of F-type diglycid chrome engraving resin and double-type A-type diglycidyl hydrazine resin, epoxy equivalent: 165g/eq, total chlorine: 0·08% by weight, viscosity: 2, 300mPa · s) 'Add 1,3-phenylene bis-di-2,6-xylene phosphate (manufactured by Daiba Chemical Industry Co., Ltd., trade name: PX-200, phosphorus content: 9. 0% by weight) as an additive type of flame retardant The amount of the agent added may be such that the phosphorus content in the epoxy resin composition becomes 2.0% by weight. [Table 5] Phosphorus-containing epoxy tree ruthenium Example 11 Example 12 Example 13 Example 14 _ Example 12 ttmi 13 Example 14 (E-1) 100 (E-3) 100 (E-6) 100 (E-7) 100 (E-12) 100 (E-13) 100 _Epoxy resin ZX-1059 100 Hardener KayahardAA 17.4 18.0 16.3 27.2 16.1 30.6 38.2 Hardening accelerator 2E4MZ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Γ Flame retardant PX-200 20.0 Note: 2E4MZ is 2-ethyl-4-曱Benzimidazole [Table 6] Example 11 Example 12 Example 13 Example 14 Comparative Example 12 Comparative Example 13 Comparative Example Η Gas ion (PPID) 30 50 70 20 320 30 50 Flame retardancy (UL94) V-0 V- 0 V-0 V-0 V-1 V-1 V-2 «Moisture rate (% by weight) 1.3 0.9 1 1.5 2.1 2.5 1.6

S 39 322722 201132668 Although Comparative Example 12 uses the filled epoxy resin of the general formula 3, the total chlorine content of the raw material epoxy resin is more than 0.45 wt%, and the chloride ion of the cured product is approximately the same as the example. More than 5 times. This means that the reliability is deteriorated. Further, since the hydroxyl group concentration is more than 23 〇meq/l 〇〇g, the α diol content is also llmeq/lOOg, and the hygroscopicity is poor. At the same time, the weight ratio of the phosphorus compound (bl)/phosphorus compound (b2) to the raw material is 53/57' lower than 50/50, so that the hardened state of the cured product is deteriorated, and the flame retardancy is somewhat poor. Although Comparative Example 13 uses the phosphorus-containing epoxy resin of the general formula 4, but the hydroxyl group concentration of the raw material epoxy resin is 262 meq/100 g, the hygroscopicity is poor, and the phosphorus compound (bl) of the raw material is obtained. The weight ratio of the phosphorus compound (b2) is 39/61' lower than 50/50, so that the hardened state of the cured product is deteriorated, and the flame retardancy is somewhat poor. Although Comparative Example 14 is an epoxy resin composition in which a flame retardant is blended in a generally low-liquid-liquid resin, even if the filling ratio is the same as the example, 'the flame retardancy is not good' and the moisture absorption resistance is also bad. In contrast to the above embodiments, sufficient flame retardancy is ensured, and the amount of gas ions is low, and moisture absorption resistance is also good. This means that the reliability is good. (Examples 15 to 17, Comparative Examples 15 to 17) A phosphorus-containing epoxy resin, a hardener, a hardening accelerator, and the like were formulated in accordance with the blending prescription shown in Table 7. A trisyl methane type phenol resin (trade name: TMP-ioo 'hydroxyl equivalent: 97. 5 g / eq, softening point. l 〇 7 ° C) was used as a hardener and heated to 120. After stirring at ° C, an epoxy resin composition can be obtained. The obtained epoxy resin composition was defoamed, molded into a mold, and hardened at a temperature of 15 〇ΐχ 12 〇 + 180 ° C x 60 minutes to obtain a cured test piece having a thickness of 2 mm 40 322722 201132668. Various physical property tests of moldability, flame retardancy, and moisture absorption rate were carried out on the obtained cured test piece. The results are shown in Table 8. Meanwhile, in Example 14, EpotohtoZX-l〇59 (as described above) was simultaneously used as an epoxy resin other than the phosphorus-containing epoxy resin, and in Comparative Example 16, 'Epoto hto ZX-1542C Dongdu Chemical Co., Ltd. was simultaneously used. A mixture of trimethylolpropane polyglycidyl ether resin, epoxy equivalent: 122 g/eq, 氱. 065 wt%, viscosity: 8 〇 mPa · s) other than phosphorus-containing epoxy resin Epoxy resin. [Table 7] Example 15 Example 16 Example 17 Comparative Example 15 Comparative Example 16 Comparative Example Π Phosphorus-containing epoxy resin (E-3) 80 (E-4) 100 (E-7) 100 (E-8 100 (E-14) 100 80 Epoxy Resin ZX-1059 20 PG-207GS 20 Hardener TMP-100 34.1 24.8 50.0 15.5 19.9 22.0 Hardening Accelerator 2E4MZ 0.2 0.2 0.2 0.2 0.2 0.2 Note: 2E4MZ is 2-ethyl- 4-methylimidazole [Table 8] Example 15 Example 16 Example 17 Comparative Example 15 Comparative Example 16 Comparative Example 难 Flame Retardancy (UL94) V-0 V-0 V-1 NG — NG b Moisture Rate (Weight ?0 0.8 0.9 1.1 1.6 - 1.8 Since Comparative Example 15 uses an aliphatic phosphorus-containing epoxy resin, it is inferior in flame retardancy and poor in moisture absorption resistance. Although Comparative Example 16 is a method described in Patent Document 4 Since the phosphorus-containing epoxy resin is not the epoxy resin containing the dish of the general formula 1, the viscosity of the epoxy resin composition is higher than 5 41 322722 201132668, and it is difficult to mold the mold, so that the epoxy resin is not formed. Test piece necessary for the test. Although Comparative Example 17 is a phosphorus-containing method obtained by the method described in Patent Document 4. In the epoxy resin, a diluent is used as the epoxy resin composition having a reduced viscosity, and the moldability can be improved, but the flame retardancy is deteriorated and the moisture resistance is also deteriorated. In contrast, in the examples, all of the examples can be sufficiently ensured. The flame retardancy is good, and the moldability is good and the moisture absorption resistance is also good. [Industrial Applicability] Since the epoxy resin composition of the present invention is a low-viscosity composition, the hardened material is hardly flammable and moisture-resistant. Excellent in properties, so it can be used in cast molding materials, laminated materials, sealing materials, composite materials, etc. [Simple description of the diagram] No [Main component symbol description] No 42 322722

Claims (1)

201132668 VII. Patent application scope: -1. A method for producing a phosphorus-containing epoxy resin, characterized by: an epoxy resin (al) represented by the formula ι , or an epoxy resin (a2) represented by the general formula 3 An epoxy resin (A) formed by at least one of the epoxy resins (a3) represented by Formula 4 and an organophosphorus compound represented by Formula 5 and/or an organophosphorus compound represented by Formula 6 (b2) The organophosphorus compound (B) is reacted to produce a hydroxyl group concentration of epoxy resin in a method of producing a phosphorus-containing epoxy resin having an epoxy equivalent of 200 to 600 g/eq and an f-rate of 1 to 6 wt%. It is 200 meq/100 g or less, and the total chlorine content is 〇·4% by weight or less, the α-diol content is 10 meq/100 g or less, and the organic scale compound (b)/organophosphorus compound (b2) of the organic scale compound (8) The weight ratio is 50/50 to loo/o, G0~H2C-R is wide CH2 - OG (1), and 1? main-1 does not have at least one aromatic ring which may contain oxygen atoms, nitrogen, and carbon The hydrocarbon group G of 6 to 31 represents any one of the hydrogen compounds; (2) CH2-CH^CH2 GO-R2-〇g (3) ^ may have a monocyclic heterocyclic ring Less than one ring-burned cycloaliphatic hydrocarbon group! 1G, =_f f, sulfur atom 6 to 17 of the fat G, either of formula 2 or hydrogen; 322722 1 201132668 『3- 〇G R4—c -fR3^〇G (4) In the formula, R3 independently represents an aliphatic nicotinyl group having a carbon number of 1 to 4 which may contain an oxygen atom and a nitrogen atom, i represents _R3_〇g or _^_7 or hydrogen. Any Ί G represents any formula of formula 2 or hydrogen, k represents an integer of 〇 or 1; 〇II (5) P-Ar-OH r6 oh r5, r6 represents hydrogen or a hydrocarbon group, which may be different or the same respectively, may be, τΙΑ left # =V' τ® ϋΝ i—» _ where ι 仰 仰 仰 取 , 仰 仰 仰 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直 直An integer representing 〇 or i means any of biphenyl, naphthalene, phenanthrene, and the like of the hydrocarbyl substituents; R, Η Ο ^1 (. 士 / / Re (8) = represents hydrogen or a hydrocarbyl group, which may be Different or identical, it can be linear, branched, or ring-shaped, and at the same time, combined to form a ring structure, m means "phantom integer. 7-8. 2.=Π? Phosphate-containing ring A method for producing an oxyresin, wherein one of the epoxy resins represented by the patent formula 7 or the formula _9 or 2 (10) 11 is used in the form of a fly 322722 2 201132668 h2c-hc-h2c-o- H2c Ch2-〇—h2c—ch—^CH2 (7) Hi〇—CH—CH2—0-CH2 Ch2—o-ch2~ch——-ch2 (8) HjC_O—HgC ^ H y CH2—O—HjC—CY^—pCH2 (9) CH3 Η2〇^〇Η CH2—O—H )-9-^ H )-〇-^H2---CH2 (10) ch3 CH2—O—CHj—CH—CH2 H3C—CH2-C—ch2—0—CH2-CH—CH2 VaCH2—0—CH2&quot;CH—CH2 ( 11) The method for producing a phosphorus-containing epoxy resin as described in claim 1 or 2, wherein the organophosphorus compound (bl) described in the first aspect of the patent application is at least Formula 12 or One of the organophosphorus compounds represented by Formula 13, 3 322722 201132668 4. The method for producing a phosphorus-containing epoxy resin according to any one of claims 1 to 3, wherein the organophosphorus compound (bl) described in the first aspect of the patent application is represented by the formula 14. Organic phosphorus compound, 5. An epoxy resin composition comprising: a filled epoxy resin obtained by the method for producing a phosphorus-containing epoxy resin according to any one of claims 1 to 4; A hardener is an essential component. A hardened material obtained by hardening the epoxy resin composition according to item 5 of the patent application. 4 322722 201132668 IV. Designated representative map: There is no schema in this case (1) The representative representative map of this case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: G〇_H2C-Ri_CH2—〇G (1) GO-R2~〇G (3) ) R3—OG 6 322722