Phosphorus-containing polycyclic aromatic hydroxyl compound, curable resin composition containing said phosphorus-containing polycyclic aromatic hydroxyl compound, and method for producing said phosphorus-containing polycyclic aromatic hydroxyl compound

Abstract

Provided is a phosphorus-containing polycyclic aromatic hydroxyl compound which has excellent flame retardancy, heat resistance, and dielectric properties in a cured product, has a low water absorption rate, and has little change in dielectric properties after water absorption. A phosphorus-containing polycyclic aromatic hydroxyl compound characterized by being represented by general formula (1). In general formula (1), m is an integer of 1-20, n1 is each independently an integer of 1-4, and Ar is each independently an optionally substituted C6-30 aromatic ring (excluding a benzene ring). Each R1 independently represents a hydrogen atom, a linear or branched alkyl group having 1-5 carbon atoms, or a substituent represented by general formula (2), but at least one R1 has a structure represented by general formula (2). X represents a linking group, and each independently represents oxygen, sulfur, a substituted or unsubstituted cycloalkylene group having 3-20 carbon atoms, or a substituted or unsubstituted aralkylene group having 8-20 carbon atoms. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a reactive phosphorus compound, in particular to a phosphorus-containing polycyclic aromatic hydroxy compound, which is useful as a flame retardant for thermosetting resins such as epoxy resins. In addition, the present invention also relates to a curable resin composition comprising the phosphorus-containing polycyclic aromatic hydroxy compound and a curable resin, and a method for producing the phosphorus-containing polycyclic aromatic hydroxy compound. Background Art

[0002] Plastic materials are used in a wide range of applications such as building materials and electrical and electronic equipment due to their excellent mechanical properties and molding processability. However, most plastic materials are easily flammable, and therefore, in applications where they are used, such as electrical and electronic products, OA equipment, and communication equipment, flame retardancy is required for safety against heat ignition and fire.

[0003] As a flame retardant technology for plastic materials, the addition of additive flame retardants such as halogen flame retardants, inorganic flame retardants, and phosphorus flame retardants is a common technology, regardless of the type of resin or application. However, among these, halogen flame retardants, mainly bromine-based ones, are pointed out to be highly carcinogenic disulfide. In response to the recent actions to reduce environmental load substances, the use of toxicants is being restricted. In addition, although inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide have a flame retardant effect by absorbing heat, they need to be added in large quantities to achieve sufficient flame retardancy, which causes various properties of plastic molded products to decrease. Therefore, phosphorus flame retardants are mostly used, which do not produce harmful substances and can be flame-retarded with a relatively small amount of addition. However, even so, it is impossible to avoid the effects on properties such as reduced processability caused by bleed-out and reduced glass transition temperature.

[0004] In order to solve the problems of these additive flame retardants, reactive flame retardants containing flame retardant components, namely phosphorus atoms and having reactive groups have been developed and widely used. As a reactive flame retardant that can be applied to epoxy resin compositions that are often used in the electronic and electrical fields, for example, Patent Document 1 discloses a phenolic resin as a curing agent for epoxy resin, wherein the phenolic resin is obtained by reacting bisphenol A with formaldehyde to obtain hydroxymethyl bisphenol A, and then reacting it with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as "DOPO"); Patent Documents 2 and 3 disclose phosphorus-containing phenolic resins obtained by modifying the hydroxyl groups of phenolic varnish resins with diphenyl chlorophosphate. Furthermore, Patent Document 4 discloses phosphorus-containing epoxy resins obtained by reacting DOPO with quinones and then reacting with epoxy resins. In these resins, processing problems such as the bleeding of flame retardants have been solved, and no deterioration of thermal properties such as heat resistance has been observed.

[0005] However, in recent years, in the field of electronic and electrical materials that must have flame retardancy, due to the rapid development of electronic devices represented by smartphones, the properties required of flame retardants are also changing to higher levels. In particular, in the field of information and communication, as the amount of information processing increases, the high frequency of signals continues to develop. In order to reduce transmission losses, flame retardant materials are also strongly required to have low dielectric constants and low dielectric loss tangents. Furthermore, the requirements involve many aspects, such as low moisture absorption and stability of its properties to environmental changes, heat resistance, etc. As a flame retardant that can be used in epoxy resin compositions that show low dielectric properties, patent document 5 discloses that phosphorus-containing active esters introduced with a DOPO skeleton exhibit flame retardancy and low dielectric. It is widely known that epoxy resins and phosphorus-containing curing agents can be given flame retardancy without reducing general properties such as heat resistance by introducing DOPO into the structure in this way, but the DOPO skeleton is easily hydrolyzed, and there is a problem that the hydroxyl groups generated by hydrolysis absorb moisture and the dielectric properties after water absorption change greatly. To address this problem, Patent Document 5 discloses a phosphate ester type phenol compound that has little change in dielectric properties after absorbing water. However, the dielectric properties and heat resistance are insufficient, and there is no flame retardant that meets the high requirements.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent No. 5678109

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 7-292050

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 2002-97260

[0011] Patent Document 4: Japanese Patent No. 5637418

[0012] Patent document 5: WO2021 / 256351 Summary of the invention

[0013] Therefore, the problem to be solved by the present invention is to provide a phosphorus-containing polycyclic aromatic hydroxy compound having excellent flame retardancy, heat resistance, and dielectric properties in a cured product, a low water absorption rate, and a small change in dielectric properties after water absorption, a curable resin composition comprising the above-mentioned phosphorus-containing polycyclic aromatic hydroxy compound and a curable resin, an epoxy resin composition using the above-mentioned phosphorus-containing polycyclic aromatic hydroxy compound as a curing agent, its cured product, and a method for producing the above-mentioned phosphorus-containing polycyclic aromatic hydroxy compound.

[0014] The present inventors have conducted intensive studies on the above-mentioned problems and have found that a phosphorus-containing polycyclic aromatic hydroxy compound having a specific structure has excellent heat resistance and dielectric properties and has little change in dielectric properties after absorbing water, thereby completing the present invention.

[0015] The present invention is a phosphorus-containing polycyclic aromatic hydroxy compound, characterized by being represented by the general formula (1).

[0016]

[0017] In the general formula (1), m is an integer of 1 to 20, n1 is an integer of 1 to 4, and Ar is an aromatic ring (excluding a benzene ring) having 6 to 30 carbon atoms which may have a substituent. 1 are independently hydrogen, a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituent represented by the general formula (2), but at least one R 1 The structure of general formula (2) is included. X represents a linking group, and each X is independently oxygen, sulfur, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, or a substituted or unsubstituted aralkylene group having 8 to 32 carbon atoms.

[0018]

[0019] In the general formula (2), R 2 and R 3 Each of n2 and n3 is independently a linear or branched alkyl group having 1 to 5 carbon atoms, and each of n2 and n3 is independently an integer of 0 to 5.

[0020] The phosphorus-containing polycyclic aromatic hydroxy compound is characterized by being represented by the following general formula (3).

[0021]

[0022] In the general formula (3), R 1 , n1, and m have the same meanings as in the general formula (1). Y is an aromatic ring group having 6 to 30 carbon atoms which may have a substituent. Ar represents a polycyclic aromatic group derived from a polycyclic aromatic compound represented by the following general formula (4), (5), or (6).

[0023]

[0024] In the above general formulae (4), (5) and (6), R4 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and n4 is an integer of 0 to 4. 1 , n1 have the same meanings as in the general formula (1).

[0025] The phosphorus-containing polycyclic aromatic hydroxy compound having a hydroxyl equivalent of 100 to 3000 g / eq and a phosphorus content of 1.5 to 15.0% by mass is preferred.

[0026] The present invention is a method for producing the above-mentioned phosphorus-containing polycyclic aromatic hydroxy compound, characterized in that 0.1 to 0.9 moles of a compound represented by the following general formula (8) are reacted with 1 mole of hydroxyl groups of the polycyclic aromatic hydroxy compound represented by the following general formula (7).

[0027]

[0028] In the general formulas (7) and (8), m, n1, Ar, X, R 2 , R 3 , n2, n3 have the same meanings as in the general formulae (1) and (2). Z represents a halogen atom.

[0029] The present invention provides a curable resin composition comprising the phosphorus-containing polycyclic aromatic hydroxy compound and a curable resin, and a cured product obtained by curing the curable resin composition.

[0030] The phosphorus-containing polycyclic aromatic hydroxy compound of the present invention has little change in dielectric properties after absorbing water, and is very useful as a flame retardant material for reducing transmission loss in electronic devices with increasing frequencies as the amount of information processing increases. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a GPC chart showing the phosphorus-containing polycyclic aromatic hydroxy compound obtained in Example 1. (The dotted line is the raw material, and the solid line is the product) DETAILED DESCRIPTION

[0032] The present invention is described in detail below.

[0033] The phosphorus-containing polycyclic aromatic hydroxy compound of the present invention is represented by the following general formula (1).

[0034]

[0035] In the phosphorus-containing polycyclic aromatic hydroxy compound represented by the general formula (1), m is an integer of 1 to 20, and includes not only a single compound with m=1 but also a mixture with m=2, m=3 or more.

[0036] Ar is independently a substituted or unsubstituted aromatic ring group having 3 to 30 carbon atoms (excluding a benzene ring). The aromatic ring group is not particularly limited and includes furan, pyrrole, thiophene, imidazole, pyrazole, Azoles, Isopropylamine An aromatic ring group obtained by removing one or two hydrogen atoms from a monocyclic aromatic compound such as oxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc.; an aromatic ring group obtained by removing one or two hydrogen atoms from a condensed aromatic compound such as naphthalene, anthracene, phenanthene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. In addition, a plurality of these aromatic compounds may be combined, for example, an aromatic ring group obtained by removing one or two hydrogen atoms from a ring-aggregated aromatic compound such as biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc.

[0037] From the viewpoint of flame retardancy and dielectric properties, condensed ring aromatic compounds such as naphthalene and anthracene and ring-aggregated aromatic compounds such as biphenyl are preferred over monocyclic compounds such as benzene.

[0038] Specifically, Ar is preferably a group selected from one or more of a condensed aromatic compound represented by the following general formula (4) or (6) and a ring-aggregated aromatic compound represented by the following general formula (5). More preferably, Ar is a group derived from a condensed aromatic compound represented by the following general formula (4). 1 are independently hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms, preferably R 1 For hydrogen.

[0039]

[0040] In the above general formulae (4), (5) and (6), R4 represents a substituent on the aromatic ring, and is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. n4 is an integer of 0 to 4.

[0041] The alkyl group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, n-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclononyl. Preferred groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. More preferred groups include methyl and ethyl.

[0042] The alkoxy group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, and nonyloxy groups.

[0043] These substituents may be used alone or in combination of two or more.

[0044] In the general formula (1), R 1 represents hydrogen, a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituent represented by the following general formula (2), and n1 is an integer of 1 to 4. Preferably R 1 is hydrogen or a substituent represented by the following general formula (2).

[0045]

[0046] In the general formula (2), R 2 and R 3 Each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms.

[0047] Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc. Among these, methyl, ethyl, propyl, isopropyl are preferred from the viewpoint of reactivity in production and availability, and methyl is particularly preferred.

[0048] n2 and n3 are each independently an integer of 0 to 5, preferably an integer of 0 to 2. When n2 and n3 are 1 or more, the substitution position of n2 and n3 on the aromatic ring is not limited, but is preferably ortho to oxygen in order to prevent hydrolysis of the phosphate.

[0049] It should be noted that in the general formula (1), at least one R 1 The phosphorus-containing polycyclic aromatic hydroxy compound of the present invention may exhibit flame retardancy by comprising the structure of the general formula (2).

[0050] From the viewpoint of heat resistance and flame retardancy, the phosphorus-containing polycyclic aromatic hydroxy compound of the present invention preferably has R 1 The substituent is a hydrogen atom and the substituent represented by the general formula (2). In addition, since the solubility is improved by partially containing a linear or branched alkyl group having 1 to 5 carbon atoms, it is preferred, but the heat resistance is reduced, so the ratio of the alkyl group is preferably 20 mol% or less relative to the total of hydrogen, the substituent represented by the general formula (2), and the alkyl group. In addition, when the molecular weight distribution is obtained by the repeating unit represented by m, all R 1 The structure of hydrogen, all R 1It is the structure of the substituent shown in the general formula (2), but when m takes the average value, it is necessary to satisfy the following hydroxyl equivalent and phosphorus content. The production method is described in detail below. The phenol compound of the present invention can be obtained by reacting the polycyclic aromatic hydroxy compound shown in the general formula (7) described later with the phosphorus compound shown in the general formula (8). Therefore, the presence rate of the substituent shown in the general formula (2) can be calculated based on the difference between the hydroxyl equivalent of the polycyclic aromatic hydroxy compound shown in the general formula (7) and the hydroxyl equivalent of the phosphorus-containing polycyclic aromatic hydroxy compound shown in the general formula (1). There is no problem as long as the presence rate of the substituent shown in the general formula (2) is not 0 mol%, but if it is low, there is a tendency for insufficient flame retardancy, and if it is high, the heat resistance is insufficient, so it is preferably 10 to 90 mol%, more preferably 25 to 80 mol%, and further preferably 30 to 60 mol%. At this time, by making the hydroxyl equivalent and the phosphorus content within the specified range, a well-balanced performance can be exhibited.

[0051] The hydroxyl equivalent of the phosphorus-containing polycyclic aromatic hydroxy compound is preferably 100 to 3000 g / eq, more preferably 200 to 2000, and further preferably 300 to 1500 g / eq. It should be noted that, from the viewpoint of flame retardancy, the higher the phosphorus content, the more preferred, but the higher the phosphorus content, the higher the viscosity, and the worse the workability, so it is preferably 1.5 to 15.0% by mass, more preferably 2.0 to 13.0% by mass, and further preferably 3.0 to 12.0% by mass.

[0052] In the general formula (1), X represents a linking group. As is clear from the description of the above chemical formula (1), one of the hydrogen atoms of the aromatic ring constituting the above aromatic ring of Ar is bonded to "X". X is independently oxygen, sulfur, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, or an aralkylene group having 8 to 32 carbon atoms.

[0053] The cycloalkylene group is not particularly limited, and examples thereof include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and cycloalkylene groups represented by the following chemical formulas (9) to (12).

[0054]

[0055] The aralkylene group is not particularly limited, and examples thereof include aralkylene groups represented by the following chemical formulas (13) to (19).

[0056]

[0057] The cycloalkylene group and the aralkylene group may have a substituent. In this case, the substituent may be an aryl group in addition to an alkyl group and an alkoxy group having 1 to 10 carbon atoms. Examples of the aryl group include phenyl, tolyl, xylyl, hydroxyphenyl, benzyl, naphthyl, and the like.

[0058] The phosphorus-containing polycyclic aromatic hydroxy compound of the present invention preferably has a structure represented by the following general formula (3).

[0059]

[0060] In the general formula (3), R 1 , Ar, n1, and m have the same meanings as in the general formula (1). 1 are independently hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms, preferably R 1 For hydrogen.

[0061] Y represents an aromatic ring group having 6 to 30 carbon atoms, and preferably, the -CH2-Y-CH2- of the linking group of Ar is a structure represented by the above formula (13), (16), or (18). More preferably, the -CH2-Y-CH2- of the linking group of Ar is a structure represented by the above formula (13).

[0062] Next, the method for producing the phosphorus-containing polycyclic aromatic hydroxy compound of the present invention is described. The phosphorus-containing polycyclic aromatic hydroxy compound of the present invention is an aromatic phosphate having one or more phenolic hydroxyl groups, and its production method can be based on the general production method of aromatic phosphate. That is, as an example of the reaction form, an esterification reaction using phosphorus oxyhalide (phosphorus oxyhalide) and a polycyclic aromatic hydroxy compound as raw materials can be performed through a dehydrohalogenation reaction to obtain the corresponding phosphate.

[0063] In order to prevent the hydrolysis reaction using hydrogen halide produced as a by-product as a catalyst and to efficiently obtain the product, the esterification reaction is performed by using a catalyst or removing the separated hydrogen halide from the reaction system.

[0064] The hydrogen halide (e.g., hydrogen chloride) that is released is a gas, and its volume increases when it is vaporized, so it is easy to be released to the outside of the reaction system for a raw material with high reactivity, but in the case of a raw material with low reactivity, the amount of hydrogen halide released is small, and it is easy to remain in the system, thereby sometimes causing a hydrolysis reaction. In this case, it is effective to capture the generated hydrogen halide so as not to cause a hydrolysis reaction, and amines are sometimes used as hydrogen halide capture agents.

[0065] The phosphorus-containing polycyclic aromatic hydroxy compound of the present invention is a compound represented by the above-mentioned general formula (1). Therefore, it is required to react a polycyclic aromatic hydroxy compound represented by the following general formula (7) corresponding to the general formula (1) as a raw material with phenols and oxyphosphorus halides as raw materials of a phosphorus halide compound represented by the following general formula (8) corresponding to the above-mentioned general formula (2).

[0066]

[0067]

[0068] In the general formulas (7) and (8), Ar, X, m, n1, and R 2 , R 3 , n2, n3 have the same meanings as in the general formulae (1) and (2). Z represents a halogen atom.

[0069] However, if the polycyclic aromatic hydroxy compound represented by the general formula (7) having multiple hydroxyl groups, which is a necessary raw material for the phosphorus-containing polycyclic aromatic hydroxy compound of the present invention, is reacted with phosphorus oxyhalide, a side reaction of the multiple hydroxyl groups reacting with the phosphorus oxyhalide occurs. Therefore, it is necessary to appropriately adjust the reaction order, the feed ratio of the raw materials, the reaction conditions, etc. in order to efficiently obtain the target compound.

[0070] Therefore, instead of reacting the three raw materials of the polycyclic aromatic hydroxy compound represented by the general formula (7) and the phenols and the phosphorus oxyhalide which are the raw materials of the phosphorus halide compound represented by the general formula (8) at one time, the phosphorus oxyhalide such as phosphorus oxychloride (POCl3) is first reacted with the phenols to obtain the phosphorus halide compound represented by the following general formula (8), and then the phosphorus halide compound represented by the general formula (8) is reacted with the polycyclic aromatic hydroxy compound represented by the general formula (7), thereby efficiently obtaining the target compound. At this time, in the front-stage reaction, the ratio of phenols to 1 mol of phosphorus oxyhalide is 2 mol. Preferably, the phenols are in the range of 1.8 to 2.2 mol, and more preferably 1.9 to 2.1 mol.

[0071] The phenols used as the raw material of the phosphorus halide compound represented by the general formula (8) are preferably monovalent phenols substituted or unsubstituted by an alkyl group having 1 to 6 carbon atoms, and specifically include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2,6-xylenol, 2,6-diethylphenol and the like.

[0072] These phenols may be used alone or in combination of two or more.

[0073] As examples of the phosphorus-containing polycyclic aromatic hydroxy compounds of the present invention, compounds of the following structures and mixtures thereof may be cited, but are not limited thereto:

[0074] In the compound of the following formula (9), R 1 A compound in which each of the following is independently hydrogen, a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituent of the following formula (10);

[0075]

[0076] In the above formula (9), m has the same meaning as in the general formula (1).

[0077]

[0078] In the compound of the above formula (9), R 1 A compound in which each of the following is independently hydrogen, a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituent of the following formula (11);

[0079]

[0080] In the compound of the above formula (9), R 1 A compound in which each of them is independently hydrogen, a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituent of the following formula (12).

[0081]

[0082] Examples of the phosphorus oxyhalide as a raw material of the phosphorus halide compound represented by the general formula (8) include phosphorus oxychloride and phosphorus oxybromide.

[0083] The phosphorus-containing polycyclic aromatic hydroxy compound of the present invention can be obtained by reacting the hydroxyl group of the polycyclic aromatic hydroxy compound represented by the general formula (7) with the phosphorus halide compound represented by the general formula (8). Therefore, by adjusting the molar ratio of the hydroxyl group of the general formula (8) relative to the polycyclic aromatic hydroxy compound, the hydroxyl equivalent and the phosphorus content can be controlled.

[0084] The molar ratio of the reaction is preferably 0.1 to 0.9 moles, more preferably 0.2 to 0.8 moles, and even more preferably 0.3 to 0.7 moles of the phosphorus halide compound represented by the general formula (8) relative to 1 mole of the hydroxyl group of the polycyclic aromatic hydroxy compound represented by the general formula (7). When the molar ratio is less than 0.1 mole, the phosphorus content decreases and the flame retardancy is insufficient, which is not preferred. When the molar ratio is more than 0.9 mole, the number of hydroxyl groups as reactive groups decreases, the heat resistance is insufficient, and the viscosity increases, which is not preferred.

[0085] The curable flame retardant resin composition of the present invention contains the phosphorus-containing polycyclic aromatic hydroxy compound as an essential component, and can be obtained by mixing the phosphorus-containing polycyclic aromatic hydroxy compound in a curable resin. As the curable resin, there is no limitation as long as it contains a resin that reacts with the hydroxyl group of the phosphorus-containing polycyclic aromatic hydroxy compound of the present invention, for example, epoxy resin, maleimide resin, etc. can be cited.

[0086] The epoxy resin that can be used for the curable resin composition is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, naphthol novolac type epoxy resin, dicyclopentadiene type epoxy resin, phenol aralkyl type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, etc. These epoxy resins can be used alone or in combination of two or more.

[0087] The amount of the phosphorus-containing polycyclic aromatic hydroxy compound and the epoxy resin is determined according to the phosphorus content of the resin composition. The phosphorus content in the resin composition is preferably 0.5 to 5.0% by mass, and more preferably 1.0 to 4.0% by mass. When it is less than 0.5% by mass, it does not exhibit flame retardancy, and when it is more than 5.0% by mass, the amount of the phosphorus-containing polycyclic aromatic hydroxy compound is large, and the hydroxyl group is too much relative to the epoxy group, and the crosslinking is insufficient and becomes a brittle cured product, so it is not preferred. In addition, when the epoxy resin is used for the curable resin, a curing agent other than the phosphorus-containing polycyclic aromatic hydroxy compound of the present invention may be included.

[0088] Examples of curing agents that can be used in combination with phosphorus-containing polycyclic aromatic hydroxy compounds include phenolic curing agents, amine compounds, amide compounds, acid anhydride compounds, naphthol curing agents, active ester curing agents, benzoic acid curing agents, and the like. Oxazine-based curing agents, cyanate-based curing agents, acid anhydride-based curing agents, etc. These can be used alone or in combination of two or more.

[0089] The amount of curing agent other than the phosphorus-containing polycyclic aromatic hydroxy compound of the present invention is preferably an amount of 0.5 to 5.0 mass % phosphorus content of the resin composition of the present invention, and the molar ratio (Nh / Ne) of the total molar number (Nh) of the reaction points of the epoxy groups of the phosphorus-containing polycyclic aromatic hydroxy compound and other curing agents to the molar number (Ne) of the epoxy groups is 0.7 to 1.3, preferably 0.9 to 1.1. When the molar ratio is outside the range, crosslinking is insufficient and a brittle cured product is obtained, which is not preferred.

[0090] The resin composition of the present invention may also contain curable resins other than epoxy resins. Examples of curable resins other than epoxy resins include free radical polymerizable resins such as vinyl ester resins, polyvinyl benzyl resins, unsaturated polyester resins, curable vinyl resins, maleimide resins, and cyanate resins.

[0091] The curable resin composition of the present invention may contain a curing accelerator as required. Examples of the curing accelerator used herein include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. The amount of the curing accelerator added is preferably 0.1 to 10.0 parts by weight relative to a total of 100 parts by weight of the phosphorus-containing polycyclic aromatic hydroxy compound, the curable resin, and other curing agents.

[0092] The resin composition of the present invention may contain, in addition to the above components, other components such as thermosetting resins, thermoplastic resins, organic fillers, inorganic fillers, organic solvents, thickeners, defoamers, adhesion-imparting agents, colorants, additives, etc. as appropriate.

[0093] Examples of thermoplastic resins include polystyrene, polyphenylene ether resins, polyetherimide resins, polyethersulfone resins, PPS resins, polycyclopentadiene resins, polycycloolefin resins, and the like; known thermoplastic elastomers such as styrene-ethylene-propylene copolymers, styrene-ethylene-butylene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, hydrogenated styrene-butadiene copolymers, hydrogenated styrene-isoprene copolymers, and the like; or rubbers such as polybutadiene and polyisoprene. Preferred examples include polyphenylene ether resins (unmodified) and hydrogenated styrene-butadiene copolymers.

[0094] Fillers can be added to the curable resin composition of the present invention. As fillers, fillers added to improve the heat resistance and flame retardancy of the cured product of the curable resin composition can be cited, and known fillers can be used, but are not particularly limited. In addition, by containing fillers, heat resistance, dimensional stability, flame retardancy, etc. can be further improved. Specifically, metal oxides such as silicon dioxide such as spherical silicon dioxide, aluminum oxide, titanium oxide and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate and calcium carbonate can be cited. When metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used, they act as flame retardant aids, and flame retardancy can be ensured even if the phosphorus content is low. Among them, silicon dioxide, mica and talc are preferred, and spherical silicon dioxide is more preferred. In addition, one of them can be used alone, or two or more can be used in combination.

[0095] The filler can be used directly, or a filler surface-treated with a silane coupling agent such as a vinyl silane type, a methacryloxy silane type, an acryloxy silane type, a styryl silane type, an epoxy silane type, an amino silane type, or a cationic silane type can be used. This improves the bonding strength with the metal foil and the interlayer bonding strength between the resins. In addition, the above-mentioned silane coupling agent can be added and used by an integral blending method rather than a method of pre-surface treating the filler.

[0096] The content of the filler is preferably 10 to 200 parts by mass, more preferably 30 to 150 parts by mass, based on 100 parts by mass of the total solid components other than the filler (including organic components such as monomers and flame retardants, excluding solvents).

[0097] The curable resin composition of the present invention may further contain additives other than those mentioned above. Examples of the additives include defoamers such as silicone defoamers and acrylate defoamers, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes or pigments, lubricants, dispersants such as wetting dispersants, and the like.

[0098] The cured product obtained by curing the curable resin composition of the present invention can be used as a molded product, a laminated product, a cast product, an adhesive, a coating film, or a film. For example, the cured product of the semiconductor sealing material is a cast product or a molded product. As a method for obtaining the cured product for this purpose, the cured product can be obtained by casting the curable resin composition or molding it using a transfer-molding machine, an injection molding machine, etc., and further heating it at 80 to 230° C. for 0.5 to 10 hours.

[0099] The curable resin composition of the present invention can also be used as a prepreg. When manufacturing a prepreg, it can be prepared in a varnish state for the purpose of being impregnated in a substrate (fibrous substrate) for forming a prepreg or for the purpose of making a circuit substrate material for forming a circuit substrate, thereby making a resin varnish.

[0100] The resin varnish is suitable for circuit substrates and can be used as a varnish for circuit substrate materials. It should be noted that the use of the circuit substrate materials mentioned here specifically includes printed wiring boards, printed circuit boards, flexible printed wiring boards, build-up wiring boards, etc.

[0101] The above-mentioned resin varnish is prepared, for example, as follows.

[0102] First, the various components of the present invention that are soluble in an organic solvent, such as the phosphorus-containing polycyclic aromatic hydroxy compound and the epoxy resin component, are put into an organic solvent and dissolved. At this time, heating can be performed as needed. Then, components that are insoluble in an organic solvent, such as an inorganic filler, are added as needed, and dispersed using a ball mill, a bead mill, a planetary mixer, a roller mill, etc., thereby preparing a varnish-like curable resin composition. As the organic solvent used here, there is no particular limitation as long as the resin component used in the epoxy resin composition of the present invention is dissolved and does not hinder the curing reaction. For example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, and butyl acetate; polar solvents such as dimethylacetamide and dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene, etc., can be used 1 type, or 2 or more types can be mixed.

[0103] When preparing the resin varnish, the amount of the organic solvent used is preferably 5 to 900 mass %, more preferably 10 to 700 mass %, and particularly preferably 20 to 500 mass %, based on 100 mass % of the curable resin composition of the present invention.

[0104] As the base material used for making prepreg, known materials can be used, for example, can be used separately or in combination with base materials such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper or more. In these base materials, coupling agent can be used as required for the purpose of improving the adhesiveness in the interface of resin and base material. As coupling agent, common coupling agents such as silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconium aluminate coupling agent can be used.

[0105] As a method for obtaining the prepreg of the present invention, there can be cited a method in which the above-mentioned resin varnish is impregnated into a substrate and then dried. The impregnation can be performed by dipping, coating, etc. The impregnation can be repeated multiple times as needed. In addition, at this time, multiple solutions with different compositions and concentrations can also be used to repeat the impregnation and adjust to the final desired resin composition and resin amount. After the impregnation, the prepreg can be obtained by heating and drying at 100 to 180° C. for 1 to 30 minutes. Here, the amount of resin in the prepreg is preferably 30 to 80% by mass of the resin component.

[0106] The curable resin composition of the present invention can also be used as a laminate. When a prepreg is used to form a laminate, one or more prepregs are stacked, and a metal foil is arranged on one side or both sides to form a laminate, and the laminate is heated and pressurized to be laminated and integrated. Here, as the metal foil, copper, aluminum, brass, nickel, etc., single, alloy, or composite metal foil can be used. As the conditions for heating and pressurizing the laminate, it is sufficient to adjust the heating and pressurization appropriately under the conditions for curing the curable resin composition. However, if the pressurization pressure is too low, sometimes bubbles remain inside the obtained laminate and the electrical properties are reduced. Therefore, it is preferable to pressurize under conditions that satisfy the formability. For example, the temperature can be set to 180-230°C, and the pressure can be set to 49.0-490.3N / cm 2 (5~50kgf / cm 2 ), and the heating and pressing time is set to 40 to 240 minutes. The single-layer laminate obtained in this way can be used as an inner layer material to make a multilayer board. At this time, the laminate is firstly subjected to circuit formation by an additive method, a subtractive method, etc., and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. An insulating layer is formed on the circuit forming surface of one side or both sides of the inner layer material with a resin sheet, a metal foil with a resin, or a prepreg, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.

[0107] The method of producing a build-up film from the curable composition of the present invention includes, for example, coating the resin varnish on a support film and drying it to form a film-like insulating layer. The film-like insulating layer thus formed can be used as a build-up film for a multilayer printed wiring board.

[0108] The drying step is preferably performed so that the organic solvent content in the layer of the build-up film resin composition is 10% by mass or less, preferably 5% by mass or less. The drying conditions vary depending on the type and amount of the organic solvent in the varnish, but the varnish can be dried at 50 to 160° C. for about 3 to 20 minutes.

[0109] The thickness of the build-up layer formed on the support is usually greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, so the thickness of the resin composition layer is preferably 10 to 100 μm.

[0110] In addition, from the viewpoint of preventing dust and the like from adhering to the surface and preventing scratches, it is preferred in the present invention that the build-up film be protected by a protective film.

[0111] Examples of the support film and the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polyimide, and release paper, copper foil, aluminum foil, and other metal foils. In addition to matte treatment and corona treatment, the support film and the protective film may also be subjected to release treatment.

[0112] The thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 μm, preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0113] The support film is peeled off after being laminated on the circuit board or after forming an insulating layer by heat curing. If the support film is peeled off after the adhesive film is heat cured, curing hindrance caused by oxygen in the curing process can be prevented, and further adhesion of dust etc. can be prevented. When peeling off after curing, the support film is usually subjected to a demolding treatment in advance.

[0114] Example

[0115] Next, the present invention will be described by way of examples, but the present invention is not limited thereto. Parts in each example are parts by weight.

[0116] In addition, the physical property measurement of each cured product sample in the example was performed by the method shown below.

[0117] (1) Molecular weight and molecular weight distribution of polymers: The molecular weight and molecular weight distribution of phosphorus-containing polycyclic aromatic hydroxy compounds were measured using GPC (HLC-8120GPC manufactured by Tosoh Corporation) with tetrahydrofuran as solvent, flow rate of 1.0 ml / min, column temperature of 38° C., and a calibration curve of monodisperse polystyrene.

[0118] (2) Hydroxyl equivalent: Accurately weigh about 6 mg / eq of a sample in a 100 mL stoppered flask, add 3 mL of a reagent mixed with acetic anhydride / pyridine = 3 / 1 (volume ratio), install a cooling tube, heat with a hot plate to reflux for 5 minutes, let cool for 5 minutes, and then add 1 mL of water. The solution is titrated potentiometrically with a 0.5 mol / L KOH / MeOH solution to calculate the equivalent.

[0119] (3) Phosphorus content: Sulfuric acid, hydrochloric acid and perchloric acid are added to the sample, heated and wet ashed to convert all phosphorus atoms into orthophosphoric acid. Metavanadate and molybdate are reacted in a sulfuric acid acid solution, and the absorbance of the generated phosphovanadomolybdic acid complex at 420 nm is measured. The phosphorus atom content calculated based on a calibration curve prepared in advance using potassium dihydrogen phosphate is expressed in mass %.

[0120] (4) Glass transition temperature: measured using a differential scanning calorimeter manufactured by Hitachi High-Tech Science Company at a heating rate of 10°C / min and determined from the baseline shift.

[0121] (5) Relative dielectric constant and dielectric loss tangent: According to IPC-TM-6502.5.5.9, the dielectric constant (Dk) and dielectric loss tangent (Df) at a frequency of 1 GHz were determined by the volumetric method using a material analyzer E4991A (manufactured by AGILENT Technologies) at 25°C and 60% humidity.

[0122] (6) Flame retardancy: According to the UL94 test method, five test pieces were used to evaluate the flame retardancy by the vertical method. The evaluation was recorded as V-0, V-1, and V-2.

[0123] (7) Water absorption: According to JIS K 7209, a cured product sample was immersed in water at 23° C., and the saturated water content was determined.

[0124] (8) Dielectric property change rate after water absorption: The change rate was calculated from the following formula using the measured value (A1) of the cured sample before the water absorption test and the measured value (A2) after the water absorption test.

[0125] Dielectric property change rate (%) = (A2-A1) / A1×100

[0126] In the Synthesis Examples, Examples and Comparative Examples, the following compounds were used as raw materials.

[0127] Phosphorus oxychloride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0128] ·Resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0129] 2,6-Dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0130] SN-485 (Naphthol aralkyl resin manufactured by Nippon Steel Chemical Materials Co., Ltd.: hydroxyl equivalent 212 g / eq)

[0131] SP-2060N (phenol novolac resin manufactured by Nippon Steel Chemical Materials Co., Ltd.: hydroxyl equivalent 107 g / eq)

[0132] ·MEH-7800 (phenol aralkyl resin manufactured by Meiwa Chemicals Co., Ltd.: hydroxyl equivalent 175 g / eq)

[0133] ·MEH-7851M (biphenyl aralkyl resin manufactured by Meiwa Chemicals Co., Ltd.: hydroxyl equivalent 199 g / eq)

[0134] (Synthesis Example 1) Synthesis of di(2,6-xylene)chlorophosphate (DXPC)

[0135] A 2L four-necked flask equipped with a stirrer, a thermometer and a hydrochloric acid recovery device (a condenser connected to a water scrubber) was charged with 767 g (5 mol) of phosphorus oxychloride (the following structural formula), 1200 g (9.8 mol) of 2,6-dimethylphenol (the following structural formula), 140 g of xylene as a solvent, and 6.2 g (0.065 mol) of magnesium chloride as a catalyst.

[0136] POCl3

[0137]

[0138] The obtained mixed solution was stirred and gradually heated to 160°C for about 3 hours to react, and the generated hydrogen chloride gas was recovered by a water scrubber. Then, the pressure in the flask was gradually reduced to 20 kPa at the same temperature, and xylene, unreacted phosphorus oxychloride and 2,6-dimethylphenol, and by-produced hydrogen chloride were removed to obtain 1700 g of a reaction product containing di(2,6-xylene) chlorophosphate (DXPC: the following structural formula) as the main component. In addition, the chlorine content of the reaction mixture was 10.9% by mass.

[0139]

[0140] (Example 1) Synthesis of phosphorus-containing polycyclic aromatic hydroxyl compound (Compound A)

[0141] In a 500 mL four-necked flask equipped with a stirrer, a thermometer, and a hydrochloric acid recovery device (a condenser connected to a water scrubber) were charged 260 g of mesitylene, 90.0 g (0.4 mol) of naphthol aralkyl resin SN-485 (structural formula shown below), 64.8 g (0.2 mol) of DXPC synthesized in Synthesis Example 1, 0.95 g (0.01 mol) of anhydrous magnesium chloride as a catalyst, and 2.0 g (0.015 mol) of anhydrous aluminum chloride.

[0142]

[0143] The obtained mixed solution was heated to 154°C for 2 hours while stirring, and the generated hydrogen chloride was collected. After further reaction for 25 hours, about 200 g of mesitylene was recovered under reduced pressure and returned to normal pressure. The reaction mixture was cooled to 60°C, 200 g of ethyl acetate was added, and acid washing was performed twice, neutralization was performed, and then water washing was performed to remove the solvent, and 125.6 g of phosphorus-containing naphthol resin (compound A) as a reaction product was obtained.

[0144] The phosphorus content of the obtained compound A was 3.6% by mass, and the hydroxyl equivalent was 514 g / eq. The modification rate of hydroxyl groups to phosphorus-containing functional groups calculated from the hydroxyl equivalent was 37.6 mol%.

[0145] (Comparative Example 1) Synthesis of Phosphorus-Containing Phenol Compound B

[0146] In a 500 mL four-necked flask equipped with a stirrer, a thermometer, and a hydrochloric acid recovery device (a condenser connected to a water scrubber) were charged 260 g of mesitylene, 58.0 g (0.5 mol) of phenol novolac resin SP-2060N (structural formula shown below), 81.8 g (0.25 mol) of DXPC synthesized in Synthesis Example 1, 1.2 g (0.01 mol) of anhydrous magnesium chloride as a catalyst, and 2.0 g (0.015 mol) of anhydrous aluminum chloride.

[0147]

[0148] The obtained mixed solution was heated to 154°C for 2 hours while stirring, and the generated hydrogen chloride was collected. After further reaction for 25 hours, about 200 g of mesitylene was recovered under reduced pressure, and the pressure was returned to normal. The reaction mixture was cooled to 60°C, 200 g of ethyl acetate was added, and acid washing was performed twice, neutralization was performed, and then water washing was performed, and the solvent was removed to obtain 113.5 g of a phosphorus-containing phenol compound (compound B).

[0149] The phosphorus content of the obtained compound B was 5.5% by mass, and the hydroxyl equivalent was 360 g / eq. The modification rate of hydroxyl groups to phosphorus-containing functional groups calculated from the hydroxyl equivalent was 38.9 mol %.

[0150] (Comparative Example 2) Synthesis of Phosphorus-Containing Phenol Compound C

[0151] Referring to the synthesis example of Japanese Patent Application Laid-Open No. 2002-97260, 97 g of phenol aralkyl resin MEH-7800 (structural formula below), 81.8 g (0.25 mol) of DXPC synthesized in Synthesis Example 1, 1.2 g (0.01 mol) of anhydrous magnesium chloride and 2.0 g (0.015 mol) of anhydrous aluminum chloride as catalysts were filled.

[0152]

[0153] Thereafter, the same operation as in Example 1 was carried out to obtain 119.4 g of a phosphorus-containing phenol compound (Compound C).

[0154] The phosphorus content of the obtained compound C was 4.1% by mass, and the hydroxyl equivalent was 460 g / eq. The modification rate of hydroxyl groups to phosphorus-containing functional groups calculated from the hydroxyl equivalent was 38.0 mol %.

[0155] (Comparative Example 3) Synthesis of Phosphorus-Containing Phenol Compound D

[0156] Referring to the synthesis example of Japanese Patent Application Laid-Open No. 2002-97260, 110 g of biphenyl aralkyl resin MEH-7851M (structural formula below), 81.8 g (0.25 mol) of DXPC synthesized in Synthesis Example 1, 1.2 g (0.01 mol) of anhydrous magnesium chloride as a catalyst, and 2.0 g (0.015 mol) of anhydrous aluminum chloride were filled.

[0157]

[0158] Thereafter, the same operation as in Example 1 was carried out to obtain 119.4 g of a phosphorus-containing phenol compound (Compound D).

[0159] The phosphorus content of the obtained compound D was 4.1% by mass, and the hydroxyl equivalent was 511 g / eq. The modification rate of hydroxyl groups to phosphorus-containing functional groups calculated from the hydroxyl equivalent was 39.1 mol%.

[0160] (Comparative Example 4) Synthesis of Phosphorus-Containing Phenol Compound E

[0161] The synthesis was carried out according to the method described in the patent publication WO2021 / 256351. Specifically, 1500 g of phosphorus oxychloride, 611 g of 2,6-dimethylphenol, and 1.2 g of magnesium chloride as a catalyst were filled in a 2-liter four-necked flask equipped with a stirrer, a thermometer, and a hydrochloric acid recovery device (a condenser connected to a water scrubber).

[0162] The obtained mixed solution was stirred and gradually heated to 110°C for about 3 hours to react, and the generated hydrogen chloride (hydrochloric acid gas) was recovered by a water scrubber. Then, the pressure in the flask was gradually reduced to 12 kPa at 120°C to remove unreacted phosphorus oxychloride and phenol, and by-produced hydrogen chloride, thereby obtaining 1200 g of mono-2,6-dimethylphenyl dichlorophosphate.

[0163] A 2-liter four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a condenser was filled with 320 g of 2,3,5-trimethylhydroquinone, 135 g of pyridine as a hydrogen chloride scavenger, and 200 g of toluene as a solvent. In addition, 203 g of the above-mentioned mono-2,6-dimethylphenyl dichlorophosphate was filled in the dropping funnel.

[0164] The mixed solution in the four-necked flask was heated to 20°C while being stirred, and mono-2,6-dimethylphenyl dichlorophosphate in the dropping funnel was added dropwise over 2 hours while being maintained at the same temperature (20°C). After the addition was completed, the mixture was heated to 65°C and stirred for 5 hours to obtain a reaction product. The obtained reaction product was washed with dilute hydrochloric acid and water, heated to 150°C, reduced pressure to 2 kPa, water, toluene, and low-boiling components were distilled off, and cooled to room temperature to obtain 330 g of a dark brown solid phosphorus-containing phenol compound (compound E, the following structural formula).

[0165]

[0166] Examples 2 to 3, Comparative Examples 5 to 17

[0167] <Preparation of epoxy resin composition and evaluation of physical properties>

[0168] Varnish was prepared by mixing various components in the ratio of Tables 1 and 2, and coated on a PET film, and dried in an oven at 130°C for 5 minutes to prepare a film of the resin composition. Next, the film was crushed to obtain a powder of the resin composition. Furthermore, the powder was sandwiched between a stainless steel mirror plate and a spacer, and a vacuum oven was used to form the sample at 190°C for 90 minutes and cured at 200°C for 5 hours to obtain a sample of the cured product.

[0169] The following compounds were used in Examples and Comparative Examples of the resin compositions.

[0170] ESN-475V: Naphthalene-type epoxy resin manufactured by Nippon Steel Chemical Materials Co., Ltd. (epoxy equivalent: 325 g / eq)

[0171] SN-485: Naphthol resin manufactured by Nippon Steel Chemical Materials Co., Ltd. (hydroxyl equivalent: 210 g / eq)

[0172] TPP: Triphenyl phosphate manufactured by Daihachi Chemical Industry Co., Ltd. (phosphorus content: 9.5% by mass)

[0173] PX-200: Aromatic condensed phosphate ester manufactured by Daihachi Chemical Industry Co., Ltd. (phosphorus content 9.02%)

[0174] LC-950PM60: DOPO-BPA manufactured by ShinA Corporation (hydroxyl equivalent 570.52 g / eq, phosphorus content 10.9% by mass, solid content 60%)

[0175] 2E4MZ: 2-ethyl-4-methylimidazole manufactured by Shikoku Chemicals Co., Ltd.

[0176] The formulations and results are shown in Tables 1 and 2.

[0177]

[0178]

[0179] Industrial Applicability

[0180] The phosphorus-containing polycyclic aromatic hydroxy compound of the present invention is useful for flame retardant plastic materials used in electrical and electronic products, OA equipment, communication equipment, building materials, etc., such as thermosetting resins such as epoxy resins, and is particularly useful as a flame retardant material for reducing transmission loss in electronic equipment as the amount of information processing increases and the frequency increases.

Claims

1. A phosphorus-containing polycyclic aromatic hydroxy compound, characterized in that: It is represented by the general formula (1); In the general formula (1), m is an integer of 1 to 20, n1 is an integer of 1 to 4, Ar is an aromatic ring having 6 to 30 carbon atoms and may have a substituent, but excluding a benzene ring; R 1 are independently hydrogen, a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituent represented by the general formula (2), but at least one R 1 A structure comprising the general formula (2); X represents a linking group, each of which is independently oxygen, sulfur, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, or a substituted or unsubstituted aralkylene group having 8 to 32 carbon atoms; In the general formula (2), R 2 and R 3 Each of n2 and n3 is independently a linear or branched alkyl group having 1 to 5 carbon atoms, and each of n2 and n3 is independently an integer of 0 to 5.

2. The phosphorus-containing polycyclic aromatic hydroxy compound according to claim 1, characterized in that: It is represented by the following general formula (3); In the general formula (3), R 1 , n1, and m have the same meanings as in the general formula (1); Y is an aromatic ring group having 6 to 30 carbon atoms which may have a substituent; Ar represents a polycyclic aromatic group derived from a polycyclic aromatic compound represented by the following general formula (4), (5) or (6); In the general formulae (4), (5) and (6), R4 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and n4 is an integer of 0 to 4; 1 , n1 have the same meanings as in the general formula (1).

3. The phosphorus-containing polycyclic aromatic hydroxy compound according to claim 1, wherein The hydroxyl equivalent is 100 to 3000 g / eq, and the phosphorus content is 1.5 to 15.0% by mass.

4. A method for producing a phosphorus-containing polycyclic aromatic hydroxy compound according to any one of claims 1 to 3, characterized in that: 0.1 to 0.9 mol of a phosphorus compound represented by the general formula (8) is reacted with 1 mol of the hydroxyl groups of the polycyclic aromatic hydroxy compound represented by the general formula (7); In the general formulas (7) and (8), m, n1, Ar, X, R 2 , R 3 , n2, n3 have the same meanings as in the general formulae (1) and (2); Z represents a halogen atom. 5 . A curable resin composition comprising the phosphorus-containing polycyclic aromatic hydroxy compound according to claim 1 , and a curable resin. 6 . A cured product obtained by curing the curable resin composition according to claim 5 .

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