JP2018168074A - Organic phosphorus compound, curable resin composition containing organic phosphorus compound, and cured product thereof, and method for producing organic phosphorus compound - Google Patents

Abstract

To provide an organic phosphorus compound useful as e.g. a flame retardant of an epoxy resin cured product, and a flame-retardant resin composition prepared therewith.SOLUTION: An organic phosphorus compound is obtained by the reaction of 1 mol of a quinone compound having a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring with 2 mol of a phosphorus compound represented by formula (2). (Rand Rare each a hydrocarbon group optionally having a hetero element, where Rand Rmay be bound to each other to form a cyclic structure; n1 and n2 are each 0 or 1).SELECTED DRAWING: None

Description

  The present invention relates to a copper clad laminate used for an electronic circuit board, a film material, an epoxy resin composition for producing a copper foil with resin, and a sealing material, a molding material, a casting material, an adhesive, and an electrical insulation used for an electronic component. The present invention relates to an organic phosphorus compound useful as a flame retardant for coating materials and the like, a flame retardant curable resin composition using the organic phosphorus compound, a cured product thereof, and a method for producing the organic phosphorus compound.

  In recent years, the flame retardancy of electronic equipment has been reduced by halogen-containing compounds typified by conventional brominated epoxy resins for the purpose of controlling toxic gases generated during combustion from the viewpoint of reducing environmental impact. From the above, halogen-free flame retardant, which has been made flame retardant with organophosphorus compounds, is already established, and is generally widely used and recognized as a phosphorus flame retardant epoxy resin.

  As a specific representative example of such an epoxy resin imparted with flame retardancy, proposals have been made to apply organic phosphorus compounds as disclosed in Patent Documents 1 to 4. Patent Document 1 describes 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO-HQ) and epoxy resins. A thermosetting resin obtained by reacting at a predetermined molar ratio is disclosed. Patent Document 2 briefly describes a method for producing diphenylphosphilhydroquinone and discloses a phosphorus-containing epoxy resin obtained by reacting an epoxy compound having two or more epoxy groups with this diphenylphosphilhydroquinone. Patent Document 3 discloses a method for producing a flame-retardant epoxy resin in which an epoxy resin, a phosphine compound having an aromatic group on a phosphorus element, and a quinone compound are reacted in the presence of an organic solvent. Patent Document 4 discloses a phosphorus-containing epoxy resin and a phosphorus-containing flame-retardant epoxy resin composition obtained by reacting a phosphorus-containing polyphenol compound and an epoxy resin.

  Patent Document 5 discloses 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO), 1,4-benzoquinone (hereinafter abbreviated as BQ) and / or 1,4. A step of obtaining a reaction composition by reacting naphthoquinone (hereinafter abbreviated as NQ) while controlling the total water content in the reaction system to be 0.3% by mass or less with respect to the total amount of DOPO used in the reaction. The phosphorus-containing flame-retardant bisphenol epoxy resin is produced by performing the step 2 of reacting with the bisphenol A type epoxy resin and / or bisphenol F type epoxy resin without purifying the reaction composition obtained in step 1 and step 1. A method is disclosed. Here, in any case, a phosphorus functional epoxy resin produced after reacting a quinone compound with an organic phosphorus compound such as DOPO or diphenylphosphine oxide to produce a bifunctional phenol compound and reacting with the epoxy resin. It is described. In any of these cases, it is natural that flame retardancy is imparted by the above-mentioned organophosphorus compound as a halogen-free solution considering the influence on the environment, but in order not to impair the heat resistance after curing of the phosphorus-containing epoxy resin, The method used as a form of the bifunctional phenol compound to increase the crosslinking density is described as a feature.

  On the other hand, about the bifunctional phenol compound which added these DOPO, patent document 6-7 has described the influence of the by-product produced | generated in the synthesis process. In Patent Document 6, after a reaction in which the content of by-products is reduced in an inert solvent having a dielectric constant of 10 or less with DOPO and NQ, this reaction composition is treated with ethylene glycol, propylene glycol, diethylene glycol, cyclohexanone, benzyl alcohol, and acetate. And a method of recrystallization purification by dissolving in a solvent selected from benzoic acid esters.

  Patent Document 7 refers to a by-product in producing a phosphorus-containing phenol compound. When the epoxy resin is reacted with this phosphorus-containing phenol compound and handled as a phosphorus-containing epoxy resin, the content of the by-product can be regulated to suppress significant curing delay during the curing reaction. And even if this by-product is a slight content level, it has a great influence on inhibiting curability, and it is described that suppression of this content is important.

  However, in any document, the organophosphorus compound of the present invention is not mentioned, and the production conditions and the effects of the organophosphorus compound are not found.

Japanese Patent Laid-Open No. 04-11626 Japanese Patent Laid-Open No. 05-214070 JP 2000-309624 A JP 2002-265562 A JP 2006-342217 A JP 2013-43910 A International Publication No. 2009/060987

  As a flame retardant formulation of a non-halogen epoxy resin cured product, an organophosphorus compound useful as a flame retardant that exhibits excellent flame retardancy without reducing the heat resistance of the cured product, and this organophosphorus compound were used. It is providing the flame-retardant curable resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific organic phosphorus compound obtained by reacting an organic phosphorus compound typified by DOPO with a quinone compound has been known in the past. Solder due to improved heat resistance and reduced water absorption, in addition to excellent flame retardancy in cured products, with resin compositions that have superior flame retardancy compared to compounds. The inventors have found that characteristics such as reflowability are improved and have completed the present invention.

ここで、Ａｒはベンゼン環、ナフタレン環、アントラセン環、又はフェナントレン環から選ばれる芳香族環基を示し、これらの芳香族環基は、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数５〜８のシクロアルキル基、炭素数６〜１０のアリール基、炭素数７〜１１のアラルキル基、炭素数６〜１０のアリールオキシ基、又は炭素数７〜１１のアラルキルオキシ基を置換基として有してもよい。Ｚは下記式（ａ）で表されるリン含有基である。 That is, this invention is an organophosphorus compound represented by following formula (1).

Here, Ar represents an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, and these aromatic ring groups are alkyl groups having 1 to 8 carbon atoms and those having 1 to 8 carbon atoms. An alkoxy group, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an aralkyloxy group having 7 to 11 carbon atoms. You may have a group as a substituent. Z is a phosphorus-containing group represented by the following formula (a).

ここで、Ｒ^１、Ｒ^２はそれぞれ独立に、ヘテロ元素を有してもよい炭素数１〜２０の炭化水素基を示し、直鎖状、分岐鎖状、環状であってもよく、また、Ｒ^１とＲ^２が結合して環状構造を形成してもよい。ｎ１、ｎ２はそれぞれ独立に、０又は１である。

Here, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero element, and may be linear, branched or cyclic, R ¹ and R ² may combine to form a cyclic structure. n1 and n2 are each independently 0 or 1.

ここで、Ｒ^３はそれぞれ独立に炭素数１〜１１の炭化水素基であり、ｍ１はそれぞれ独立に０〜４の整数である。ここで、Ｒ^４はそれぞれ独立に炭素数１〜１１の炭化水素基であり、ｍ２はそれぞれ独立に０〜５の整数である。 Z in the above formula (1) is preferably a phosphorus-containing group represented by the following formula (b1) and / or (b2).

Here, R ³ is each independently a hydrocarbon group having 1 to 11 carbon atoms, and m 1 is each independently an integer of 0 to 4. Here, R ⁴ is each independently a hydrocarbon group having 1 to 11 carbon atoms, and m 2 is each independently an integer of 0 to 5.

  Moreover, this invention is a curable resin composition characterized by including the said organophosphorus compound and a thermosetting resin.

  The thermosetting resin material preferably contains an epoxy resin and a curing agent.

  Moreover, this invention is the material for circuit boards which consists of the said curable resin composition, a sealing material, or a casting material. Moreover, this invention is a hardened | cured material formed by hardening | curing this curable resin composition.

ここで、Ｒ^１、Ｒ^２、ｎ１及びｎ２は上記式（ａ）のＲ^１、Ｒ^２、ｎ１及びｎ２と同義である。 The present invention also provides a method for producing the organophosphorus compound,
With respect to 1 mol of the phosphorus compound represented by the following formula (2), the quinone compound is present in an amount of 0.5 to less than 1.0 mol and water in an amount of 0.05 to 0.5 mol. Step 1 of reacting at ~ 200 ° C,
Step 2 of dissolving the reaction product obtained in Step 1 in a good solvent to remove insoluble impurities, and
Step 3 in which the solution obtained in Step 2 is mixed with a poor solvent to obtain a product by precipitation separation,
It is a manufacturing method of the organophosphorus compound characterized by having.

^Wherein, R ^1, R ^2, n1 and n2 have the same meanings as ^{R 1, R 2,} n1 and n2 in the formula (a).

  The good solvent is preferably one solvent selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, cyclohexanone, benzyl alcohol, acetic acid ester, and benzoic acid ester, or a mixed solvent of two or more, and the poor solvent is methanol. One solvent or a mixed solvent of two or more selected from the group consisting of ethanol, butanol and acetone is preferred. The reaction in the above step 1 is preferably performed under reflux conditions.

ここで、Ｒ^３及びｍ１は式（ｂ１）のＲ^３及びｍ１と同義である。Ｒ^４及びｍ２は式（ｂ２）のＲ^４及びｍ２と同義である。 The phosphorus compound is preferably a compound represented by the following formula (2a) and / or (2b).

Here, ^{R 3} and m1 have the same meanings as ^{R 3} and m1 of formula (b1). R ⁴ and m2 have the same meanings as ^{R 4} and m2 of the formula (b2).

  The quinone compounds are benzoquinone, naphthoquinone, anthraquinone, phenanthrenequinone, methyl-benzoquinone, ethyl-benzoquinone, dimethyl-benzoquinone, methyl-methoxy-benzoquinone, phenyl-benzoquinone, methyl-naphthoquinone, cyclohexyl-naphthoquinone, methoxy-naphthoquinone, methyl- It is preferably at least one selected from the group of anthraquinone, diphenoxy-anthraquinone, and methyl-phenanthrenequinone.

  The cured product of the resin composition using the organic phosphorus compound of the present invention has significantly improved flame retardancy as compared with the cured product using the conventional organic phosphorus compound. That is, since the phosphorus content, which is the purpose of imparting flame retardancy, can be kept low, a reduction in the water absorption of the cured product can be achieved. Therefore, it is possible to provide an electronic circuit board material excellent in thermal stability such as solder reflow property of a cured product such as a laminate.

1 is a GPC chart of an organic phosphorus compound obtained in Example 1. 2 is a FT-IR chart of the organic phosphorus compound obtained in Example 1. FIG. 2 is a NMR chart of the organic phosphorus compound obtained in Example 1. FIG.

The organophosphorus compound of the present invention is represented by the above formula (1).
In the formula (1), Ar represents a tetravalent aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring. The aromatic ring group may consist of only a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, and may have a substituent.
The substituent in the case of having a substituent is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 carbon atoms. -11 aralkyl group, aryloxy group having 6 to 10 carbon atoms, or aralkyloxy group having 7 to 11 carbon atoms, and when the substituent has an aromatic ring, the aromatic ring is further an alkyl group or an alkoxy group It may be substituted with.

  Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and a hexyl group. Examples of the group include a cyclohexyl group, and examples of the aryl group or aryloxy group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a naphthyl group, a methoxyphenyl group, an ethoxyphenyl group, a phenoxy group, and a naphthyloxy group. Examples of the aralkyl group or aralkyloxy group having 7 to 11 carbon atoms include a benzyl group, a phenethyl group, a 1-phenylethyl group, a benzyloxy group, and a naphthylmethyloxy group.

  Preferred Ar includes a benzene ring group, a methyl group-substituted benzene ring group, a 1-phenylethyl group-substituted benzene ring group, a naphthalene ring group, a methyl group-substituted naphthalene ring group, or a 1-phenylethyl group-substituted naphthalene ring group. Here, the benzene ring group is a group generated by removing 4 H from the benzene ring, the naphthalene ring group is a group generated by removing 4 H from the naphthalene ring, and the position of removing H is not limited.

Z is a phosphorus-containing group represented by the above formula (a).
In the formula (a), R ¹ and R ² each represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero element, each of which may be different or the same, linear, branched, It may be annular. Further, R ¹ and R ² may be bonded to form a cyclic structure. In particular, an aromatic ring group such as a benzene ring is preferable. When R ¹ and R ² are aromatic ring groups, the substituent is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 10 carbon atoms. An aryl group having 7 to 11 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an aralkyloxy group having 7 to 11 carbon atoms. Examples of the hetero element include an oxygen element and the like, which can be contained between carbons constituting a hydrocarbon chain or a hydrocarbon ring.

  n1 and n2 are 0 or 1, and are independent of each other.

The phosphorus-containing group represented by the above formula (a) is preferably the one represented by the above formula (b1) or (b2).
In the formulas (b1) and (b2), R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 11 carbon atoms, specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group, A phenyl group, a tolyl group, and a benzyl group are mentioned, A methyl group, a phenyl group, and a benzyl group are preferable. m1 is an integer of 0-4 each independently, 0-2 are preferable and 0 or 1 is more preferable. m2 is each independently an integer of 0 to 5, preferably 0 to 2, and more preferably 0 or 1.

  Other preferable examples of the phosphorus-containing group represented by the formula (a) include phosphorus-containing groups represented by the following formulas (a1) to (a10).

  The organic phosphorus compound production method of the present invention is used in an amount of 0.5 mol or more and less than 1.0 mol of the quinone compound with respect to 1 mol of the organic phosphorus compound represented by the formula (2). It has the process 1 made to react at 100-200 degreeC in the organic solvent in which the water | moisture content of 0.05-0.5 mol existed with respect to mol. This reaction is preferably carried out under reflux conditions. In this reaction, a reaction represented by the following reaction formula (3) is performed.

  After the above step 1 is completed, the reaction mixture is then mixed with a good solvent to dissolve the target organic phosphorus compound, and the by-product phosphorus compound (3) and phosphorus compound (4) are insoluble. Remove as an ingredient. Most of the organophosphorus compound (1), which is the target product, is present in the solution after separation of the solid content, but a slight amount of by-product phosphorus compound (3) and phosphorus compound (4) remain, so the process Subsequent to 3 further purification.

  In step 3, the solution is mixed with a poor solvent to precipitate crystals of the organophosphorus compound (1) that is the target product. The by-product phosphorus compounds are dissolved in the poor solvent solution.

An example of the reaction formula of step 1 is shown below.
The following reaction formula (3) is a reaction example of the phosphorus compound (2) and the quinone compound (q). In this reaction example, in addition to the organic phosphorus compound (1) of the present invention, by-product phosphorus compound (3) and phosphorus compound (4) are by-produced, and further, raw material phosphorus compound (2) remains as an impurity. is there.

ここで、［Ａｒ］は下記反応式（４）が成立する芳香族環基である。

Here, [Ar] is an aromatic ring group that satisfies the following reaction formula (4).

  In the present specification, in the formulas (1) to (4), (1 ′), (a), (b1), (b2), (2a) and (2b), common symbols are synonymous unless otherwise specified. It is. Therefore, Ar and Z in the above formulas (3) to (4) are synonymous with Ar and Z in formula (1).

  Regarding the above reaction formula (3), an example using DOPO (2-2) and NQ (q) as specific compounds is represented by the following reaction formula (3-1).

  For example, when the quinone compound is BQ, there are three types of organophosphorus compounds represented by the formula (1). In the case of NQ, there are nine types, but an organophosphorus compound represented by the following formula (1 ') is preferred.

  In the reaction represented by the reaction formula (3), a competitive reaction occurs between the organophosphorus compound (1) of the present invention and the by-product phosphorus compounds (3) and (4). In order to increase the yield of the organic phosphorus compound, it is preferable to increase the molar ratio of the quinone compound (q) to the phosphorus compound (2). The quinone compound is in the range of 0.5 mol or more and less than 1.0 mol, preferably 0.75 mol or more and less than 1.0 mol, more preferably 0.8 mol or more and 1. mol with respect to 1 mol of the phosphorus compound. The amount is less than 0 mol, more preferably 0.9 mol or more and less than 1.0 mol. When the molar ratio is low, the residual amount of unreacted phosphorus compound is increased and the reaction efficiency is deteriorated. On the other hand, when the molar ratio is 1.0 or more, it is effective for the production of the organophosphorus compound of the present invention, but on the other hand, unreacted raw material quinone compound tends to remain and is a complicated treatment step for removing after the reaction. Is essential and industrially disadvantageous.

  In addition to the above molar ratio, the reaction temperature affects the formation of the organophosphorus compound. The reaction temperature is preferably 100 to 200 ° C., and more preferably azeotropic with water at that temperature. Therefore, it is preferable to use an organic solvent capable of maintaining the reflux temperature at 100 to 200 ° C. Since the reflux temperature is lowered by moisture, the boiling point is preferably increased, more preferably 100 to 220 ° C, and still more preferably 110 to 180 ° C. Further, an organic solvent having a low boiling point may be used in combination as long as the reflux temperature can be maintained. The organic solvent is not particularly limited as long as it is a ketone organic solvent reactive with an organic phosphorus compound, but other organic solvents satisfying the above conditions. However, a good solvent that dissolves the raw material and the target organophosphorus compound is preferred.

  Examples of the solvent that can be used include alcohols such as 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, 1,3-butanediol, isopropyl alcohol, and butyl acetate. , Acetate esters such as methoxybutyl acetate, cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, benzyl alcohol acetate, benzoate esters such as methyl benzoate and ethyl benzoate, and methyl Cellosolves such as cellosolve, cellosolve and butylcellosolve, carbitols such as methylcarbitol and butylcarbitol, and dimethoxydiethylene glycol Ethers such as ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylene, N, N-dimethylformamide, N, N-dimethylacetamide Amides such as dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone and the like, but are not limited thereto. These organic solvents may be used alone or in combination of two or more.

  In addition, the amount of water in the reaction system is also important for promoting the formation of the organophosphorus compound (1). It is effective to adjust the water content to a range of 0.05 to 0.5 mol with respect to 1 mol of the raw material phosphorus compound. The factors that promote the formation of this organophosphorus compound are currently unknown, but the reaction mechanism is the affinity for water when the phosphorus compound reacts and bonds to the carbon adjacent to the C = O group of the quinone compound. It is presumed that an addition reaction occurs almost simultaneously by partial hydrogen bonding between two molecules of a good phosphorus compound. The water content relative to 1 mol of the raw material phosphorus compound is more preferably 0.1 to 0.5 mol, and still more preferably 0.2 to 0.4 mol.

  In addition, the quinone compound used in the production method of the present invention can be used without any problem as long as the purity is 90% or more as an industrial product. If the purity is less than this, a large amount of impurities may be produced as a by-product, which may make it difficult to achieve high purity of the target organophosphorus compound. A preferred purity is 96% or more, and a more preferred purity is 98% or more. These quinone compounds may be sold in advance by a manufacturer in a water-containing state to prevent scattering because of their harmfulness. In this case, the reaction needs to be adjusted in advance in consideration of the amount of water in the quinone compound. These quinone compounds may be used alone or in combination of two or more.

  When Ar in formula (1) becomes a benzene ring as the quinone compound used in the present invention, for example, benzoquinone, methyl-benzoquinone, ethyl-benzoquinone, butyl-benzoquinone, dimethyl-benzoquinone, diethyl-benzoquinone, dibutyl- Examples include, but are not limited to, benzoquinone, methyl-isopropyl-benzoquinone, diethoxy-benzoquinone, methyl-dimethoxy-benzoquinone, methyl-methoxy-benzoquinone, phenyl-benzoquinone, tolyl-benzoquinone, ethoxyphenyl-benzoquinone, and diphenyl-benzoquinone. It is not a thing.

  When Ar in formula (1) is a naphthalene ring, for example, naphthoquinone, methyl-naphthoquinone, cyclohexyl-naphthoquinone, methoxy-naphthoquinone, ethoxy-naphthoquinone, dimethyl-naphthoquinone, dimethyl-isopropyl-naphthoquinone, methyl-methoxy-naphthoquinone However, it is not limited to these.

  In the case where Ar in formula (1) is an anthracene ring, examples include anthraquinone, methyl-anthraquinone, ethyl-anthraquinone, methoxy-anthraquinone, dimethoxy-anthraquinone, diphenoxy-anthraquinone, and the like. Absent.

  When Ar in formula (1) becomes a phenanthrene ring, examples thereof include phenanthrenequinone, methyl-phenanthrenequinone, isopropyl-phenanthrenequinone, methoxy-phenanthrenequinone, butoxy-phenanthrenequinone, and dimethoxy-phenanthrenequinone. It is not limited to.

  Examples of the raw material phosphorus compound used in the above reaction include dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, dibenzylphosphine oxide, cyclooctylenephosphine oxide, tolylphosphine oxide, bis (methoxyphenyl). Phosphine oxide, phenyl phenylphosphinate, ethyl phenylphosphinate, tolyl tolylphosphinate, benzyl benzylphosphinate, DOPO, 8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, 8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-phenyl-9,10-dihydro-9-oxa-10 Phosphaphenanthrene-10-oxide, 2,6,8-tri-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dicyclohexyl-9,10- Examples include dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenyl phosphonate, ditolyl phosphonate, dibenzyl phosphonate, 5,5-dimethyl-1,3,2-dioxaphosphorinane, and the like. However, it is not limited to these. These phosphorus compounds may be used alone or in combination of two or more.

  After completion of the reaction, the reaction solution is filtered into an organic solvent and a product, and then subjected to the above step 2 in order to reduce by-products from the product. In step 2, it is preferable to mix and dissolve the reaction mixture with a good solvent and then remove insoluble by-products by filtration or the like. Examples of the good solvent include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, cyclohexanone, benzyl alcohol, acetate ester, and benzoate ester. These solvents may be used alone or in combination of two or more. Of these solvents, acetate esters are preferred, and benzyl acetate is more preferred.

  Thereafter, in order to obtain the organophosphorus compound of the present invention with high purity from the solution, it is subjected to the above step 3. In step 3, it is preferable to obtain a product by precipitation separation by mixing with a poor solvent. Examples of the poor solvent include, but are not limited to, methanol, ethanol, butanol, and acetone. These solvents may be used alone or in combination of two or more. Of these solvents, methanol, ethanol, and acetone are preferable, and methanol and ethanol are more preferable. These solvents may be water-containing products. In this case, water may contain up to 100 parts by mass with respect to 100 parts by mass of the solvent.

  In addition, as other purification methods, purification operations such as extraction, washing, and distillation can be performed.

  Examples of the preferred organophosphorus compound represented by the above formula (1) thus obtained include organophosphorus compounds represented by the following formulas (1-1) to (1-4).

Next, the curable resin composition of the present invention will be described.
The curable resin composition of the present invention contains the organophosphorus compound of the present invention and a thermosetting resin.

  Examples of the thermosetting resin include phenol resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, diallyl phthalate resins, thermosetting polyimide resins, and epoxy resin compositions containing an epoxy resin and a curing agent. An epoxy resin composition is preferable.

  Although it does not specifically limit as a compounding composition of a curable resin composition, The organic phosphorus compound of this invention is 0.1-100 mass parts normally with respect to 100 mass parts of thermosetting resins, 50 mass parts is preferable and 5-30 mass parts is more preferable. Moreover, it is preferable to use together the inorganic filler and phosphorus flame retardant which are mentioned later in this composition. In view of flame retardancy, it is preferable to determine the blending by the phosphorus content rather than managing by the blending amount of the organophosphorus compound.

  As the epoxy resin contained in the epoxy resin composition, it is preferable to use one having 2 or more, preferably 3 or more epoxy groups in the molecule. Specific examples include, but are not limited to, polyglycidyl ether compounds, polyglycidyl amine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone, or two or more of the same type of epoxy resins may be used in combination, or different types of epoxy resins may be used in combination. Among these epoxy resins, phenol novolac type epoxy resins are particularly preferred because of their excellent versatility from the viewpoints of cost, heat resistance, flame retardancy, and other characteristics.

  Specific examples of polyglycidyl ether compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, tetramethylbisphenol F type epoxy resins, biphenol type epoxy resins, hydroquinone type epoxy resins, bisphenol fluorene type epoxy resins, and naphthalenediol. Type epoxy resin, bisphenol S type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, resorcinol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, styrenated phenol novolak type epoxy Resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, β-naphthol alla Kill type epoxy resin, naphthalene diol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, biphenyl aralkyl phenol type epoxy resin, trihydroxyphenyl methane type epoxy resin, tetrahydroxyphenyl ethane type epoxy resin, dicyclopentadiene type epoxy resin, Examples include, but are not limited to, alkylene glycol type epoxy resins and aliphatic cyclic epoxy resins.

  Specific examples of the polyglycidylamine compound include diaminodiphenylmethane type epoxy resin, metaxylenediamine type epoxy resin, 1,3-bisaminomethylcyclohexane type epoxy resin, isocyanurate type epoxy resin, aniline type epoxy resin, hydantoin type Examples thereof include, but are not limited to, epoxy resins and aminophenol type epoxy resins.

  Specific examples of the polyglycidyl ester compound include, but are not limited to, a dimer acid type epoxy resin, a hexahydrophthalic acid type epoxy resin, and a trimellitic acid type epoxy resin.

  Examples of the alicyclic epoxy compound include, but are not limited to, aliphatic cyclic epoxy resins such as Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.).

  Specific examples of other modified epoxy resins include urethane-modified epoxy resins, oxazolidone ring-containing epoxy resins, epoxy-modified polybutadiene rubber derivatives, CTBN-modified epoxy resins, polyvinylarene polyoxides (for example, divinylbenzene dioxide, trivinylnaphthalenetri). Oxides), phosphorus-containing epoxy resins, and the like, but are not limited thereto.

  The curing agent is not particularly limited as long as it cures an epoxy resin. A phenolic curing agent, an acid anhydride curing agent, an amine curing agent, a hydrazide curing agent, an active ester curing agent, and a phosphorus-containing curing. A curing agent such as an agent can be used. These curing agents may be used alone, or two or more of the same type of curing agents may be used in combination, or different types of curing agents may be used in combination. Of these, dicyandiamide and phenolic curing agents are preferred.

  In the epoxy resin composition, the use amount of the curing agent is such that the active hydrogen group of the curing agent is 0.2 to 1.5 mol with respect to 1 mol of the epoxy group of the epoxy resin. When the active hydrogen group is less than 0.2 mol or exceeds 1.5 mol with respect to 1 mol of the epoxy group, curing may be incomplete and good cured properties may not be obtained. A preferable range is 0.3 to 1.5 mol, a more preferable range is 0.5 to 1.5 mol, and a further preferable range is 0.8 to 1.2 mol. For example, when a phenolic curing agent, an amine curing agent or an active ester curing agent is used, an active hydrogen group is blended in an approximately equimolar amount with respect to an epoxy group, and when an acid anhydride curing agent is used, an epoxy group An acid anhydride group is added in an amount of 0.5 to 1.2 mol, preferably 0.6 to 1.0 mol, per mol.

The active hydrogen group in this specification is a functional group having an active hydrogen reactive with an epoxy group (a functional group having a latent active hydrogen that generates active hydrogen by hydrolysis or the like, or a functional group having an equivalent curing action) Specifically, an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group, and the like can be given. Regarding the active hydrogen group, a carboxyl group (-COOH) or a phenolic hydroxyl group (-OH) is one mole, an amino group (-NH ₂₎ is calculated to 2 moles. If the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, by reacting a monoepoxy resin with known epoxy equivalent such as phenylglycidyl ether with a curing agent with unknown active hydrogen equivalent, and measuring the amount of monoepoxy resin consumed, the active hydrogen equivalent of the used curing agent Can be requested. In the present specification, the unit of each equivalent is “g / eq.”.

  As a phenol type hardening | curing agent, the polyfunctional phenol compound which can be used as said various epoxy resin modifier is mentioned.

  Among these phenolic curing agents, those containing a large amount of aromatic skeleton in the molecular structure are particularly preferable. For example, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin Naphthol novolak resin, naphthol-phenol co-condensation novolak resin, naphthol-cresol co-condensation novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, and aminotriazine-modified phenol resin.

  Further, a benzoxazine compound that is ring-opened upon heating to become a phenol compound is also useful as a curing agent. Specific examples include, but are not limited to, bisphenol F-type or bisphenol S-type benzoxazine compounds.

  Specific examples of the acid anhydride curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, and hydrogenated trimellit. Acid anhydride, methyl nadic anhydride, succinic anhydride, maleic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-biphthalic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride Product, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2, , 4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, and the like but not limited thereto.

  Examples of the amine curing agent include amine compounds that can be used as the above various epoxy resin modifiers. Other amine compounds such as 2,4,6-tris (dimethylaminomethyl) phenol, dimeramine, dicyandiamide and derivatives thereof, and polyamidoamines that are condensates of acids such as dimer acid and polyamines However, it is not limited to these.

  Specific examples of the hydrazide-based curing agent include, but are not limited to, adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and the like.

  Examples of the active ester curing agent include a reaction product of a polyfunctional phenol compound and an aromatic carboxylic acid as described in Japanese Patent No. 5152445, and commercially available products include Epicron HPC-8000-65T (DIC Corporation). However, it is not limited to these.

  Specific examples of other curing agents include phosphine compounds such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, n-butyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, and ethyltriphenylphosphonium. Phosphonium salts such as iodide, tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, etc. Imidazoles, imidazole salts that are salts of imidazoles with trimellitic acid, isocyanuric acid, boric acid, etc., tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium Hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide Quaternary ammonium salts such as benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride, diazabicyclo compounds, salts of diazabicyclo compounds and phenol compounds, boron trifluoride and amines or ether compounds, etc. And complex compounds with Although iodonium salts, and the like are not limited thereto.

  A hardening accelerator can be used for the curable resin composition as needed. Examples of the curing accelerator include, but are not limited to, organic phosphorus compounds such as imidazole derivatives, tertiary amines, and phosphines, metal compounds, Lewis acids, amine complex salts, and the like. These curing accelerators may be used alone or in combination of two or more.

  The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton. For example, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4- Alkyl-substituted imidazole compounds such as dimethylimidazole and 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1- Aryl groups such as benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2′-cyanoethyl) imidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole Contains ring structures such as aralkyl groups That imidazole compounds substituted with a hydrocarbon group, and the like, but is not limited thereto.

  Examples of tertiary amines include 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo [5.4.0] -7-undecene ( DBU) and the like, but are not limited thereto.

  Examples of phosphines include, but are not limited to, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, and the like.

  Examples of the metal compound include, but are not limited to, tin octylate.

  Examples of amine complex salts include boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenylamine complex, boron trifluoride benzylamine complex, and boron trifluoride. Examples thereof include, but are not limited to, boron trifluoride complexes such as aniline complexes or mixtures thereof.

  Among these curing accelerators, when used as a build-up material application or a circuit board application, 2-dimethylaminopyridine, 4-dimethylaminopyridine, and the like have excellent heat resistance, dielectric properties, solder resistance, and the like. Imidazoles are preferred. Moreover, when using as a semiconductor sealing material use, a triphenylphosphine and DBU are preferable from the point which is excellent in sclerosis | hardenability, heat resistance, an electrical property, moisture-resistant reliability, etc.

  The blending amount of the curing accelerator may be appropriately selected according to the purpose of use, but 0.01 to 15 parts by mass is used as necessary with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition. The Preferably it is 0.01-10 mass parts, More preferably, it is 0.05-8 mass parts, More preferably, it is 0.1-5 mass parts. By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

  For the purpose of improving the flame retardancy of the resulting cured product, various non-halogen flame retardants that do not substantially contain halogen can be used in combination with the curable resin composition as long as the reliability is not lowered. Examples of the non-halogen flame retardant that can be used include organic phosphorus compounds other than the present invention (phosphorus flame retardant), nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. It is done. These non-halogen flame retardants are not limited in use, and may be used alone or in combination with a plurality of flame retardants of the same system or in combination with flame retardants of different systems. It is also possible to do.

  As the phosphorus flame retardant, any of inorganic phosphorus compounds and organic phosphorus compounds can be used in combination. Examples of inorganic phosphorus compounds include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and nitrogen-containing inorganic phosphorus compounds such as phosphate amides. However, it is not limited to these.

  Further, red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis and the like, and examples of the surface treatment method include (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, hydroxide A method of coating with an inorganic compound such as titanium, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof, (2) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and phenol (3) Thermosetting resin such as phenol resin on a film of inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc. However, it is not limited to these methods.

  Examples of organic phosphorus compounds other than the present invention include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, condensed phosphate esters, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, and nitrogen-containing organic compounds. In addition to phosphorus compounds, phosphinic acid metal salts, etc., organic phosphorus compounds having active hydrogen groups directly linked to phosphorus elements (for example, DOPO, diphenylphosphine oxide, etc.) and phosphorus-containing phenol compounds (for example, DOPO-HQ, 10- (2,7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO-NQ), diphenylphosphinylhydroquinone, diphenylphosphenyl-1,4-dioxy Naphthalene, 1,4-cyclooctylenephosphinyl- , 4-phenyldiol, 1,5-cyclooctylenephosphinyl-1,4-phenyldiol, etc.), and these organic phosphorus compounds are reacted with compounds such as epoxy resins and phenol resins. However, it is not limited to these.

  When the phosphorus flame retardant is a phosphorus-containing epoxy resin or a phosphorus-containing curing agent that also serves as an epoxy resin or a curing agent, the reactive organic phosphorus compound used for them is the same as the organic phosphorus compound of the present invention. A divalent phosphorus compound (3) having a phosphorus-containing group represented by the formula (a) and a phosphorus compound used as a raw material are preferable.

  Examples of the phosphorus-containing epoxy resin that can be used in combination include, but are not limited to, Epototo FX-305, FX-289B, TX-1320A, TX-1328 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like. .

  The epoxy equivalent of the phosphorus containing epoxy resin which can be used becomes like this. Preferably it is 200-800, More preferably, it is 300-780, More preferably, it is 400-760. A phosphorus content rate becomes like this. Preferably it is 0.5-8 mass%, More preferably, it is 1-6 mass%, More preferably, it is 2-3.5 mass%.

  As a phosphorus containing hardening | curing agent, it has a phosphorus containing group represented by Formula (a) with a manufacturing method as shown to a special table 2008-501063 gazette and patent 4548547 gazette other than the said organic phosphorus type compound. A phosphorus compound can be obtained by reacting a phosphorus compound with an aldehyde and a phenol compound. In this case, the phosphorus compound having a phosphorus-containing group represented by the formula (a) is incorporated into the molecule by condensation addition to the aromatic ring of the phenol compound via an aldehyde. Further, in the production method as shown in JP2013-185002A, by reacting an aromatic carboxylic acid, a phosphorus compound-containing activity is obtained from a phosphorus compound phenol compound having a phosphorus-containing group represented by the formula (a). An ester compound can be obtained. Further, a phosphorus-containing benzoxazine compound having a phosphorus-containing group represented by the formula (a) can be obtained by a production method as shown in WO2008 / 010429.

  The compounding amount of the phosphorus flame retardant used in combination is appropriately selected depending on the type and phosphorus content of the phosphorus flame retardant, the components of the curable resin composition, and the desired degree of flame retardancy. In the case where the phosphorus-based flame retardant is a reactive organic phosphorus compound, that is, a raw material phosphorus compound, a by-product phosphorus compound (3), (4), a phosphorus-containing epoxy resin or a phosphorus-containing curing agent, an epoxy resin, a curing agent, The phosphorus content is preferably 0.2 to 6% by mass or less with respect to the solid content (nonvolatile content) in the curable resin composition containing all of the flame retardant and other fillers and additives. 4-4 mass% or less is more preferable, 0.5-3.5 mass% or less is still more preferable, and 0.6-3.3 mass% or less is still more preferable. If the phosphorus content is low, it may be difficult to ensure flame retardancy, and if it is too high, the heat resistance may be adversely affected. The phosphorus content in the curable resin composition referred to here includes not only the phosphorus content of the phosphorus-based flame retardant that can be used in combination, but also the phosphorus content of the organic phosphorus compound (1) of the present invention.

  The compounding amount when the phosphorus flame retardant used in combination is an additive system is in the range of 0.1 to 2 parts by mass when using red phosphorus in 100 parts by mass of the solid content (nonvolatile content) in the curable resin composition. In the case of using an organophosphorus compound, it is preferably blended in the range of 0.1 to 10 parts by mass, particularly preferably in the range of 0.5 to 6 parts by mass. .

  In the present invention, for example, hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, calcium carbonate, zinc molybdate and the like may be used in combination with the curable resin composition as a flame retardant aid.

  In the present invention, the flame retardant used in combination is preferably a phosphorus-based flame retardant, but the flame retardant described below can also be used in combination.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable. The compounding amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, in the epoxy resin composition It is preferable to mix | blend in the range of 0.05-10 mass parts in 100 mass parts of solid content (nonvolatile content), and it is preferable to mix | blend especially in the range of 0.1-5 mass parts. Moreover, when using a nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon element. Examples thereof include, but are not limited to, silicone oil, silicone rubber, and silicone resin. The compounding amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, in the epoxy resin composition It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the solid content (nonvolatile content). Moreover, when using a silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include, but are not limited to, metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. The amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, a curing agent, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the solid content (non-volatile content) in the epoxy resin composition containing all of the flame retardant and other fillers and additives, especially 0. It is preferable to mix | blend in 5-15 mass parts.

  Examples of the organometallic salt flame retardant include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonate metal salt, metal element and aromatic compound or heterocyclic compound. Examples of such compounds include, but are not limited to, compounds having a coordinate bond. The amount of the organic metal salt flame retardant is appropriately selected according to the type of the organic metal salt flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to blend in the range of 0.005 to 10 parts by mass in 100 parts by mass of the solid content (non-volatile content) of the epoxy resin composition containing all of the curing agent, flame retardant, and other fillers and additives. .

  In the curable resin composition, an organic solvent or a reactive diluent can be used for viscosity adjustment.

  Examples of the organic solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and ethers such as ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether. , Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl diglycol , Alcohol such as pine oil, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate Acetic esters such as ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and benzyl alcohol acetate; benzoic acid esters such as methyl benzoate and ethyl benzoate; and cellosolves such as methyl cellosolve, cellosolve, and butylcellosolve And carbitols such as methyl carbitol, carbitol, and butyl carbitol, aromatic hydrocarbons such as benzene, toluene, and xylene, dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone, and the like. Is not to be done.

  Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and tolyl glycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like. Bifunctional glycidyl ethers such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane Polyglycidyl ether, trimethylolethane polyglycidyl ether, pentaerythritol polyglycidyl ether Of or polyfunctional glycidyl ethers, and glycidyl esters such as neodecanoic acid glycidyl ester, phenyl diglycidyl amine, although glycidyl amines such as tolyl diglycidyl amines are not limited thereto.

  These organic solvents or reactive diluents are preferably used alone or in a mixture of a plurality of types at 90% by mass or less as a non-volatile content, and appropriate types and amounts used are appropriately selected depending on the application. For example, in a printed wiring board application, a polar solvent having a boiling point of 160 ° C. or less such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol is preferable, and the amount used is preferably 40 to 80% by mass in terms of nonvolatile content. For adhesive film applications, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the amount used is non-volatile. 30 to 60% by mass is preferable.

  In the curable resin composition, if necessary, fillers, thermoplastic resins, silane coupling agents, antioxidants, mold release agents, antifoaming agents, emulsifiers, thixotropic additions, as long as properties are not impaired. Other additives such as an agent, a smoothing agent, and a pigment can be blended.

  Examples of the filler include fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, Inorganic fillers such as zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester Examples thereof include fibrous fillers such as fibers, cellulose fibers, aramid fibers, and ceramic fibers, organic rubber components such as styrene-butadiene copolymer rubber, butadiene rubber, butyl rubber, and butadiene-acrylonitrile copolymer rubber, and fine particle rubber. Among these, those that are not decomposed or dissolved by an oxidizing compound such as an aqueous permanganate solution used for the surface roughening treatment of the cured product are preferable, and fused silica and crystalline silica are particularly preferable because fine particles are easily obtained. Further, when the blending amount of the filler is particularly increased, it is preferable to use fused silica. The fused silica can be used in either crushed or spherical shape, but in order to suppress the increase in the melt viscosity of the molding material while increasing the blending amount of the fused silica, it is more preferable to mainly use the spherical one. . In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filler may be treated with a silane coupling agent or an organic acid such as stearic acid. In general, the reason for using the filler includes the effect of improving the impact resistance of the cured product and the low linear expansion of the cured product. Moreover, when metal hydroxides, such as aluminum hydroxide, boehmite, and magnesium hydroxide, are used, there exists an effect which acts as a flame retardant adjuvant and improves a flame retardance. When used for applications such as conductive paste, conductive fillers such as silver powder and copper powder can be used.

  A larger amount of the filler is preferable in consideration of the low linear expansion of the cured product and flame retardancy. 1-90 mass% is preferable with respect to solid content (nonvolatile content) in an epoxy resin composition, 5-80 mass% is more preferable, and 10-60 mass% is still more preferable. If the blending amount is too large, the adhesiveness required for the laminate application may be lowered, and further, the cured product may be brittle and sufficient mechanical properties may not be obtained. Moreover, when there are few compounding quantities, there exists a possibility that the compounding effect of a filler, such as an improvement of the impact resistance of hardened | cured material, may not be obtained.

  Moreover, 0.05-1.5 micrometers is preferable and, as for the average particle diameter of an inorganic filler, 0.1-1 micrometer is more preferable. If the average particle diameter of the inorganic filler is within this range, the fluidity of the epoxy resin composition can be kept good. The average particle diameter can be measured with a particle size distribution measuring device.

  Mixing the thermoplastic resin is particularly effective when the epoxy resin composition is molded into a sheet or film. Examples of the thermoplastic resin include phenoxy resin, polyurethane resin, polyester resin, polyolefin resin (polyethylene resin, polypropylene resin, etc.), polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer. (AS resin), vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, polyether Imide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether sulfone resin, polysulfone resin, polyether ether ketone resin, polyphenyle Sulfide resin, polyvinyl formal resins are not limited thereto. Phenoxy resins are preferable from the viewpoint of compatibility with epoxy resins, and polyphenylene ether resins and modified polyphenylene ether resins are preferable from the viewpoint of low dielectric properties.

  Other additives include, for example, organic pigments such as quinacridone, azo, and phthalocyanine, inorganic pigments such as titanium oxide, metal foil pigments, and rust preventive pigments, hindered amines, benzotriazoles, benzophenones, etc. UV absorbers, hindered phenol-based, phosphorus-based, sulfur-based, hydrazide-based antioxidants, silane-based, titanium-based coupling agents, stearic acid, palmitic acid, zinc stearate, calcium stearate And other additives such as mold release agents, leveling agents, rheology control agents, pigment dispersants, repellency inhibitors, antifoaming agents, and the like. The blending amount of these other additives is preferably in the range of 0.01 to 20% by mass with respect to the solid content (nonvolatile content) in the epoxy resin composition.

  The cured product of the present invention can be obtained by curing the curable resin composition of the present invention in the same manner as known epoxy resin compositions. As a method for obtaining a cured product, a method similar to a known curable resin composition can be used, such as casting, pouring, potting, dipping, drip coating, transfer molding, compression molding, resin sheets, A method of forming a laminated board by laminating it in the form of a resin-coated copper foil, a prepreg or the like and curing it by heating and pressing is suitably used. The curing temperature at that time is usually in the range of 100 to 300 ° C., and the curing time is usually about 10 minutes to 5 hours.

  The curable resin composition of the present invention can be obtained by uniformly mixing the above components. An epoxy resin composition containing an epoxy resin, a curing agent, and, if necessary, various additives can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, molded products, adhesive layers, insulating layers, and films.

  Applications for which the curable resin composition, particularly the epoxy resin composition is used include circuit board materials, sealing materials, casting materials, conductive pastes, adhesives, and the like. Circuit board materials include prepregs, resin sheets, resin-coated metal foils, resin compositions for printed wiring boards and flexible wiring boards, insulating materials for circuit boards such as interlayer insulation materials for build-up boards, and adhesion for build-ups. Examples include films and resist inks.

Among these various applications, in printed circuit board materials, circuit board insulating materials, and build-up adhesive film applications, passive components such as capacitors and active components such as IC chips are embedded in the substrate. Can be used as an insulating material.
Among these, circuit boards such as printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulation materials for build-up boards, etc. due to characteristics such as high flame resistance, high heat resistance, low dielectric properties, and solvent solubility ( It is preferable to use it as a material for a laminate and a semiconductor sealing material.

  When the epoxy resin composition is in the form of a plate such as a laminated board, the filler used is preferably a fibrous material in terms of its dimensional stability, bending strength, etc., glass cloth, glass mat, glass roving cloth Is more preferable.

  A prepreg used for a printed wiring board or the like can be prepared by impregnating a curable resin composition into a fibrous reinforcing substrate. As the fibrous reinforcing base material, inorganic fibers such as glass, and woven or non-woven fabrics of organic fibers such as polyester resins, polyamine resins, polyacrylic resins, polyimide resins, and aromatic polyamide resins can be used. It is not limited to.

  The method for producing the prepreg from the curable resin composition is not particularly limited. For example, the varnish-like epoxy resin composition containing the organic solvent is further adjusted to an appropriate viscosity by further blending the organic solvent. It is obtained by making a resin varnish and impregnating the fibrous varnish with the resin varnish, followed by drying by heating and semi-curing (B-stage) the resin component. The heating temperature is preferably 50 to 200 ° C, more preferably 100 to 170 ° C, depending on the type of organic solvent used. The heating time is adjusted according to the type of the organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes. At this time, the mass ratio of the epoxy resin composition to be used and the reinforcing substrate is not particularly limited, but it is usually preferable to adjust the resin content in the prepreg to be 20 to 80% by mass.

  The curable resin composition of the present invention can be used in the form of a sheet or film. In this case, it is possible to form a sheet or a film using a conventionally known method.

The method for producing the resin sheet is not particularly limited. For example, the resin varnish is applied to the support base film that does not dissolve in the resin varnish using a coating machine such as a reverse roll coater, a comma coater, or a die coater. After coating, the resin component is obtained by heating and drying to make a B-stage. If necessary, another support base film is stacked on the coated surface (adhesive layer) as a protective film and dried to obtain an adhesive sheet having release layers on both sides of the adhesive layer.
Examples of the supporting base film include metal foil such as copper foil, polyolefin film such as polyethylene film and polypropylene film, polyester film such as polyethylene terephthalate film, polycarbonate film, silicon film, and polyimide film. A polyethylene terephthalate film that is free from defects, has excellent dimensional accuracy, and is excellent in cost is preferable. Moreover, a metal foil, particularly a copper foil, that facilitates multilayering of the laminate is preferred. The thickness of the support base film is not particularly limited, but is preferably 10 to 150 μm and more preferably 25 to 50 μm because it has strength as a support and hardly causes poor lamination.

Although the thickness of a protective film is not specifically limited, 5-50 micrometers is common. In addition, in order to peel easily the shape | molded adhesive sheet, it is preferable to surface-treat with a mold release agent previously.
Moreover, the thickness after apply | coating a resin varnish is 5-200 micrometers in thickness after drying, and 5-100 micrometers is more preferable.
The heating temperature is preferably 50 to 200 ° C, more preferably 100 to 170 ° C, depending on the type of organic solvent used. The heating time is adjusted according to the type of the organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes.

  The resin sheet thus obtained usually becomes an insulating adhesive sheet having insulating properties, but the conductive adhesive sheet is obtained by mixing conductive metal or metal-coated fine particles with the epoxy resin composition. It can also be obtained. The support base film is peeled off after being laminated on the circuit board or after being heat-cured to form an insulating layer. If the support base film is peeled after the adhesive sheet is heat-cured, adhesion of dust and the like in the curing process can be prevented. Here, the insulating adhesive sheet is also an insulating sheet.

  The resin-coated metal foil obtained from the curable resin composition will be described. As the metal foil, copper, aluminum, brass, nickel or the like alone, alloy, or composite metal foil can be used. It is preferable to use a metal foil having a thickness of 9 to 70 μm. The method for producing the flame retardant resin composition comprising the organophosphorus compound of the present invention and the metal foil with resin from the metal foil is not particularly limited. For example, the organophosphorus compound is provided on one surface of the metal foil. The resin varnish whose viscosity is adjusted with a solvent is applied using a roll coater or the like, and then dried by heating to semi-cure the resin component (B-stage) to form a resin layer. In semi-curing the resin component, for example, it can be dried by heating at 100 to 200 ° C. for 1 to 40 minutes. Here, as for the thickness of the resin part of metal foil with resin, it is desirable to form in 5-110 micrometers.

  Moreover, in order to harden a prepreg or an insulation adhesive sheet, the hardening method of a laminated board when manufacturing a printed wiring board can be generally used, However It is not limited to this. For example, when a prepreg is used to form a laminate, one or a plurality of prepregs are laminated, a metal foil is disposed on one or both sides to form a laminate, and the laminate is heated under pressure. Thus, the prepreg can be cured and integrated to obtain a laminate. Here, as the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel or the like can be used.

  The conditions for heating and pressurizing the laminate may be adjusted as appropriate under the conditions for curing the curable resin composition, and heating and pressing may be performed. However, if the amount of pressurization is too low, bubbles are formed inside the resulting laminate. May remain and electrical characteristics may deteriorate, so it is desirable to apply pressure under conditions that satisfy moldability. The heating temperature is preferably 160 to 250 ° C, and more preferably 170 to 220 ° C. The pressurizing pressure is preferably 0.5 to 10 MPa, and more preferably 1 to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. If the heating temperature is low, the curing reaction may not proceed sufficiently, and if it is high, the cured product may be thermally decomposed. If the pressure is low, air bubbles may remain inside the resulting laminate and the electrical characteristics may deteriorate. If it is high, the resin will flow before curing, and a laminate with the desired thickness cannot be obtained. There is a fear. Further, if the heating and pressing time is short, the curing reaction may not proceed sufficiently, and if it is long, the cured product may be thermally decomposed.

  Furthermore, a multilayer board can be produced using the laminated sheet of metal foil with a single layer resin thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution to perform a blackening process to obtain an inner layer material. The inner layer material is formed with a prepreg, a resin sheet, an insulating adhesive sheet or a resin-attached metal foil on one or both sides of the circuit forming surface, and a conductor layer is formed on the surface of the insulating layer. To form.

  When an insulating layer is formed using a prepreg, a laminate in which one or a plurality of prepregs are laminated on the circuit forming surface of the inner layer material, and a metal foil is further arranged on the outer side thereof. Form. Then, the laminate is heated and pressed and integrally molded, whereby a cured product of the prepreg is formed as an insulating layer, and the outer metal foil is formed as a conductor layer. Here, as a metal foil, the thing similar to what was used for the laminated board used as an inner layer board can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. A printed wiring board can be molded by further forming via holes or circuits by an additive method or a subtractive method on the surface of the multilayer laminate thus molded. Further, by repeating the above method using this printed wiring board as an inner layer material, a multilayer board can be formed.

  For example, when an insulating layer is formed with an insulating adhesive sheet, the insulating adhesive sheet is disposed on the circuit forming surface of the plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is disposed between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressed to be integrally molded, thereby forming a cured product of the insulating adhesive sheet as an insulating layer, and forming a multilayered inner layer material. Alternatively, a cured product of the insulating adhesive sheet is formed as an insulating layer between the inner layer material and the metal foil as the conductor layer. Here, as a metal foil, the thing similar to what was used for the laminated board used as an inner layer material can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.

  Moreover, when apply | coating curable resin composition to a laminated board and forming an insulating layer, after apply | coating curable resin composition to the thickness of preferably 5-100 micrometers, it is 100-200 degreeC, Preferably it is 150- It is heated and dried at 200 ° C. for 1 to 120 minutes, preferably 30 to 90 minutes, to form a sheet. It is generally formed by a method called a casting method. The thickness after drying is 5 to 150 μm, preferably 5 to 80 μm. The viscosity of the curable resin composition is preferably in the range of 10 to 40,000 mPa · s at 25 ° C., more preferably 200 to 30000 mPa · s, because sufficient film thickness is obtained and coating unevenness and streaks are less likely to occur. s. A printed wiring board can be formed by further forming a via hole or a circuit by the additive method or the subtractive method on the surface of the multilayer laminate formed as described above. Further, by repeating the above construction method using this printed wiring board as an inner layer material, a multilayer laminate can be formed.

  Examples of the sealing material obtained by using the curable resin composition of the present invention include tape-shaped semiconductor chips, potting type liquid sealing, underfill, and semiconductor interlayer insulating films. It can be preferably used. For example, as semiconductor package molding, an epoxy resin composition is cast, or molded using a transfer molding machine, an injection molding machine, etc., and further heated at 50 to 200 ° C. for 2 to 10 hours to form a molded product. The method of obtaining is mentioned.

  In order to prepare the curable resin composition for a semiconductor encapsulating material, the epoxy resin composition is blended as necessary, such as a compounding agent such as an inorganic filler, a coupling agent, a release agent, etc. An example is a method in which the additive is premixed and then sufficiently melt-mixed until uniform using an extruder, kneader, roll, or the like. In that case, although silica is normally used as an inorganic filler, in that case, it is preferable to mix | blend an inorganic filler in the ratio used as 70-95 mass% in curable resin composition.

When the curable resin composition thus obtained is used as a tape-shaped encapsulant, this is heated to produce a semi-cured sheet to obtain an encapsulant tape. A method in which a tape is placed on a semiconductor chip, heated to 100 to 150 ° C., softened and molded, and completely cured at 170 to 250 ° C. can be mentioned.
In addition, when used as a potting type liquid sealing material, after dissolving the obtained curable resin composition in a solvent as necessary, it can be applied on a semiconductor chip or electronic component and directly cured. Good.

  Further, the curable resin composition of the present invention can be further used as a resist ink. In this case, a curable resin composition is blended with a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent, and further a pigment, talc, and filler are added to form a resist ink composition. After making it into a product, after applying on a printed board by a screen printing method, a method of forming a resist ink cured product can be mentioned. The curing temperature at this time is preferably in the temperature range of about 20 to 250 ° C.

  As a result of preparing the curable resin composition of the present invention and evaluating the cured product by heat curing, it has better flame retardancy than a cured product obtained from a curable resin composition containing a conventional organic phosphorus compound. . Therefore, since the phosphorus content can be kept low, the heat resistance and water absorption are improved in a laminate having a necessary and sufficient amount of phosphorus, which is useful in a laminate used under more severe conditions.

  Moreover, the organophosphorus compound of this invention can be used as a raw material of the phosphorus containing epoxy resin obtained by reacting with an epoxy resin.

EXAMPLES The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these unless it exceeds the gist. Unless otherwise specified, parts represent parts by mass, and% represents mass%.
The analysis method and measurement method are shown below.

(1) Phosphorus content:
Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample and heated to wet ash to convert all phosphorus elements to orthophosphoric acid. Metavanadate and molybdate were reacted in a sulfuric acid acidic solution, the absorbance at 420 nm of the resulting limpavande molybdate complex was measured, and the phosphorus content determined by a previously prepared calibration curve was expressed in mass%. The phosphorus content of the laminate was expressed as the content relative to the resin content of the laminate. Here, the resin component of the laminated board refers to a component corresponding to an organic component (such as an epoxy resin, a curing agent, and an organic phosphorus compound) excluding a solvent among components blended in the epoxy resin composition.

(2) Copper foil peel strength and interlayer adhesion strength:
According to JIS C6481, 5.7, the measurement was performed in an atmosphere at 25 ° C. The interlayer adhesion was measured by peeling between the seventh and eighth layers.

(3) Glass transition temperature (Tg):
IPC-TM-650 2.4.25. c DSC / Tgm (on the tangent line between glass and rubber) when measured with a differential scanning calorimeter (EXSTA16000 DSC6200, manufactured by Hitachi High-Tech Science Co., Ltd.) at 20 ° C / min. In contrast, the temperature was represented by the temperature of the intermediate temperature of the mutation curve.

(4) Dielectric constant and dielectric loss tangent:
It evaluated by calculating | requiring the dielectric constant and dielectric loss tangent in a frequency of 1 GHz by the capacity | capacitance method using the material analyzer (made by AGILENT Technologies) according to IPC-TM-650 2.5.5.9.

(5) Flame retardancy:
According to the UL94 standard, the vertical method was used for evaluation. Evaluation was described by V-0, V-1, and V-2. In addition, when the test piece was a film form, it described with VTM-0, VTM-1, and VTM-2. However, X was completely burned.

(6) GPC (gel permeation chromatography) measurement:
A main body (manufactured by Tosoh Corporation, HLC-8220GPC) equipped with columns (manufactured by Tosoh Corporation, TSKgel G4000H _XL , TSKgel G3000H _XL , TSKgel G2000H _XL ) in series was used, and the column temperature was 40 ° C. Tetrahydrofuran (THF) was used as the eluent, the flow rate was 1 mL / min, and a differential refractive index detector was used as the detector. As a measurement sample, 50 μL of 0.1 g of sample dissolved in 10 mL of THF and filtered through a microfilter was used. Data processing used GPC-8020 model II version 6.00 made by Tosoh Corporation.

(7) FT-IR:
The transmittance at a wave number of 650 to 4000 cm ⁻¹ was measured by a total reflection measurement method (ATR method) of a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer Precision, Spectrum One FT-IR Spectrometer 1760X).

(8) NMR:
Using a Fourier transform nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., JNM-ECA400), ¹ H liquid measurement was performed at room temperature using THF-d8 as a solvent.

  The abbreviations used in Examples and Comparative Examples are as follows.

[Phosphorus compounds]
DOPO: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (active hydrogen equivalent 216, phosphorus content 14.3%)
DPPO: Diphenylphosphine oxide (active hydrogen equivalent 202, phosphorus content 15.3%)
DOPO-NQ: 10- (2,7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Chemical Co., Ltd., product name: HCA-NQ, hydroxyl equivalent: 187, phosphorus Content 8.2%)
PX-200: Aromatic condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd., product name: PX-200, phosphorus content 9%)

[Quinone compound]
NQ: 1,4-naphthoquinone (reagent, purity 99%)
BQ: Para-benzoquinone (reagent, purity 99%)

[Epoxy resin]
PN-E: phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: Epototo YDPN-638, epoxy equivalent 176)
DCPD-E: dicyclopentadiene / phenol co-condensed epoxy resin (Kunito Chemical Co., Ltd., product name: KDCP-130, epoxy equivalent 254)
BPA-E: bisphenol A type solid epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: Epototo YD-903, epoxy equivalent 812)
OCN-E: Orthocresol novolak type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: Epototo YDCN-700-7, epoxy equivalent 202)

[Curing agent]
PN: phenol novolac resin (manufactured by Showa Denko KK, product name: Shonor BRG-557, softening point 80 ° C., phenolic hydroxyl group equivalent 105)
DICY: Dicyandiamide (Nippon Carbide Industries Co., Ltd., product name: DIHARD, active hydrogen equivalent 21)
DCPD-P: dicyclopentadiene / phenol cocondensation resin (Gunei Chemical Co., Ltd., GDP 9140, phenolic hydroxyl group equivalent 196)

[Curing accelerator]
2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name: Curesol 2E4MZ)

[Others]
YP-50S: bisphenol A type phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: phenototo YP-50S, weight average molecular weight = 40000)
BMB: Alumina monohydrate (manufactured by Kawai Lime Industry Co., Ltd., product name: BMB, average particle size 1.5 μm)

Example 1
In a reactor equipped with a stirrer, thermometer, nitrogen gas introduction device, cooling pipe and water separator, 200 parts of propylene glycol monomethyl ether acetate (PMA), 108 parts of DOPO, and 4.2 parts of water at room temperature. Parts (water / DOPO molar ratio = 0.47) were heated to 70 ° C. under a nitrogen atmosphere and completely dissolved. NQ78.9 parts (NQ / DOPO molar ratio = 0.999) was charged there over 30 minutes. After completion of the preparation, the temperature was raised to 145 ° C. where refluxing started, and the reaction was continued for 5 hours while maintaining the reflux temperature.
The product obtained was cooled to room temperature and filtered off with suction. After 2500 parts of benzyl acetate was added to the filter cake and heated to dissolve completely, it was cooled to room temperature and allowed to stand for 1 day, and the resulting precipitate was separated by suction filtration. The filtrate was poured into 39% water-containing methanol, and the produced precipitate was separated by suction filtration to obtain organophosphorus compound 1 (purity 99% or more) as a filter cake. FIG. 1 shows a GPC chart, FIG. 2 shows an FT-IR chart, and FIG. 3 shows an NMR chart. In addition, according to FIGS. 1-3, the obtained phosphorus compound 1 is represented by the said Formula (1-1).

Example 2
In an apparatus similar to Synthesis Example 1, at room temperature, DOPO was 108 parts, BQ was 53 parts (BQ / DOPO molar ratio = 0.98), and water was 1.8 parts (water / DOPO molar ratio = 0). 20), 200 parts of PMA was charged, the temperature was raised to 145 ° C. at which refluxing started in a nitrogen atmosphere, and the reaction was continued for 3 hours while maintaining the refluxing state.
The product obtained was cooled to room temperature and filtered off with suction. After 2500 parts of benzyl acetate was added to the filter cake and heated to dissolve completely, it was cooled to room temperature and allowed to stand for 1 day, and the resulting precipitate was separated by suction filtration. The filtrate was put into 39% water-containing methanol, and the produced precipitate was separated by suction filtration to obtain organophosphorus compound 2 as a filter cake. The obtained phosphorus compound 2 is represented by the above formula (1-2).

Example 3
In the same apparatus as in Synthesis Example 1, DPPO is 101 parts, NQ is 78 parts (NQ / DPPO molar ratio = 0.99), water is 2.7 parts (water / DPPO molar ratio = 0.30), 200 parts of PMA was charged, the temperature was raised to 145 ° C. at which refluxing began in a nitrogen atmosphere, and the reaction was continued for 3 hours while maintaining the refluxing state.
The product obtained was cooled to room temperature and filtered off with suction. After 2500 parts of benzyl acetate was added to the filter cake and heated to dissolve completely, it was cooled to room temperature and allowed to stand for 1 day, and the resulting precipitate was separated by suction filtration. The filtrate was put into 39% water-containing methanol, and the produced precipitate was separated by suction filtration to obtain organophosphorus compound 3 as a filter cake. The obtained phosphorus compound 3 is represented by the above formula (1-3).

Example 4
25 parts of the organophosphorus compound 1 obtained in Example 1 as a flame retardant, 100 parts of PN-E as an epoxy resin, 6.0 parts of DICY as a curing agent, and 0.1 part of 2E4MZ as a curing accelerator , An epoxy resin varnish having a nonvolatile content of 50%, dissolved in a mixed solvent prepared with methyl ethyl ketone (hereinafter referred to as MEK), propylene glycol monomethyl ether (hereinafter referred to as PGM), and N, N-dimethylformamide (hereinafter referred to as DMF). Got.
The obtained resin varnish was impregnated into a glass cloth (manufactured by Nitto Boseki Co., Ltd., WEA2116, 0.1 mm thickness). The impregnated glass cloth was dried in a hot air circulating oven at 150 ° C. for 10 minutes to obtain a prepreg. Eight prepregs obtained and a copper foil (Mitsui Metal Mining Co., Ltd., 3EC-III, thickness 35 μm) are stacked on top and bottom, the degree of vacuum is 0.5 kPa, the pressing pressure is 2 MPa, and 130 ° C. × 15 minutes + 170 ° C. × 70. A vacuum press was performed under a temperature condition of 1 minute to obtain a 1 mm thick laminate. The copper foil portion of the obtained laminate was removed by immersing in an etching solution, washed and dried, and then cut into a size of 127 mm × 12.7 mm to obtain a flame retardant test piece. Table 1 shows the results of the copper foil peel strength, interlayer adhesion, glass transition temperature (Tg), and flame retardancy of the laminate.

Examples 5-6 and Comparative Examples 1-2
A resin varnish was obtained by the same operation using the same apparatus as in Example 4 with the blending ratio (parts) shown in Table 1, and further a laminate and a flame retardant test specimen were obtained. The same test as in Example 4 was performed and the results are shown in Table 1. In addition, "-" in a table | surface represents non-use.

Examples 7-9 and Comparative Examples 3-5
A resin varnish was obtained by the same operation using the same apparatus as in Example 4 with the blending ratio (parts) shown in Table 2, and further a laminate and a flame retardant test specimen were obtained. The same test as in Example 4 was performed, and the results are shown in Table 2. In addition, “(A) / (B)” in the table represents an equivalent ratio (molar ratio) between the functional groups of the epoxy resin (A) and the curing agent (B). “*” Indicates no measurement.

Example 10
48 parts of the organophosphorus compound 1 obtained in Example 1 as a flame retardant, 97 parts of PN-E as an epoxy resin, 5 parts of DICY as a curing agent, 0.2 part of 2E4MZ as a curing accelerator, other components As a mixture, 100 parts of YP-50S and 50 parts of BMB were blended and dissolved in a mixed solvent prepared with MEK, PGM, and DMF to obtain a resin varnish having a nonvolatile content of 50%.
The obtained resin varnish was applied onto a separator film (polyimide film) using a roll coater and dried in an oven at 130 ° C. for 10 minutes to obtain a resin film having a thickness of 60 μm. The resin film was peeled off from the separator film, and the resin film was further cured in an oven at 200 ° C. for 120 minutes to obtain a cured film. The cured film was cut into a size of 200 mm × 50 mm to obtain a flame retardant test piece. Table 3 shows the Tg and flame retardancy results of the cured film.

Example 11 and Comparative Examples 6-7
Using the same apparatus as in Example 10, the resin varnish was obtained in the same manner using the blending ratio (parts) shown in Table 3, and further a cured film and a flame retardant test specimen were obtained. The same test as in Example 10 was performed and the results are shown in Table 3.

Examples 10 to 11 (Comparative Examples 6 to 7) are examples of cured films. Even in this case, flame retardancy and heat resistance were improved. In addition, the compounding quantity of an epoxy resin (PN-E) makes the compounding quantity with respect to a hardening | curing agent (DICY) the same quantity, and also added the epoxy resin of the quantity equivalent to an equimolar with respect to the functional group of a flame retardant. It was.

Claims (13)

An organophosphorus compound represented by the following formula (1).

(Here, Ar represents an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, and these aromatic ring groups are an alkyl group having 1 to 8 carbon atoms and 1 to 8 carbon atoms. An alkoxy group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an aralkyl having 7 to 11 carbon atoms. (It may have an oxy group as a substituent. Z is a phosphorus-containing group represented by the following formula (a).)

(Here, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero element, and may be linear, branched or cyclic, R ¹ and R ² may combine to form a cyclic structure, and n1 and n2 are each independently 0 or 1.) The organophosphorus compound according to claim 1, wherein Z is a phosphorus-containing group represented by the following formula (b1) and / or (b2).

(Here, R ³ is each independently a hydrocarbon group having 1 to 11 carbon atoms, and m 1 is each independently an integer of 0 to ^4. R ⁴ is each independently a hydrocarbon group having 1 to 11 carbon atoms.) And m2 is each independently an integer of 0 to 5.)   A curable resin composition comprising the organophosphorus compound according to claim 1 and a thermosetting resin.   The curable resin composition according to claim 3, wherein the thermosetting resin contains an epoxy resin and a curing agent.   A circuit board material comprising the curable resin composition according to claim 3.   The sealing material which consists of a curable resin composition of Claim 3 or 4.   A casting material comprising the curable resin composition according to claim 3 or 4.   Hardened | cured material formed by hardening | curing the curable resin composition of Claim 3 or 4. A method for producing an organophosphorus compound according to claim 1 or 2,
For 1 mol of the phosphorus compound represented by the following formula (2),
Step 1, in which 0.5 to 0.5 mol of quinone compound and 0.05 to 0.5 mol of water are present and reacted in an organic solvent at 100 to 200 ° C.,
Step 2 in which the reaction product obtained in Step 1 is dissolved in a good solvent to remove insoluble impurities, and the solution obtained in Step 2 is mixed with a poor solvent to obtain a product by precipitation separation. ,
A process for producing an organophosphorus compound, comprising:

^(Wherein, R ^1, R ^2, n1 and n2 have the same meanings as ^{R 1, R 2,} n1 and n2 of formula (a).)   The production method according to claim 9, wherein the good solvent is one solvent selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, cyclohexanone, benzyl alcohol, acetic acid ester, and benzoic acid ester, or two or more mixed solvents.   The manufacturing method according to claim 9 or 10, wherein the poor solvent is one solvent selected from the group consisting of methanol, ethanol, butanol, and acetone, or a mixed solvent of two or more. The method according to any one of claims 9 to 11, wherein the phosphorus compound is a compound represented by the following formula (2a) and / or (2b).

(Wherein, ^{R 3} and m1 have the same meanings as ^{R 3} and m1 of formula (b1).)

(Wherein, ^{R 4} and m2 have the same meanings as ^{R 4} and m2 of the formula (b2).) The quinone compound is benzoquinone, naphthoquinone, anthraquinone, phenanthrenequinone, methyl-benzoquinone, ethyl-benzoquinone, dimethyl-benzoquinone, methyl-methoxy-benzoquinone, phenyl-benzoquinone, methyl-naphthoquinone, cyclohexyl-naphthoquinone, methoxy-naphthoquinone, methyl-anthraquinone The production method according to any one of claims 9 to 12, which is at least one selected from the group consisting of diphenoxy-anthraquinone and methyl-phenanthrenequinone.

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