Phosphorus-containing (meth) acryloyl compound, phosphorus-containing vinylbenzyl compound, method for producing same, flame-retardant resin composition containing same, and laminate for electronic circuit board

Abstract

Provided are: a phosphorus-containing compound which can be used as a reactive phosphorus-based flame retardant and has excellent heat resistance and dielectric properties in a cured product; a curable resin composition containing the phosphorus-containing compound; and a cured product thereof. A phosphorus-containing (meth) acryloyl compound or a phosphorus-containing vinylbenzyl ether compound characterized by being represented by general formula (1). In general formula (1), m is a number of 1-20, n1 is each independently a number of 1-4, and Ar is an optionally substituted aromatic ring having 6-30 carbon atoms. Each R1 independently represents a substituent represented by general formula (2) or general formulae (3A) and (3B);

Description

Technical Field

[0001] The present invention relates to a reactive phosphorus compound, in particular to a phosphorus-containing (meth)acryloyl compound and a phosphorus-containing vinylbenzyl compound, which can be used as a reactive flame retardant for plastic materials. Background Art

[0002] Plastics are used in a wide range of applications, from building materials to electrical and electronic equipment, due to their excellent mechanical properties and moldability. However, many plastics are flammable, necessitating flame retardancy for safety against overheating and fire in applications such as electrical and electronic products, office automation equipment, and communications equipment.

[0003] Halogen-based flame retardants, inorganic flame retardants, and phosphorus-based flame retardants are commonly used to flame-retard plastic materials, regardless of the type of resin or intended use. However, halogen-based flame retardants, primarily bromine-based ones, have been cited as potential sources of highly carcinogenic dioxins, leading to restrictions on their use in response to the current trend toward reducing environmentally hazardous substances. Furthermore, while inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide offer a flame-retardant effect by absorbing heat, they must be added in large quantities to achieve sufficient flame retardancy, which can degrade the properties of various plastic molded products.

[0004] Therefore, phosphorus-based flame retardants are often used because they do not generate harmful substances and can achieve flame retardancy with relatively small addition amounts. However, even these agents inevitably affect properties, such as reduced processability due to bleed-out and a lowered glass transition temperature.

[0005] To address the issues with these additive flame retardants, reactive flame retardants containing phosphorus atoms as a flame-retardant component and possessing reactive groups have been developed and are becoming increasingly widespread. For example, Patent Document 1 discloses a phenolic resin obtained by reacting bisphenol A with formaldehyde to produce hydroxymethylbisphenol A, followed by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as "DOPO") as a curing agent for epoxy resins. Patent Document 2 discloses a phosphorus-containing epoxy resin obtained by reacting DOPO with quinones and then with an epoxy resin. These resins address processability issues such as flame retardant bleed-out, and no degradation of thermal properties such as heat resistance has been observed. Thus, compared to additive flame retardants, the use of reactive flame retardants can compensate for the shortcomings of conventional additive flame retardants, leading to the development of numerous flame-retardant epoxy resins.

[0006] On the other hand, in recent years, in the electronic-electrical material field of needs flame retardancy, due to the rapid development of the electronic equipment represented by smart phone, the requirement for the resin composition comprising flame retardant changes to more stringent requirement.Particularly in information, communication field, along with the increase of information processing amount, the high-frequency development of signal, in order to reduce transmission loss, for the resin composition used in this field, strongly need low dielectric constant, low dielectric loss tangent. Therefore, in the electronic-electrical material field represented by circuit substrate, instead of epoxy resin, widely use gradually and can realize the free radical polymerizable resin of lower dielectric constant, lower dielectric loss tangent. Therefore, not only need reactive group and epoxy group, epoxy resin to have reactive flame retardant, and need to be able to react with the resin of free radical polymerizable low dielectric constant, low dielectric loss tangent without halogen flame retardant.

[0007] As halogen-free flame retardants having free-radically polymerizable functional groups, patent documents 3 and 4 disclose vinyl benzyl ether compounds containing a DOPO skeleton. Furthermore, patent documents 5 and 6 disclose vinyl benzyl compounds or (meth)acryloyl compounds containing a phosphate ester structure. However, these compounds do not exhibit sufficient properties in terms of the currently required low dielectric constant and low dielectric loss tangent. There is no flame retardant containing a free-radically polymerizable group that satisfies both halogen-free flame retardancy and thermal and dielectric properties such as heat resistance.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2013-166938

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 11-279258

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 2004-331537

[0013] Patent Document 4: Japanese Patent Application Laid-Open No. 2004-277322

[0014] Patent Document 5: Japanese Patent Application Laid-Open No. 2022-16423

[0015] Patent Document 6: Japanese Patent Application Laid-Open No. 2022-16422 Summary of the Invention

[0016] Therefore, an object of the present invention is to provide a phosphorus-containing compound that can be used as a reactive phosphorus-based flame retardant and has excellent heat resistance and dielectric properties in its cured product, a curable resin composition containing the same, and its cured product.

[0017] The present inventors have conducted intensive studies on the above-mentioned problems and, as a first invention, have found that a phosphorus-containing (meth)acryloyl compound having a specific structure is excellent in heat resistance and dielectric properties, thereby completing the present invention.

[0018] That is, the first present invention is a phosphorus-containing (meth)acryloyl compound characterized by being represented by the general formula (1A).

[0019]

[0020] In general formula (1A), m is a number from 1 to 20, n1 is each independently a number from 1 to 4, and Ar is an aromatic ring having 6 to 30 carbon atoms that may have a substituent. R1 is each independently a substituent represented by general formula (2A) or general formula (3A), and the compound contains at least one substituent represented by general formula (2A) and at least one substituent represented by general formula (3A). X represents a linking group and is each independently oxygen, sulfur, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, or an aralkylene group having 8 to 32 carbon atoms.

[0021]

[0022] In the general formula (2A), R2 and R3 are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, and n2 and n3 are each independently a number of 0 to 5.

[0023]

[0024] Wherein, R4 is hydrogen or methyl.

[0025] The present invention preferably relates to the aforementioned phosphorus-containing (meth)acryloyl compound, characterized by being represented by the following general formula (4A).

[0026]

[0027] In the general formula (4A), R1, n1, and m are the same as those in the general formula (1A). Y is an aromatic ring group having 6 to 30 carbon atoms which may have a substituent. k is 0 or 1. Ar represents an aromatic group derived from an aromatic compound represented by the following general formula (5), (6), (7), or (8).

[0028]

[0029] In the above general formulae (5), (6), (7) and (8), R5 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. R1 and n1 are the same as those in general formula (1A).

[0030] The present invention preferably comprises the aforementioned phosphorus-containing (meth)acryloyl compound, wherein the phosphorus content is 1.5 to 12.0% by weight.

[0031] The present invention is a method for producing the above-mentioned phosphorus-containing (meth)acryloyl compound, characterized in that a phosphorus-containing phenol compound represented by general formula (9) is reacted with one or more of (meth)acrylic acid, (meth)acrylic halide or (meth)acrylic anhydride.

[0032]

[0033] In the general formula (9), m, n1, Ar, and X are the same as those in the general formula (1A). R6 is hydrogen or a substituent represented by the above general formula (2A).

[0034] The present invention provides a flame-retardant resin composition comprising one or more thermosetting resins or thermoplastic resins and the aforementioned phosphorus-containing (meth)acryloyl compound. The present invention also provides a laminate for an electronic circuit board obtained using the flame-retardant resin composition.

[0035] The present inventors have conducted intensive studies on the above-mentioned problems and, as a second invention, have found that a phosphorus-containing vinylbenzyl compound having a specific structure has excellent heat resistance and dielectric properties, thereby completing the present invention.

[0036] That is, the second present invention is a phosphorus-containing vinyl benzyl ether compound characterized by being represented by the general formula (1B).

[0037]

[0038] In general formula (1B), m is a number from 1 to 20, n1 is each independently a number from 1 to 4, and Ar is an aromatic ring having 6 to 30 carbon atoms that may have a substituent. R1 is each independently a substituent represented by general formula (2B) or a vinylbenzyl group represented by general formula (3B), and the compound contains at least one substituent represented by general formula (2B) and at least one substituent represented by general formula (3B). X represents a linking group and is each 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.

[0039]

[0040] In the general formula (2B), R2 and R3 are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, and n2 and n3 are each independently a number of 0 to 5.

[0041]

[0042] The present invention preferably relates to the phosphorus-containing vinyl benzyl ether compound described above, characterized in that it is represented by the following general formula (4B):

[0043]

[0044] In the general formula (4B), R1, n1, and m are the same as those in the general formula (1B). Y is an aromatic ring group having 6 to 30 carbon atoms which may have a substituent. k is 0 or 1. Ar represents an aromatic group derived from an aromatic compound represented by the following general formula (5), (6), (7), or (8).

[0045]

[0046] In the above general formulae (5), (6), (7) and (8), R5 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. R1 and n1 are the same as those in general formula (1B).

[0047] The present invention preferably comprises the above-mentioned phosphorus-containing vinylbenzyl compound, wherein the phosphorus content is 1.5 to 12.0% by weight.

[0048] The present invention is a method for producing the above-mentioned phosphorus-containing vinylbenzyl ether compound, characterized in that a phosphorus-containing phenol compound represented by the general formula (9) is reacted with a vinylbenzyl halide.

[0049]

[0050] In the general formula (9B), m, n1, Ar, and X are the same as those in the general formula (1B). R6 is hydrogen or a substituent represented by the above general formula (2B).

[0051] The present invention provides a flame-retardant resin composition comprising the phosphorus-containing vinyl benzyl ether compound and one or more thermosetting or thermoplastic resins. The present invention also provides a laminate for an electronic circuit board obtained using the flame-retardant resin composition.

[0052] The phosphorus-containing (meth)acryloyl compound or phosphorus-containing vinylbenzyl compound of the present invention has excellent heat resistance and dielectric properties and is very useful as a reactive phosphorus-based flame retardant for reducing transmission loss at higher frequencies associated with increased information processing capacity of electronic devices. DETAILED DESCRIPTION

[0053] First, the phosphorus-containing (meth)acryloyl compound of the first present invention will be described in detail.

[0054] In the description of the present invention, the names of acrylic resins, acrylic compounds, acrylate compounds, etc. are generally referred to as follows. For example, "acryl" and "methacryl" are sometimes collectively referred to as "(meth)acryl", "acrylic" and "methacrylic" are sometimes collectively referred to as "(meth)acrylic", and "acrylate" and "methacrylate" are sometimes collectively referred to as "(meth)acrylate".

[0055] The phosphorus-containing (meth)acryloyl compound or phosphorus-containing phenol compound includes not only a single compound but also a mixture (resin).

[0056] The phosphorus-containing (meth)acryloyl compound of the present invention is represented by the following general formula (1A).

[0057]

[0058] In the general formula (1A), m is a repeating number and represents a number from 1 to 20. The phosphorus-containing (meth)acryloyl compound (resin) is usually a mixture of a plurality of compounds having different repeating numbers, and the average value (number average) of m is in the range of 0.1 to 15, preferably 0.5 to 10, and more preferably 1.0 to 5.

[0059] Each Ar is independently a substituted or unsubstituted aromatic ring group having 3 to 30 carbon atoms. The aromatic ring group is not particularly limited, and examples thereof include groups obtained by removing one or two hydrogen atoms from monocyclic aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine; and groups obtained by removing one or two hydrogen atoms from fused-ring aromatic compounds such as naphthalene, anthracene, phenanthren, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Furthermore, the aromatic ring group may be a combination of multiple of these aromatic compounds, for example, groups obtained by removing one or two hydrogen atoms from ring-aggregated aromatic compounds such as biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl.

[0060] Specifically, Ar is preferably a group derived from one or more aromatic hydroxy compounds represented by the following general formula (5), (6), (7) or (8).

[0061]

[0062] In the above general formulae (5), (6), (7) and (8), R4 represents a substituent on the aromatic ring, and each is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. n4 is an integer of 0 to 4.

[0063] 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.

[0064] 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.

[0065] These substituents may be used alone or in combination of two or more.

[0066] In the general formulae (1A), (5), (6), (7) and (8), R1 represents a substituent represented by the following general formula (2A) or (3A), and n1 is an integer of 1 to 4.

[0067]

[0068] In the general formula (2A), R2 and R3 are each independently a linear or branched alkyl group having 1 to 5 carbon atoms.

[0069] 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, and neopentyl. Among these, methyl is particularly preferred from the viewpoint of reactivity in production and availability.

[0070] 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 greater, the substitution position on the aromatic ring of n2 and n3 is not limited, but is preferably ortho to oxygen to prevent hydrolysis of the phosphate.

[0071]

[0072] wherein R4 represents hydrogen or methyl.

[0073] In general formulae (1A), (5), (6), (7), and (8), n1 represents the number of substitutions of the (meth)acryloyl groups represented by general formula (2A) or (3A) bonded to each benzene ring. Here, n1 is an integer of 1 to 5.

[0074] The phosphorus-containing (meth)acryloyl compound of the present invention has structures represented by both the aforementioned general formula (2A) and general formula (3A). The phosphorus-containing (meth)acryloyl compound of the present invention exhibits flame retardancy by including the structure of general formula (2A). Furthermore, by including the (meth)acryloyl group represented by general formula (3A), the flame retardant component is immobilized in the cured product, particularly in a vinyl resin, preventing bleeding and suppressing a decrease in heat resistance.

[0075] The phosphorus-containing (meth)acryloyl compound (mixture) of the present invention may contain a reaction raw material, for example, a polyvalent hydroxy compound represented by the general formula (20) described below, as long as the effect is not impaired.

[0076] The phosphorus-containing (meth)acryloyl compound of the present invention preferably has both substituents represented by general formula (2A) and general formula (3A) in its structure. However, in the case of a molecular weight distribution derived from a repeating unit represented by m, it may include a structure in which all R1s are of general formula (2A) and a structure in which all R1s are substituents represented by general formula (3A). However, in order to achieve balanced flame retardancy and heat resistance, the following phosphorus content must be satisfied when m is averaged. That is, the phosphorus content of the phosphorus-containing (meth)acryloyl compound of the present invention is 1.5 to 12.0% by weight, preferably 2.0 to 11% by weight, and more preferably 3.0 to 10% by weight.

[0077] In the phosphorus-containing (meth)acryloyl compound of the present invention, the presence ratio of the substituent represented by the general formula (2A) (the ratio of the number of moles of the general formula (2A) to the total number of moles of the general formula (2A) and the general formula (3A)) can also be calculated from the phosphorus content. The presence ratio of the phosphorus-containing substituent represented by the general formula (2A) is not problematic as long as it is not 0 mol%. If it is too low, the flame retardancy tends to be insufficient, while if it is too high, the heat resistance tends to be insufficient. Therefore, it is preferably 10 to 90 mol%, more preferably 25 to 80 mol%, and even more preferably 30 to 60 mol%. In other words, the presence ratio of the (meth)acryloyl substituent represented by the general formula (3A) is preferably 10 to 90 mol%, more preferably 20 to 75 mol%, and even more preferably 40 to 70 mol%.

[0078] The average molecular weight (Mw) of the phosphorus-containing (meth)acryloyl compound (resin) of the present invention is preferably in the range of 300 to 2,000, and more preferably in the range of 500 to 1,500.

[0079] In the general formula (1A), X represents a linking group. As can be seen from the description of the above chemical formula (1A), one of the hydrogen atoms of the aromatic ring constituting the aromatic ring of Ar is bonded to "X". Each X is independently oxygen, sulfur, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, or an aralkylene group having 8 to 20 carbon atoms.

[0080] The alkylene group is not particularly limited, and examples thereof include methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, and hexylene.

[0081] 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).

[0082]

[0083] The aralkylene group is not particularly limited, and examples thereof include aralkylene groups represented by the following chemical formulas (13) to (19).

[0084]

[0085] 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 or an alkoxy group having 1 to 10 carbon atoms. Examples of the aryl group include phenyl, tolyl, xylyl, hydroxyphenyl, benzyl, and naphthyl.

[0086] The phosphorus-containing (meth)acryloyl compound of the present invention further preferably has a structure represented by the following general formula (4).

[0087]

[0088] In the general formula (4A), R1, Ar, n1, and m are the same as those in the general formula (1).

[0089] k is 0 or 1. When k is 0, the linking group of Ar becomes a methylene group. Y represents an aromatic ring having 6 to 30 carbon atoms, and when k is 1, the linking group of Ar becomes a structure represented by the above formulae (13), (16), and (18).

[0090] Next, the method for producing the phosphorus-containing (meth)acryloyl compound of the first present invention is described. The phosphorus-containing (meth)acryloyl compound of the present invention is obtained by reacting a phosphorus-containing phenol compound represented by general formula (9A) with (meth)acrylic acid, (meth)acrylic halide, or (meth)acrylic anhydride.

[0091]

[0092] In general formula (9A), m, n1, Ar, and X are the same as those in general formula (1A), and R6 is hydrogen or a substituent represented by general formula (2A). m, n1, Ar, X, and general formula (2A) are as described above in detail. In formula (9), the substitution position of -OR6 on the aromatic ring is not particularly limited.

[0093] The phosphorus content of the phosphorus-containing phenol compound represented by general formula (9) is preferably 1.0 to 20% by weight, more preferably 3.0 to 10% by weight, and even more preferably 5.0 to 8.0% by weight. The hydroxyl equivalent is preferably 100 to 1000, more preferably 150 to 500, and even more preferably 200 to 350. The average molecular weight (Mw) of the phosphorus-containing phenol compound (resin) is preferably 200 to 1900, and more preferably 400 to 1400.

[0094] The phosphorus-containing phenol compound represented by general formula (9A) is an aromatic phosphate having one or more phenolic hydroxyl groups. Its production method follows a general method for producing aromatic phosphates. Specifically, as an example of a reaction form, an esterification reaction using a phosphorus oxyhalide (phosphorus oxyhalide) and a phenol as raw materials is performed, followed by a dehydrohalogenation reaction to obtain the corresponding phosphate.

[0095] This esterification reaction is a reversible reaction, and in order to efficiently obtain the product, operations such as using a catalyst and removing the separated hydrogen chloride from the reaction system are performed.

[0096] The released hydrogen chloride is a gas, and its volume increases as it vaporizes. Therefore, when using highly reactive raw materials, it is easily released outside the reaction system. However, when using less reactive raw materials, the amount of hydrogen halide released is small, and it tends to remain in the system, causing a reverse reaction, which may prevent the reaction from proceeding. In such cases, it is effective to capture the generated hydrogen halide to prevent the reverse reaction. Amines are sometimes used as hydrogen halide scavengers.

[0097] In the case of the phosphorus-containing phenol compound represented by the general formula (9), it is necessary to react the raw materials of the polyhydroxy compound represented by the following general formula (20) corresponding to the general formula (9) and the phosphorus halide compound represented by the following general formula (21) corresponding to the above-mentioned general formula (2A), namely, phenols and phosphorus oxyhalides.

[0098]

[0099] In the general formula (20), Ar, X, m, and n1 are the same as those in the general formula (1A).

[0100]

[0101] In the compound represented by the general formula (21), R2, R3, n2, and n3 are the same as those in the general formula (2A). Z represents a halogen atom.

[0102] However, if the essential raw material of the phosphorus-containing phenol compound represented by the general formula (9), that is, the polyhydroxy compound represented by the general formula (20) having multiple hydroxyl groups, is reacted with a 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 sequence, the feed ratio of the raw materials, the reaction conditions, etc., so that the target compound can be effectively obtained.

[0103] Therefore, instead of reacting the three raw materials, namely, phenols and phosphorus oxyhalides, which are the raw materials of the polyvalent hydroxy compound represented by the general formula (20) and the phosphorus halide compound represented by the general formula (9), simultaneously, a phosphorus oxyhalide, such as phosphorus oxychloride (POCl3), is first reacted with the phenols to obtain a phosphorus halide compound represented by the following general formula (21). Then, the obtained phosphorus halide compound represented by the general formula (21) is reacted with the polyvalent hydroxy compound represented by the general formula (20), thereby efficiently obtaining the target compound. In this case, in the first stage reaction, the phenols are added in a ratio of 2 moles to 1 mole of the phosphorus oxyhalide. The amount of the phenols is preferably in the range of 1.8 to 2.2 moles, more preferably in the range of 1.9 to 2.1 moles.

[0104] Examples of the polyvalent hydroxy compound represented by the general formula (20) include bisphenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, and 4,4'-thiobis(3-methyl-6-tert-butylphenol); dihydroxybenzenes such as catechol, resorcinol, methylresorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, and di-tert-butylhydroquinone; hydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, and trihydroxynaphthalene; phenol novolac resins, cresol novolac resins, aromatic modified phenol novolac resins, bisphenol A novolac resins, trihydroxyphenylmethane novolac resins, and naphthol novolac resins.

[0105] In the case of a novolac type phenolic resin, examples of the raw material phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol; examples of the naphthols include 1-naphthol and 2-naphthol; and examples of the raw material aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chloral, bromoaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, heptanedialdehyde, sebacic acid dialdehyde, acrolein, crotonaldehyde, salicylaldehyde, o-phthalaldehyde, and hydroxybenzaldehyde.

[0106] The phenols used as raw materials for the phosphorus halide compound represented by the general formula (21) are preferably monovalent phenols substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, and specifically include phenol, o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, tert-butylphenols, phenylphenols, 2,6-xylenol, 2,6-diethylphenol, and the like.

[0107] These phenols may be used alone or in combination of two or more.

[0108] Examples of the phosphorus oxyhalide as a raw material of the phosphorus halide compound represented by the general formula (9) include phosphorus oxychloride and phosphorus oxybromide.

[0109] The phosphorus-containing phenol compound of the present invention can be obtained by reacting the hydroxyl group of a polyvalent hydroxy compound represented by the general formula (20) with the phosphorus halide compound represented by the general formula (21). Therefore, by adjusting the molar ratio of the compound represented by the general formula (21) relative to the hydroxyl group of the polyvalent hydroxy compound, the hydroxyl equivalent and the phosphorus content can be controlled. The hydroxyl equivalent of the compound represented by the general formula (9) obtained in this reaction can be measured and compared with the hydroxyl equivalent of the compound represented by the general formula (20) used as the raw material to calculate the proportion of the compound represented by the general formula (2A) in the general formula (9). This value is equivalent to the proportion of the compound represented by the general formula (2A) in the general formula (1A) described above.

[0110] In terms of the molar ratio of the reaction, the phosphorus halide compound represented by the general formula (21) 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 per 1 mole of the hydroxyl group of the polyvalent hydroxy compound represented by the general formula (20). If it is less than 0.1 mole, the phosphorus content is reduced, and the flame retardancy is insufficient, so it is not preferred. If it is more than 0.9 moles, the hydroxyl group as a reactive group is reduced, the heat resistance is insufficient, and the viscosity is increased, so it is not preferred. This esterification reaction is a reversible reaction. In order to efficiently obtain the product, operations such as using a catalyst or removing the separated hydrogen chloride from the reaction system are performed.

[0111] The released hydrogen chloride is a gas, and its volume increases as it vaporizes. Therefore, when using highly reactive raw materials, it is easily released outside the reaction system. However, with less reactive raw materials, the amount of hydrogen halide released is small, and it tends to remain in the system, causing a reverse reaction, which may prevent the reaction from proceeding. In such cases, it is effective to capture the generated hydrogen halide to prevent the reverse reaction. Amines are sometimes used as hydrogen halide scavengers.

[0112] The reaction of the phosphorus-containing phenol compound represented by formula (9) with (meth)acrylic acid, (meth)acrylic acid halide or (meth)acrylic anhydride is not particularly limited and can be carried out in the same manner as a conventional (meth)acrylation reaction of a phenol compound.

[0113] For example, when (meth)acrylic acid is used, it can be produced by condensing a phosphorus-containing phenol compound represented by formula (3A) with 1 to 10 times the amount of (meth)acrylic acid relative to the number of hydroxyl groups in the presence of a strong acid catalyst such as sulfuric acid, p-toluenesulfonic acid, or methanesulfonic acid. Since this reaction must be carried out while removing the by-produced condensation water from the reaction system, a hydrocarbon-based solvent such as toluene that azeotropes with water is used as the reaction solvent, and the reaction solution is heated to approximately 70 to 140°C.

[0114] The phosphorus-containing (meth)acryloyl compound of the present invention can be obtained by reacting a phosphorus-containing phenol compound represented by formula (9) with a (meth)acryloyl halide or (meth)acrylic anhydride. Examples of usable (meth)acryloyl halides include acryloyl fluoride, acryloyl chloride, acryloyl bromide, and acryloyl iodide; and methacryloyl fluoride, methacryloyl chloride, methacryloyl bromide, and methacryloyl iodide.

[0115] In the practice of the present invention, (meth)acrylic acid halide or (meth)acrylic acid anhydride may be used alone or as a mixture of two or more. In the present invention, (meth)acrylic acid chloride and / or (meth)acrylic acid anhydride are preferably used due to their availability.

[0116] The amount of (meth)acrylic acid halide and / or (meth)acrylic anhydride used is 0.8 to 5 mol, preferably 0.95 to 4 mol, per 1 mol of hydroxyl groups in the phosphorus-containing phenolic compound used as a raw material. If the amount of (meth)acrylic acid halide and / or (meth)acrylic anhydride used is below the above range, the heat resistance of the resulting phosphorus-containing (meth)acrylic compound decreases, and the amount of residual hydroxyl groups increases, thereby deteriorating dielectric properties, which is not preferred. If the amount exceeds the above range, the reactor efficiency decreases and the cost increases, which is not preferred.

[0117] When using a (meth)acryloyl halide, hydrogen halide corresponding to the (meth)acryloyl halide is generated as a by-product. Therefore, it is preferable to use a basic compound in combination to capture the generated hydrogen halide while the reaction proceeds. The basic compound is not particularly limited, and examples thereof include aliphatic amines such as trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyldiethylamine, N-ethyldimethylamine, and N-ethyldipentylamine; aromatic amines such as N,N-dimethylaniline and diethylaniline; alicyclic amines such as N,N-dimethylcyclohexylamine and N,N-diethylcyclohexylamine; heterocyclic amines such as N,N-dimethylaminopyridine, N-methylmorpholine, diazabicycloundecene (DBU), diazabicyclononene (DBN), N-methylpyridine, and N-methylpyrrolidine; and diamines such as tetramethylethylenediamine and triethylenediamine. In view of their availability, aliphatic amines such as trimethylamine and triethylamine, and pyridine are particularly preferred.

[0118] The amount of the basic compound used is, for example, 0.8 to 7 moles, preferably about 0.95 to 5 moles, per 1 mole of the hydroxyl group of the phosphorus-containing phenolic compound used as a raw material. If the amount of the tertiary amine used is below this range, the hydrogen halide cannot be completely captured, resulting in corrosion of the reaction apparatus. If the amount is above this range, the cost tends to increase.

[0119] When using (meth)acrylic anhydride for the reaction, a catalyst may not be used. However, if the reaction is difficult to proceed, an ester catalyst, acid catalyst, base catalyst, or Lewis acid catalyst may be used. Examples of ester catalysts include alkali metal salts of lower carboxylic acids such as sodium acetate, potassium propionate, and sodium (meth)acrylate. Examples of acid catalysts include inorganic acids such as sulfuric acid and boric acid; and organic acids such as methanesulfonic acid and p-toluenesulfonic acid. Examples of base catalysts include organic bases such as nitrogen-containing aliphatic compounds such as triethylamine and triethylenediamine; and nitrogen-containing aromatic heterocyclic compounds such as pyridine and 4-(dimethylamino)pyridine. Examples of Lewis acid catalysts include aluminum chloride and zinc chloride.

[0120] The amount of catalyst used is preferably 10% or less, and more preferably 5% or less, relative to the (meth)acrylic anhydride used. If the amount of catalyst used exceeds the above range, catalyst removal will take time and catalyst residues may easily remain in the product, leading to deterioration of properties.

[0121] In the reaction of the phosphorus-containing phenol compound represented by formula (9) with (meth)acrylic acid halide or / and (meth)acrylic anhydride, it is preferred to use an organic solvent as the reaction solvent and conduct the reaction in solution. The solvent that can be used is not particularly limited as long as it is a solvent that is not reactive with the phenol compound and (meth)acrylic acid halide or / and (meth)acrylic anhydride. Examples thereof include tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, and water. These solvents can be used in combination as needed.

[0122] In the reaction of the phosphorus-containing phenol compound represented by formula (9) with (meth)acrylic acid halide or / and (meth)acrylic anhydride, the reaction temperature is preferably -50 to 150°C. Since the possibility of polymerization reaction increases when the reaction is carried out at a high temperature, the reaction temperature is more preferably -25 to 100°C. Furthermore, the reaction time is appropriately set depending on the set reaction temperature, but is preferably set within the range of 1 to 48 hours.

[0123] The reaction of the phosphorus-containing phenol compound represented by formula (9) with (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride can be carried out in the presence of a polymerization inhibitor. By adding a polymerization inhibitor, it is possible to prevent the (meth) acrylic acid, (meth) acrylic acid halide or (meth) acrylic anhydride supplied to the reaction and the (meth) acrylic acid ester as the target product from polymerizing and producing oligomers. As the polymerization inhibitor, known polymerization inhibitors can be used without restriction. In addition to organic compounds such as hydroquinone, hydroxy monomethyl ether, tert-butylcatechol, tert-butyl hydroquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and phenothiazine, copper compounds such as copper chloride and copper sulfide can be listed, and these can be used in combination.

[0124] After completion of the reaction, the obtained reaction solution (reaction mixture) can be subjected to distillation of the reaction solvent, solvent replacement, etc. as needed, and can be purified by washing with water or the like, activated carbon treatment, silica gel chromatography, etc., to extract the target (meth)acryloyl compound of the present invention.

[0125] Next, the phosphorus-containing vinylbenzyl compound of the second present invention will be described in detail.

[0126] The phosphorus-containing vinylbenzyl compound of the present invention is represented by the following general formula (1B).

[0127]

[0128] In the general formula (1B), m, Ar, and X are the same as those described in the general formula (1A).

[0129] In the general formula (1B) and the formulas (5), (6), (7) and (8) of Ar, R1 represents a substituent represented by the following general formula (2B) or (3B), and n1 is an integer of 1 to 4.

[0130]

[0131] In the general formula (2B), R2 and R3 are each independently a linear or branched alkyl group having 1 to 5 carbon atoms.

[0132] 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, and neopentyl. Among these, methyl is particularly preferred from the viewpoint of reactivity and availability in production.

[0133] 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 greater, the substitution position on the aromatic ring of n2 and n3 is not limited, but is preferably ortho to oxygen to prevent hydrolysis of the phosphate.

[0134]

[0135] In formula (3B), the substitution position of the vinyl group on the benzene ring is not particularly limited, but the bonding position to the methylene chain is preferably the meta-position or the para-position.

[0136] In the general formula (1B) and formulas (5), (6), (7), and (8) of Ar, n1 represents the number of substitutions by the vinylbenzyl groups represented by the general formula (2B) or (3B) bonded to each benzene ring. Here, n1 is an integer of 1 to 5.

[0137] The phosphorus-containing vinylbenzyl compound of the present invention has structures represented by both the aforementioned general formula (2B) and general formula (3B). The phosphorus-containing vinylbenzyl compound of the present invention exhibits flame retardancy by including the structure of general formula (2B). Furthermore, the inclusion of the vinylbenzyl group represented by general formula (3B) immobilizes the flame retardant component in the cured product, particularly in a vinyl resin system, preventing bleeding and suppressing a decrease in heat resistance.

[0138] The phosphorus-containing vinylbenzyl compound (mixture) of the present invention may contain a reaction raw material, for example, a polyvalent hydroxy compound represented by the general formula (20) described later, as long as the effect is not inhibited.

[0139] The phosphorus-containing vinylbenzyl compound of the present invention preferably has both substituents represented by general formula (2B) and general formula (3B) in its structure. However, in the case of a molecular weight distribution derived from a repeating unit represented by m, it may include structures in which all R1s are of general formula (2B) and structures in which all R1s are substituents represented by general formula (3B). However, in order to achieve balanced flame retardancy and heat resistance, the phosphorus content must be satisfied when m is averaged. Specifically, the phosphorus content of the phosphorus-containing vinylbenzyl compound of the present invention is 1.5 to 12.0% by weight, preferably 2.0 to 11% by weight, and more preferably 3.0 to 10% by weight.

[0140] In the phosphorus-containing vinylbenzyl compound of the present invention, the presence ratio of the substituent represented by the general formula (2B) (the ratio of the number of moles of the general formula (2B) to the total number of moles of the general formula (2B) and the general formula (3B)) can also be calculated from the phosphorus content. The presence ratio of the substituent represented by the general formula (2B) is not problematic as long as it is not 0 mol%. If it is too low, the flame retardancy tends to be insufficient, while if it is too high, the heat resistance tends to be insufficient. Therefore, it is preferably 10 to 90 mol%, more preferably 25 to 80 mol%, and even more preferably 30 to 60 mol%. In other words, the presence ratio of the vinylbenzyl substituent represented by the general formula (3B) is preferably 10 to 90 mol%, more preferably 20 to 75 mol%, and even more preferably 40 to 70 mol%.

[0141] The average molecular weight (Mw) of the phosphorus-containing vinylbenzyl compound (resin) of the present invention is preferably in the range of 300 to 2300, more preferably 500 to 2000.

[0142] The phosphorus-containing vinylbenzyl compound of the present invention more preferably has a structure represented by the following general formula (4B).

[0143]

[0144] In the general formula (4B), R1, Ar, n1, and m are the same as those in the general formula (1B).

[0145] k is 0 or 1. When k is 0, the linking group of Ar becomes a methylene group. Y represents an aromatic ring having 6 to 30 carbon atoms, and when k is 1, the linking group of Ar becomes a structure represented by the above formulae (13), (16), and (18).

[0146] The second phosphorus-containing vinylbenzyl ether compound of the present invention is obtained by reacting a phosphorus-containing phenol compound represented by the general formula (9) with a vinylbenzyl halide.

[0147]

[0148] The phosphorus-containing phenol compound represented by the general formula (9) is the same as that described in the production of the phosphorus-containing (meth)acryloyl compound of the first present invention.

[0149] Examples of the vinylbenzyl halide used in the second present invention include p-vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl bromide, and m-vinylbenzyl bromide, but are not limited thereto. Each of these compounds may be used alone or in combination of two or more. Commercially available products include CMS-14 (p-vinylbenzyl chloride, manufactured by AGC Seimi Chemical Co., Ltd.) and CMS-P (a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride, manufactured by AGC Seimi Chemical Co., Ltd.).

[0150] The mixing ratio of the phosphorus-containing phenol compound to the vinylbenzyl halide is 0.8 to 4.0 mol, preferably 0.95 to 2.0 mol, and more preferably 1.0 to 1.5 mol of the vinylbenzyl halide per 1 mol of the hydroxyl groups in the phosphorus-containing phenol compound. If the vinylbenzyl halide content is less than 0.8 mol per 1 mol of the phosphorus-containing phenol compound, the number of residual hydroxyl groups increases, resulting in reduced heat resistance. If the vinylbenzyl halide content exceeds 4.0 mol, the amount of unreacted vinylbenzyl halide remaining increases, or side-reaction polymers excessively increase.

[0151] In the reaction of the phosphorus-containing phenol compound represented by formula (9) with the vinylbenzyl halide, it is preferable to add a basic compound in order to react with the halogen of the vinylbenzyl halide and promote the reaction with the phosphorus-containing phenol compound. Examples of the basic compound include basic compounds such as alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Among them, alkali metal carbonates are preferred from the perspectives of reaction promotion and hydrolysis suppression. They may be used alone or in combination of two or more. They may be used as a solid or as a solution such as an aqueous solution, but an aqueous solution is preferred. The amount of the basic compound used is 0.5 to 5.0 mol, preferably 1 to 4 mol, and more preferably 1.2 to 3 mol, relative to 1 mol of the vinylbenzyl halide. If the amount of the basic compound used is less than 0.5 mol, the reaction does not proceed sufficiently. On the other hand, if the amount exceeds 5.0 mol, a large amount of acid is required for neutralization, which is not economically preferable.

[0152] In the reaction, as required, catalyzer can also be used.As the catalyzer used, for example, quaternary ammonium salts such as tertiary amines such as benzyldimethylamine, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, triphenylphosphine, tris (2,6-dimethoxyphenyl) phosphine, phosphonium salts such as benzyltriphenylphosphonium chloride, tetrabutylphosphonium bromide, ethyltriphenylphosphonium bromide, tetrabutylphosphonium iodide, 2-methylimidazole, 2-ethyl-4-methylimidazole and the like various catalyzers such as imidazoles can be listed, are not limited to these, can be used alone, also can use more than two kinds in combination.The usage amount of catalyzer is less than 10 weight parts relative to 100 weight parts of raw materials.

[0153] The solvent used in the reaction is not particularly limited, and examples thereof include hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and ethylbenzene; alcohols such as methanol, ethanol, propanol, butanol, pentanol, amyl alcohol, hexanol, methylpentanol, heptanol, cyclohexanol, benzyl alcohol, and furfuryl alcohol; ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, methyl phenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methylfuran, tetrahydrofuran, and the like. Ethers such as furan, ketones such as acetone, methyl acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl amyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, and cyclohexanone, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, and dimethyl sulfoxide are examples of the solvents, but are not limited to these. These solvents may be used alone or in combination of two or more. In the case of removing salts generated during the reaction by washing with water, it is preferred to use a solvent that allows the aqueous layer to separate. Examples include benzene, toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone.

[0154] The reaction can be carried out in the presence of a polymerization inhibitor. By adding a polymerization inhibitor, it is possible to prevent the vinylbenzyl halide provided for the reaction or the vinylbenzyl ether compound as the target product from polymerizing and producing by-product oligomers. As the polymerization inhibitor, known polymerization inhibitors can be used without restriction. In addition to organic compounds such as hydroquinone, hydroxy monomethyl ether, tert-butylcatechol, tert-butylhydroquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and phenothiazine, copper compounds such as copper chloride and copper sulfide can be listed, and these can be used in combination.

[0155] After completion of the reaction, the obtained reaction solution (reaction mixture) can be subjected to distillation of the reaction solvent, solvent replacement, etc. as needed, and then purified by washing with water, etc., activated carbon treatment, silica gel chromatography, etc. to obtain the target vinyl benzyl ether compound of the present invention.

[0156] Next, a flame-retardant resin composition comprising the phosphorus-containing (meth)acryloyl compound of the first invention or the phosphorus-containing vinylbenzyl compound of the second invention as an essential component and blended with a curable resin or a thermoplastic resin will be described.

[0157] The flame-retardant resin composition of the present invention has no particular limitation on the proportion of the compounding. For example, the phosphorus-containing (meth)acryloyl compound may be added in an amount of 10 to 300 parts by weight, preferably 20 to 200 parts by weight, and more preferably 50 to 150 parts by weight, per 100 parts by weight of the total amount of the curable resin and the thermoplastic resin.

[0158] Examples of curable resins include unsaturated polyester resins, curable maleimide resins, epoxy resins, polycyanate resins, phenolic resins, and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule. Preferred are epoxy resins and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule.

[0159] When curable resin is epoxy resin, be preferably the epoxy resin more than one that is selected from the epoxy resin with 2 or more epoxy groups in 1 molecule.As this epoxy resin, can enumerate cresol novolac type epoxy resin, triphenylmethane type epoxy resin, biphenyl epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin and bisphenol F type epoxy resin etc. These can be used alone, also can be used in combination of 2 or more.Think that by using such epoxy resin, thereby make the excellent dielectric properties that curable resin composition of the present invention has and the influence of fluidity stay on minimum limit, fully improve heat resistance and the adhesion of cured product.

[0160] Furthermore, when epoxy resin is included, a curing agent may be used in addition to the epoxy resin. The curing agent is not particularly limited, and examples thereof include phenolic curing agents, amine compounds, amide compounds, acid anhydride compounds, naphthol curing agents, active ester curing agents, benzoxazine curing agents, and cyanate curing agents. These may be used alone or in combination of two or more.

[0161] Furthermore, when adding an epoxy resin, a curing accelerator can be used as needed. Examples include amines, imidazoles, organic phosphines, and Lewis acids. The amount added is generally in the range of 0.2 to 5 parts by weight per 100 parts by weight of the epoxy resin.

[0162] The curable resin is not particularly limited in type, provided it is one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule (hereinafter referred to as vinyl compounds). Specifically, the vinyl compound may be any compound capable of forming crosslinks and curing by reacting with the phosphorus-containing (meth)acryloyl compound of the present invention. More preferred are compounds in which the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and even more preferred are compounds having two or more carbon-carbon unsaturated double bonds in the molecule.

[0163] The average number of carbon-carbon unsaturated double bonds per molecule of the vinyl compound as a curable resin (the number of vinyl groups (including substituted vinyl groups). It is also referred to as the number of terminal double bonds.) varies depending on the Mw of the vinyl compound, and is, for example, preferably 1 to 20, and more preferably 2 to 18. If the number of terminal double bonds is too small, it tends to be difficult to obtain sufficient heat resistance as the heat resistance of the cured product. In addition, if the number of terminal double bonds is too large, there is a possibility of excessively increased reactivity, such as a decrease in the storage stability of the curable resin composition or a decrease in the fluidity of the curable resin composition.

[0164] As the above-mentioned vinyl compounds, isocyanuric acid triallyl ester compounds such as triallyl isocyanurate (TAIC), terminal (methyl) acryloyl, styrene-modified modified polyphenylene ether (PPE), multifunctional (methyl) acrylate compounds with more than 2 (methyl) acryloyl groups in molecule, vinyl compounds (multifunctional vinyl compounds) with more than 2 vinyl groups in molecule such as polybutadiene, and vinyl benzyl compounds such as styrene and divinylbenzene, etc. can be listed. Wherein, preferably there are more than 2 carbon-carbon double bonds in molecule, specifically, TAIC, multifunctional (methyl) acrylate compounds, modified PPE resin, multifunctional vinyl compounds and divinylbenzene compounds, etc. can be listed. If these are used, it is believed that by curing reaction, crosslinking is more suitably formed, and the heat resistance of the cured product of curable resin composition can be further improved. In addition, these compounds can be used alone, or two or more combinations can be used. In addition, compounds with 1 carbon-carbon unsaturated double bond in molecule can be used in combination. Examples of the compound having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).

[0165] Examples of the thermoplastic resin include polystyrene, polyphenylene ether resin, polyetherimide resin, polyethersulfone resin, PPS resin, polycyclopentadiene resin, polycycloolefin resin, and the like; known thermoplastic elastomers (e.g., styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, and the like); and rubbers (e.g., polybutadiene and polyisoprene). Preferred examples include unmodified or modified polyphenylene ether resin and hydrogenated styrene-butadiene copolymer.

[0166] The flame retardant resin composition of the present invention may be combined with a free radical polymerization initiator (polymerization catalyst or crosslinking agent) that generates free radicals by light or / and heat. Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one; and Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-dimethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc.

[0167] As thermal radical initiators, there are benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, tert-butylcumyl peroxide, 1,3-bis(butylperoxyisopropyl)benzene, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di( In some embodiments, the free radical polymerization initiator may be 2,3-dimethyl-2,3-diphenylbutane, 2,4-dimethyl-3-propene, 2,5-dimethyl- ...

[0168] The amount of the radical polymerization initiator to be added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the phosphorus-containing (meth)acryloyl compound.

[0169] Fillers can be incorporated into the flame retardant resin composition of the present invention. Fillers include fillers added to improve the heat resistance and flame retardancy of the cured product of the curable resin composition, and known fillers can be used without particular limitation. In addition, by containing fillers, heat resistance, dimensional stability, flame retardancy, etc. can be further improved. Specifically, metal oxides such as 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 included. 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 these can be used alone, or two or more can be used in combination.

[0170] The filler can be used directly or surface-treated with a silane coupling agent such as an epoxysilane or aminosilane type. Preferred silane coupling agents are vinylsilane, methacryloxysilane, acryloxysilane, and styrylsilane types, based on their reactivity with free radical polymerization initiators. This improves the bonding strength with the metal foil and the interlayer bonding strength between the resins. Alternatively, instead of pre-surface-treating the filler, the silane coupling agent can be added by a bulk blending method.

[0171] 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 content excluding the filler (including organic components such as monomers and flame retardants, excluding solvents).

[0172] The flame-retardant resin composition of the present invention may further contain additives other than those mentioned above. Examples of such additives include defoamers such as silicone defoamers and acrylate defoamers, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes, pigments, lubricants, dispersants such as wetting and dispersing agents, and the like.

[0173] The cured product obtained by curing the flame retardant resin composition of the present invention can be used as a molded product, a laminate, a casting, an adhesive, a coating, or a film. For example, the cured product of a semiconductor encapsulating material is a casting or a molded product. As a method for obtaining a cured product for such an application, the cured product can be obtained by casting the curable resin composition or molding it using a transfer molding machine, an injection molding machine, or the like, and then heating it at 80 to 230°C for 0.5 to 10 hours.

[0174] The flame retardant resin composition of the present invention can also be used as a prepreg. When manufacturing a prepreg, for the purpose of being impregnated in a base material (fibrous base material) for forming a prepreg or for the purpose of making a circuit substrate material for forming a circuit substrate, it is prepared into a varnish-like state and can be made into a resin varnish. 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 material mentioned here specifically includes printed wiring boards, printed circuit boards, flexible printed wiring boards, build-up wiring boards, etc.

[0175] The organic solvent used in the resin varnish is not particularly limited as long as it does not inhibit the curing reaction. Examples include 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; and aromatic hydrocarbon solvents such as toluene and xylene. These solvents may be used alone or in combination. From the perspective of dielectric properties, aromatic hydrocarbons such as benzene, toluene, and xylene are preferred.

[0176] When preparing the resin varnish, the amount of the organic solvent used is preferably 5 to 900 parts by weight, more preferably 10 to 700 parts by weight, and particularly preferably 20 to 500 parts by weight, based on 100 parts by weight of the curable resin composition of the present invention.

[0177] As the base material for making prepreg material, use known material, for example base materials such as glass fibre, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper can be used separately or use more than 2 kinds.In these base materials, as required, in order to improve the adhesiveness at the interface of resin and base material, coupling agent can be used.As coupling agent, general coupling agents such as silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconium aluminate coupling agent can be used.

[0178] As a method for obtaining a prepreg material, there can be cited a method in which the above-mentioned resin varnish is impregnated into a substrate and then dried. The impregnation is carried out by dipping (immersion), coating, etc. The impregnation can be repeated multiple times as needed. In addition, at this time, it is also possible to use multiple solutions with different compositions and concentrations, and repeatedly impregnate to finally adjust to the desired resin composition and resin amount. After impregnation, the prepreg material can be obtained by heating and drying at 100 to 180°C for 1 to 30 minutes. Among them, the resin amount in the prepreg material is preferably 30 to 80 weight % of the resin content.

[0179] 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. The laminate is heated and pressurized to be laminated and integrated. Here, as the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel, etc. can be used. As the conditions for heating and pressurizing the laminate, it is sufficient to appropriately adjust the heating and pressurizing under the conditions for curing the curable resin composition. If the pressurizing pressure is too low, bubbles will remain inside the obtained laminate, and sometimes the electrical properties will be reduced. Therefore, it is preferred to pressurize under conditions that meet the formability. For example, the temperature can be set to 180 to 250°C, and the pressure can be set to 49.0 to 490.3N / cm 2 (5~50kgf / cm 2 ), and the heating and pressing time is set to 40 to 240 minutes. Furthermore, the single-layer laminate thus obtained can be used as the inner layer material to produce a multilayer board. In this case, first, a circuit is formed on the laminate using an additive method, a subtractive method, or the like. The formed circuit surface is then treated with an acid solution to perform a blackening treatment to obtain the inner layer material. On one or both sides of the inner layer material, an insulating layer is formed using a resin sheet, a metal foil with resin, or a prepreg material. Simultaneously, a conductive layer is formed on the surface of the insulating layer to form the multilayer board.

[0180] Furthermore, the curable composition of the present invention can also be used in build-up films. A method for producing a build-up film from the resin composition of the present invention includes, for example, coating the resin varnish described above 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.

[0181] Example

[0182] Next, the present invention will be described based on examples, but the present invention is not limited to these examples. Parts in each example are parts by weight.

[0183] In addition, the physical property measurement of each cured product sample in the examples was performed by the method shown below.

[0184] (1) Molecular weight and molecular weight distribution of polymers: The molecular weight and molecular weight distribution of the phosphorus-containing phenol compound (polymer) were measured using GPC (HLC-8120GPC manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent, a flow rate of 1.0 ml / min, a column temperature of 38°C, and a calibration line obtained using monodisperse polystyrene.

[0185] (2) Hydroxyl Equivalent: Accurately weigh approximately 6 mg / eq of sample in a 100 mL stoppered flask. Add 3 mL of a reagent mixed at a volume ratio of anhydrous acetic acid and pyridine = 3 / 1. Install a condenser and heat under reflux on a hot plate for 5 minutes. After cooling for 5 minutes, add 1 mL of water. Calculate the hydroxyl equivalent by potentiometric titration of this solution with a 0.5 mol / L KOH / MeOH solution.

[0186] (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 solution. The absorbance of the resulting phosphovanadomolybdic acid complex is measured at 420 nm. The phosphorus content is expressed in % using a calibration curve prepared previously using potassium dihydrogen phosphate.

[0187] (4) Glass transition temperature: The glass transition temperature was determined by using a differential scanning calorimeter manufactured by Hitachi High-Technologies Corporation at a heating rate of 10°C / min and from the baseline shift.

[0188] (5) Relative dielectric constant and dielectric loss tangent: In accordance with IPC-TM-650 2.5.5.9, the dielectric constant (Dk) and dielectric loss tangent (Df) at a frequency of 1 GHz were determined using a material analyzer (manufactured by AGILENT Technologies) at 25°C and 60% humidity using the capacitance method.

[0189] (6) Flame retardancy: According to UL94, five test pieces were used and evaluated by the vertical method. The evaluation was marked with V-0, V-1, and V-2.

[0190] The following compounds were used as raw materials in Synthesis Examples and Examples.

[0191] SP-2060N (phenol novolac resin manufactured by Nippon Steel Chemicals Co., Ltd.: hydroxyl equivalent 107 g / eq)

[0192] DC-5 (cresol novolac resin manufactured by Nippon Steel Chemicals Co., Ltd.: hydroxyl equivalent weight 121 g / eq)

[0193] SN-485 (naphthol aralkyl resin manufactured by Nippon Steel Chemicals Co., Ltd.: hydroxyl equivalent weight 212 g / eq)

[0194] Phosphorus oxychloride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0195] Resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0196] 2,6-Dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0197] Synthesis examples and Examples of the first present invention will be described.

[0198] (Synthesis Example 1A) Synthesis of di(2,6-diphenylyl)chlorophosphate (DXPC)

[0199] A 2 L 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),

[0200] POCl3

[0201] 2,6-dimethylphenol (structural formula below) 1200g (9.8mol),

[0202]

[0203] The resulting mixed solution consisted of 140 g of xylene as a solvent and 6.2 g (0.065 mol) of magnesium chloride as a catalyst. The resulting mixture was stirred and slowly heated to 160°C over approximately 3 hours to react. The generated hydrogen chloride gas was recovered using a water scrubber. The pressure in the flask was then gradually reduced to 20 kPa at this temperature to remove the xylene, unreacted phosphorus oxychloride, 2,6-dimethylphenol, and by-product hydrogen chloride, yielding 1700 g of a reaction product composed primarily of di(2,6-dimethylphenyl)chlorophosphate (DXPC: structural formula shown below). The chlorine content of the reaction mixture was 10.9% by mass.

[0204]

[0205] (Synthesis Example 2A) Synthesis of Phosphorus-Containing Phenolic Compound A

[0206] 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) was charged with 260 g of mesitylene, 58.0 g (0.5 mol) of a phenol novolac resin (the following structural formula),

[0207]

[0208] 81.8 g (0.25 mol) of DXPC synthesized in Synthesis Example 1A, 1.2 g (0.01 mol) of anhydrous magnesium chloride, and 2.0 g (0.015 mol) of anhydrous aluminum chloride as a catalyst were added. The resulting mixed solution was heated to 154°C over 2 hours while stirring, and the generated hydrogen chloride was collected. After the reaction was continued for 2.5 hours, approximately 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, acid-washed, neutralized, and then washed twice with water. The solvent was removed to obtain 113.5 g of phosphorus-containing phenolic compound A. The resulting material had a weight-average molecular weight (Mw) of 750, a phosphorus content of 5.5% by weight, and a hydroxyl equivalent of 360 g / eq. The modification rate of the phosphorus-containing functional groups with hydroxyl groups, calculated from the hydroxyl equivalent, was 38.9 mol%.

[0209] (Synthesis Example 3A) Synthesis of Phosphorus-Containing Phenolic Compound B

[0210] 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) was charged with 260 g of mesitylene, 62.7 g (0.5 mol) of a cresol novolac resin (the following structural formula),

[0211]

[0212] 81.8 g (0.25 mol) of DXPC synthesized in Synthesis Example 1A, 1.2 g (0.01 mol) of anhydrous magnesium chloride, and 2.0 g (0.015 mol) of anhydrous aluminum chloride as a catalyst were added. The same procedures as in Synthesis Example 2A were then repeated to obtain 119.4 g of phosphorus-containing phenol compound B. The resulting compound had a weight-average molecular weight (Mw) of 1032, a phosphorus content of 5.0% by weight, and a hydroxyl group equivalent of 385 g / eq. The modification rate of the phosphorus-containing functional groups with hydroxyl groups, calculated from the hydroxyl group equivalent, was 39.1 mol%.

[0213] (Synthesis Example 4) Synthesis of Phosphorus-Containing Phenol (Compound C)

[0214] 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) was charged with 260 g of mesitylene, 90.0 g (0.4 mol) of a naphthol aralkyl resin (the following structural formula),

[0215]

[0216] 64.8 g (0.2 mol) of DXPC synthesized in Synthesis Example 1A, 0.95 g (0.01 mol) of anhydrous magnesium chloride as a catalyst, and 2.0 g (0.015 mol) of anhydrous aluminum chloride were added. The same procedures as in Synthesis Example 2A were then repeated to obtain 125.6 g of phosphorus-containing phenol compound C. The resulting compound had a weight-average molecular weight (Mw) of 1160, a phosphorus content of 3.6% by weight, and a hydroxyl group equivalent of 514 g / eq. The modification rate of phosphorus-containing functional groups with hydroxyl groups, calculated from the hydroxyl group equivalent, was 37.6 mol%.

[0217] (Example 1A) Synthesis of phosphorus-containing (meth)acryloyl compound A

[0218] In a glass separable flask equipped with a stirrer, thermometer, condenser, and dropping funnel, 100.0 g of phosphorus-containing phenol compound A, 150.0 g of tetrahydrofuran, 28.3 g of triethylamine, and 2.1 g of 4-dimethylaminopyridine were placed and dissolved at room temperature. Under a nitrogen atmosphere, 52.3 g of methacrylic anhydride (structural formula shown below) was added dropwise over 1 hour, and the reaction was continued at 50°C for 6 hours.

[0219]

[0220] The reaction solution was then concentrated, dissolved in 277.7 g of toluene, and washed sequentially with hydrochloric acid, aqueous sodium carbonate solution, and water. After washing with water, the mixture was dehydrated, filtered, and the solvent concentrated to obtain 214.2 g of a toluene solution of phosphorus-containing methacryloyl compound A. Compound A had a molecular weight (Mw) of 750, a phosphorus content of 4.7%, and a (meth)acryloyl substituent ratio of 61.9 mol%. In this case, the (meth)acryloyl substituent ratio is the value that assumes that all hydroxyl groups are (meth)acryloylated (the same applies to the following examples).

[0221] (Example 2A) Synthesis of phosphorus-containing (meth)acryloyl compound B

[0222] In a glass separable flask equipped with a stirrer, thermometer, condenser, and dropping funnel, 100.0 g of phosphorus-containing phenol compound B, 100.0 g of tetrahydrofuran, 26.4 g of triethylamine, and 2.0 g of 4-dimethylaminopyridine were placed and dissolved at room temperature. Under a nitrogen atmosphere, 49.3 g of methacrylic anhydride was added dropwise over 1 hour, and the reaction was continued at 50°C for 6 hours.

[0223] The reaction solution was then concentrated, dissolved in 275.8 g of toluene, and then washed and concentrated in the same manner as in Example 1A to obtain 211.9 g of a toluene solution of phosphorus-containing methacryloyl compound B having a solids concentration of 50%. Compound B had a molecular weight (Mw) of 1130, a phosphorus content of 4.5%, and a (meth)acryloyl substituent ratio of 60.9 mol%.

[0224] (Example 3A) Synthesis of Phosphorus-Containing (Meth) Acryloyl Compound C

[0225] In a glass separable flask equipped with a stirrer, thermometer, condenser, and dropping funnel, 100.0 g of phosphorus-containing phenol compound C, 150.0 g of tetrahydrofuran, 19.7 g of triethylamine, and 1.5 g of 4-dimethylaminopyridine were placed and dissolved at room temperature. Under a nitrogen atmosphere, 36.8 g of methacrylic anhydride was added dropwise over 1 hour, and the reaction was continued at 50°C for 6 hours.

[0226] The reaction solution was then concentrated, dissolved in 264.2 g of toluene, and then washed and concentrated in the same manner as in Example 1A to obtain 203.9 g of a toluene solution of a phosphorus-containing methacryloyl compound C having a solids concentration of 50%. Compound C had a molecular weight (Mw) of 1260, a phosphorus content of 3.2%, and a (meth)acryloyl substituent ratio of 62.4 mol%.

[0227] (Comparative Synthesis Example A) Synthesis of Phosphorus-Containing Methacryloyl Compound D

[0228] The synthesis was carried out according to the method described in Japanese Patent Application Laid-Open No. 2022-16422. Specifically, 1500 g of phosphorus oxychloride, 611 g of 2,6-dimethylphenol, and 1.2 g of magnesium chloride as a catalyst were added to 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).

[0229] The resulting mixed solution was stirred and slowly heated to 110°C over approximately 3 hours to react, and the generated hydrogen chloride (hydrochloric acid gas) was recovered using a water scrubber. The pressure in the flask was then slowly reduced to 12 kPa at 120°C to remove unreacted phosphorus oxychloride, phenol, and by-produced hydrogen chloride, thereby obtaining 1200 g of mono(2,6-dimethylphenyl)dichlorophosphate.

[0230] A 2-liter four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a condenser was charged 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. Separately, the dropping funnel was charged with 203 g of the mono(2,6-dimethylphenyl)dichlorophosphate.

[0231] The mixed solution in the four-necked flask was heated to 20°C while stirring. While maintaining this temperature (20°C), mono(2,6-dimethylphenyl)dichlorophosphate in the dropping funnel was added dropwise over 2 hours. After the addition was complete, the mixture was heated to 65°C and stirred for 5 hours to obtain a reaction product. The resulting reaction product was washed with dilute hydrochloric acid and water, then heated to 150°C, reduced to 2 kPa, and water, toluene, and low-boiling components were distilled off. The mixture was then cooled to room temperature to obtain 330 g of phosphorus-containing phenol compound D as a dark brown solid.

[0232] In a glass separable flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel, 200 g of the phosphorus-containing phenol compound D, 133.2 g of tetrahydrofuran, and 19.5 g of triethylamine were placed and dissolved, followed by cooling to below 5°C in an ice bath. 78.0 g of methacryloyl chloride was added dropwise over 1 hour under a nitrogen atmosphere, and the reaction was continued for a further 2 hours.

[0233] The reaction mixture was then concentrated, dissolved in 601.6 g of toluene, and washed sequentially with hydrochloric acid, aqueous sodium carbonate solution, and water. After washing with water, the mixture was dehydrated, filtered, and the solvent concentrated to obtain 227.6 g of a toluene solution of phosphorus-containing methacryloyl compound D. The resulting compound D had a molecular weight (Mw) of 560 and a phosphorus content of 5.2%.

[0234] Examples 4A to 9A, Comparative Examples 1A to 5A

[0235] <Preparation of curable resin composition and production of cured product>

[0236] A varnish was prepared by mixing the various components in the proportions shown in Table 1A. This was then applied to a PET film and dried in a 130°C oven for 5 minutes to produce a film of the resin composition. The film was then pulverized to obtain a powder of the resin composition. This powder was then sandwiched between a stainless steel mirror plate and spaced with a spacer. The mixture was then formed in a vacuum oven at 210°C for 90 minutes to obtain a sample of the cured product.

[0237] <Preparation of flame retardant test pieces>

[0238] A varnish was prepared by mixing various components in the ratios shown in Table 1A. Glass cloth (manufactured by Nitto Bosho Co., Ltd.; Type 7628; Product No. H258) was impregnated with the resin varnish and then dried by heating at 130°C for 5 minutes to obtain a prepreg.

[0239] Eight sheets of the resulting prepreg were stacked with upper and lower copper foils (Mitsui Mining & Smelting Co., Ltd., 3EC-III, 35 μm thick) and vacuum pressed at 2 MPa under the conditions of 130°C for 15 minutes followed by 190°C for 80 minutes to produce a 1.6 mm thick laminate. The copper foil was etched and cut to produce flame retardancy test pieces.

[0240] OPE-2St: A terminal styrene-modified polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0241] PX-200: Aromatic condensed phosphate ester manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 9.0%

[0242] PerbutylP: 1,3-bis(butylperoxyisopropyl)benzene manufactured by NOF Corporation. The results are shown in Table 1A.

[0243] [Table 1A]

[0244]

[0245] Next, synthesis examples and examples of the second invention will be described.

[0246] (Synthesis Example 1B) Synthesis of di(2,6-diphenylyl)chlorophosphate (DXPC)

[0247] A 2 L 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),

[0248] POCl3

[0249] 2,6-dimethylphenol (structural formula below) 1200g (9.8mol),

[0250]

[0251] The resulting mixed solution consisted of 140 g of xylene as a solvent and 6.2 g (0.065 mol) of magnesium chloride as a catalyst. The resulting mixture was stirred and slowly heated to 160°C over approximately 3 hours to react. The generated hydrogen chloride gas was recovered using a water scrubber. The pressure in the flask was then gradually reduced to 20 kPa at this temperature to remove the xylene, unreacted phosphorus oxychloride, 2,6-dimethylphenol, and by-product hydrogen chloride, yielding 1700 g of a reaction product composed primarily of di(2,6-dimethylphenyl)chlorophosphate (DXPC: structural formula shown below). The chlorine content of the reaction mixture was 10.9% by mass.

[0252]

[0253] (Synthesis Example 2B) Synthesis of Phosphorus-Containing Phenolic Compound A

[0254] 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) was charged with 260 g of mesitylene, 58.0 g (0.5 mol) of a phenol novolac resin (the following structural formula),

[0255]

[0256] 81.8 g (0.25 mol) of DXPC synthesized in Synthesis Example 1B, 1.2 g (0.01 mol) of anhydrous magnesium chloride, and 2.0 g (0.015 mol) of anhydrous aluminum chloride as a catalyst were added. The resulting mixed solution was heated to 154°C over 2 hours while stirring, and the generated hydrogen chloride was collected. After the reaction was continued for 2.5 hours, approximately 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, acid-washed, neutralized, and then washed twice with water. The solvent was removed to obtain 113.5 g of phosphorus-containing phenolic compound A. The resulting material had a weight-average molecular weight (Mw) of 750, a phosphorus content of 5.5% by weight, and a hydroxyl equivalent of 360 g / eq. The modification rate of the phosphorus-containing functional groups with hydroxyl groups, calculated from the hydroxyl equivalent, was 38.9 mol%.

[0257] (Synthesis Example 3B) Synthesis of Phosphorus-Containing Phenolic Compound B

[0258] 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) was charged with 260 g of mesitylene, 62.7 g (0.5 mol) of a cresol novolac resin (the following structural formula),

[0259]

[0260] 81.8 g (0.25 mol) of DXPC synthesized in Synthesis Example 1B, 1.2 g (0.01 mol) of anhydrous magnesium chloride, and 2.0 g (0.015 mol) of anhydrous aluminum chloride as a catalyst were added. The same procedures as in Synthesis Example 2B were then repeated to obtain 119.4 g of phosphorus-containing phenol compound B. The resulting compound had a weight-average molecular weight (Mw) of 1032, a phosphorus content of 5.0% by weight, and a hydroxyl group equivalent of 385 g / eq. The modification rate of the phosphorus-containing functional groups with hydroxyl groups, calculated from the hydroxyl group equivalent, was 39.1 mol%.

[0261] (Synthesis Example 4B) Synthesis of Phosphorus-Containing Phenol (Compound C)

[0262] 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) was charged with 260 g of mesitylene, 90.0 g (0.4 mol) of a naphthol aralkyl resin (the following structural formula),

[0263]

[0264] 64.8 g (0.2 mol) of DXPC synthesized in Synthesis Example 1B, 0.95 g (0.01 mol) of anhydrous magnesium chloride as a catalyst, and 2.0 g (0.015 mol) of anhydrous aluminum chloride were added. The same procedures as in Synthesis Example 2B were then repeated to obtain 125.6 g of phosphorus-containing phenol compound C. The resulting compound had a weight-average molecular weight (Mw) of 1160, a phosphorus content of 3.6% by weight, and a hydroxyl group equivalent of 514 g / eq. The modification rate of phosphorus-containing functional groups with hydroxyl groups, calculated from the hydroxyl group equivalent, was 37.6 mol%.

[0265] (Example 1B) Synthesis of phosphorus-containing vinylbenzyl compound A

[0266] In a glass separable flask equipped with a stirrer, thermometer, and condenser, 100.0 g of phosphorus-containing phenol compound A and 66.7 g of diethylene glycol dimethyl ether were placed and dissolved under a nitrogen atmosphere by heating to 75°C. 48.6 g of vinylbenzyl chloride (CMS-P, structural formula shown below) was added, and after homogenization, 4.5 g of tetrabutylammonium bromide and 115.2 g of a 50% aqueous potassium carbonate solution were added, and the reaction was allowed to proceed for 10 hours.

[0267]

[0268] The reaction solution was then concentrated and dissolved in 319.6 g of toluene. The solution was then neutralized with a 10% aqueous sodium dihydrogen phosphate solution and washed with water. The solution was then dehydrated, filtered, and the solvent concentrated to yield 233.0 g of a 50% toluene solution of phosphorus-containing vinylbenzyl ether compound A. Compound A had a weight-average molecular weight (Mw) of 850, a phosphorus content of 4.4%, and a vinylbenzyl substituent presence of 61.9 mol%. In this case, the vinylbenzyl substituent presence is a value that assumes that all hydroxyl groups are vinylbenzylated (the same applies to the following examples).

[0269] (Example 2B) Synthesis of phosphorus-containing vinyl benzyl ether compound B

[0270] In a glass separable flask equipped with a stirrer, thermometer, and condenser, 100.0 g of phosphorus-containing phenol compound B and 66.7 g of diethylene glycol dimethyl ether were placed and dissolved under a nitrogen atmosphere by heating to 75°C. 45.4 g of CMS-P was added, and after the mixture became homogeneous, 4.4 g of tetrabutylammonium bromide and 107.7 g of a 50% aqueous potassium carbonate solution were added, and the reaction was allowed to proceed for 10 hours.

[0271] The reaction solution was then concentrated, dissolved in 314.0 g of toluene, neutralized with a 10% aqueous sodium dihydrogen phosphate solution, and washed with water. The solution was then dehydrated, filtered, and the solvent concentrated to yield 229.0 g of a 50% toluene solution of phosphorus-containing vinylbenzyl ether compound B. Compound B had a weight-average molecular weight (Mw) of 1250, a phosphorus content of 4.2%, and a vinylbenzyl substituent content of 60.9 mol%.

[0272] (Example 3B) Synthesis of Phosphorus-Containing Vinyl Benzyl Ether Compound C

[0273] In a glass separable flask equipped with a stirrer, thermometer, and condenser, 100.0 g of the phosphorus-containing phenol compound C and 66.7 g of diethylene glycol dimethyl ether were placed and dissolved under a nitrogen atmosphere by heating to 75°C. 34.0 g of CMS-P was added, and after the mixture became homogeneous, 4.0 g of tetrabutylammonium bromide and 80.7 g of a 50% aqueous potassium carbonate solution were added, and the reaction was allowed to proceed for 10 hours.

[0274] The reaction solution was then concentrated, dissolved in 293.8 g of toluene, neutralized with a 10% aqueous sodium dihydrogen phosphate solution, and washed with water. The solution was then dehydrated, filtered, and the solvent concentrated to yield 214.0 g of a 50% toluene solution of phosphorus-containing vinylbenzyl ether compound C. Compound C had a weight-average molecular weight (Mw) of 1350, a phosphorus content of 3.1%, and a vinylbenzyl substituent content of 62.4 mol%.

[0275] (Comparative Synthesis Example 1B)

[0276] Synthesized according to Japanese Patent Application Laid-Open No. 2022-16423. Specifically, a four-necked flask with a capacity of 2 liters equipped with a stirrer, a thermometer, a dropping funnel and a condenser was filled with 320g of 2,3,5-trimethylhydroquinone, 135g of pyridine as a hydrogen chloride capture agent, and 200g of toluene as a solvent. In addition, 203g of DXPC was filled in the dropping funnel. The mixed solution in the four-necked flask was heated to a temperature of 20°C while stirring, and the DXPC in the dropping funnel was dropped over 2 hours while being maintained at this temperature (20°C). After the dropwise addition was completed, it was heated to 65°C and stirred for 5 hours to obtain a reaction product. After the obtained reaction product was washed with dilute hydrochloric acid and water, it was heated to a temperature of 150°C, reduced to 2kPa, water, toluene, and low-boiling-point components were distilled off, and cooled to room temperature to obtain 330g of a dark brown solid containing phosphorus phenol compound D.

[0277] In a glass separable flask equipped with a stirrer, thermometer, condenser, and dropping funnel, 200 g of phosphorus-containing phenol compound D and 133.2 g of diethylene glycol dimethyl ether were placed and dissolved under a nitrogen atmosphere by heating to 75°C. 128.6 g of CMS-P was added, and after homogenization, 8.2 g of tetrabutylammonium bromide and 213.4 g of a 50% aqueous potassium carbonate solution were added, and the reaction was allowed to proceed for 15 hours.

[0278] The reaction solution was then concentrated and dissolved in 665.0 g of toluene. The solution was then neutralized with a 10% aqueous sodium dihydrogen phosphate solution and washed with water. The solution was then dehydrated, filtered, and the solvent concentrated to obtain 381.5 g of a toluene solution of phosphorus-containing vinyl benzyl ether compound D. The resulting compound D had a weight-average molecular weight (Mw) of 560 and a phosphorus content of 5.2%.

[0279] Examples 4B to 9B, Comparative Examples 1B to 5B

[0280] <Preparation of curable resin composition and production of cured product>

[0281] A varnish was prepared by mixing the various components in the proportions shown in Table 1B. This was then applied to a PET film and dried in a 130°C oven for 5 minutes to produce a film of the resin composition. The film was then pulverized to obtain a powder of the resin composition. This powder was then sandwiched between a stainless steel mirror plate and spaced with a spacer. The mixture was then formed in a vacuum oven at 210°C for 90 minutes to obtain a cured product sample.

[0282] <Preparation of flame retardant test pieces>

[0283] A varnish was prepared by mixing various components in the ratios shown in Table 1B. Glass cloth (manufactured by Nitto Bosho Co., Ltd.; Type 7628; Product No. H258) was impregnated with the resin varnish and then dried by heating at 130°C for 5 minutes to obtain a prepreg.

[0284] Eight sheets of the resulting prepreg were stacked with upper and lower copper foils (Mitsui Mining & Smelting Co., Ltd., 3EC-III, 35 μm thick) and vacuum pressed at 2 MPa under the conditions of 130°C for 15 minutes followed by 190°C for 80 minutes to produce a 1.6 mm thick laminate. The copper foil was etched and cut to produce flame retardancy test pieces.

[0285] OPE-2St: A terminal styrene-modified polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0286] PX-200: Aromatic condensed phosphate ester manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 9.0%

[0287] PerbutylP: 1,3-bis(butylperoxyisopropyl)benzene manufactured by NOF Corporation. The results are shown in Table 1B.

[0288] [Table 1B]

[0289]

[0290] Industrial applicability

[0291] The phosphorus-containing (meth)acryloyl compound and phosphorus-containing vinyl benzyl ether compound of the present invention can be used to impart flame retardancy to plastic materials used in electrical and electronic products, OA equipment, communication equipment, building materials, and thermosetting resins such as epoxy resins. In particular, they can be used as flame retardant materials for reducing transmission loss at higher frequencies associated with the increase in the amount of information processed by electronic devices.

Claims

1. A phosphorus-containing (meth)acryloyl compound, characterized in that Represented by general formula (1A), In the general formula (1A), m is a number from 1 to 20, n1 is each independently a number from 1 to 4, Ar is an aromatic ring having 6 to 30 carbon atoms which may have a substituent, R1 is each independently a substituent represented by the general formula (2A) or the general formula (3A), and the compound contains at least one substituent represented by the general formula (2A) and at least one substituent represented by the general formula (3A), and X represents a linking group and is each independently oxygen, sulfur, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, or an aralkylene group having 8 to 32 carbon atoms. In the general formula (2A), R2 and R3 are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, n2 and n3 are each independently a number from 0 to 5, Wherein, R4 is hydrogen or methyl.

2. The phosphorus-containing (meth)acryloyl compound according to claim 1, wherein It is represented by the following general formula (4A), In the general formula (4A), R1, n1, and m are the same as those in the general formula (1A), Y is an aromatic ring group having 6 to 30 carbon atoms which may have a substituent, k is 0 or 1, and Ar represents an aromatic group derived from an aromatic compound represented by the following general formula (5), (6), (7), or (8). In the above general formulas (5), (6), (7) and (8), R5 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, n4 is an integer of 0 to 4, and R1 and n1 are the same as in general formula (1A).

3. The phosphorus-containing (meth)acryloyl compound according to claim 1, wherein The phosphorus content is 1.5 to 12.0% by weight.

4. The method for producing a phosphorus-containing (meth)acryloyl compound according to claim 1, wherein The phosphorus-containing phenol compound represented by the general formula (9) is reacted with one or more of (meth)acrylic acid, (meth)acrylic halide or (meth)acrylic anhydride, In the general formula (9), m, n1, Ar, and X are the same as those in the general formula (1A), and R6 is hydrogen or a substituent represented by the above-mentioned general formula (2A).

5. A flame retardant resin composition, characterized in that The phosphorus-containing (meth)acryloyl compound according to claim 1 and one or more thermosetting resins or thermoplastic resins are blended therein. 6 . A laminate for an electronic circuit board obtained by using the flame-retardant resin composition according to claim 5 .

7. A phosphorus-containing vinyl benzyl ether compound, characterized in that Represented by general formula (1B), In the general formula (1B), m is a number from 1 to 20, n1 is each independently a number from 1 to 4, Ar is an aromatic ring having 6 to 30 carbon atoms which may have a substituent, R1 is each independently a substituent represented by the general formula (2B) or a vinylbenzyl group represented by the general formula (3B), and the compound contains at least one substituent represented by the general formula (2B) and at least one substituent represented by the general formula (3B), and X represents a linking group and is each 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. In the general formula (2B), R2 and R3 are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, n2 and n3 are each independently a number from 0 to 5, 8. The phosphorus-containing vinyl benzyl ether compound according to claim 7, characterized in that It is represented by the following general formula (4B), In the general formula (4B), R1, n1, and m are the same as those in the general formula (1B), Y is an aromatic ring group having 6 to 30 carbon atoms which may have a substituent, k is 0 or 1, and Ar represents an aromatic group derived from an aromatic compound represented by the following general formula (5), (6), (7), or (8). In the above general formulas (5), (6), (7) and (8), R5 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, n4 is an integer of 0 to 4, and R1 and n1 are the same as in general formula (1B).

9. The phosphorus-containing (meth)acryloyl compound according to claim 7, wherein The phosphorus content is 1.5 to 12.0% by weight.

10. The method for producing a phosphorus-containing vinyl benzyl ether compound according to claim 7, wherein The phosphorus-containing phenol compound represented by the general formula (9) is reacted with a vinylbenzyl halide. In the general formula (9), m, n1, Ar, and X are the same as those in the general formula (1B), and R6 is hydrogen or a substituent represented by the above-mentioned general formula (2B).

11. A flame retardant resin composition, characterized in that The phosphorus-containing vinyl benzyl ether compound according to claim 7 and one or more thermosetting resins or thermoplastic resins are mixed therein. 12 . A laminate for an electronic circuit board obtained by using the flame-retardant resin composition according to claim 11 .

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