WO2002014334A1

WO2002014334A1 - Phenol compounds, resin compositions and products of curing thereof

Info

Publication number: WO2002014334A1
Application number: PCT/JP2001/006847
Authority: WO
Inventors: Kenichi Kuboki
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 2000-08-10
Filing date: 2001-08-09
Publication date: 2002-02-21

Abstract

Phenol compounds including those of the general formula [|], which are prepared by polycondensation of 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide with formaldehyde and mono- or poly-hydric phenols; resin compositions prepared by using the phenol compounds, which are reduced in water absorbance and exhibit flame retardance; and products of curing and plastics, made from the resin compositions. [|]

Description

Specification

Phenol compound, resin composition and cured product thereof

The present invention is applicable to various plastics (Polycarbonate, PEEK :, PPO, Polysulfone, etc.) raw materials or additives, thermosetting resins (epoxy resins, cyanate resins, acrylate resins, etc.) raw materials, or highly reliable semiconductor encapsulation Insulation materials for electric and electronic parts, including composites, and various composite materials such as laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastic), components such as adhesives, paints, molding materials, etc. Phenol compounds useful as intermediates for seed industry and high-reliability semiconductor encapsulations containing them, including electrical and electronic component insulation materials, as well as laminates (printed wiring boards, build-up boards) and CFRP (Carbon fiber reinforced plastics), optical materials and other composite materials, adhesives, paints, and other useful resin compositions and cured products Than it is. Technology background

Phenol compounds are used in the fields of thermoplastic plastic raw materials and additives (such as antioxidants), thermosetting resin raw materials, and components such as insulating materials for electric and electronic parts, structural materials, adhesives, and paints. Widely used in

In addition, in the flame retardation of organic polymer materials, mainly organic compounds such as phosphorus-based and octogen-based flame retardants, aluminum hydroxide, and trioxide are used in combination as necessary. . In particular, bromine-based flame retardants and antimony trioxide are often used in electrical and electronic components that require high reliability, including semiconductors.

However, in recent years, it has been pointed out that halogen-based flame retardants contribute to the generation of toxic substances such as dioxin by improper treatment after disposal, and antimony trioxide is also considered to be toxic. Most of the phosphorus-based flame retardants that are commonly used are phosphoric acid esters. There is a concern about corrosion of steel. Therefore, a flame-retardant polymer material that does not contain halogen or antimony and has a structure that does not easily cause hydrolysis or the like in a phosphorus system has been demanded. Not enough.

The present invention synthesizes a phenolic compound which is a raw material or additive of a variety of new plastics (polycarbonate, PEEK, PPO, polysulfone, etc.) and a raw material of a thermosetting resin (epoxy resin, cyanate resin, acrylate resin, etc.). By using these in a resin composition, the cured product can exhibit excellent low water absorption and flame retardancy, and can be used as an insulating material for electrical and electronic parts (such as a highly reliable semiconductor sealing material) and a laminate. Provide useful materials for boards (printed wiring boards, build-up boards, etc.) and various composite materials including CFRP, adhesives, paints, etc. Disclosure of the invention

Means for Solving the Problems The inventors of the present invention have made various studies to solve the above problems, and have completed the present invention. That is, the present invention

(1) Equation (1)

A phenol compound obtained by polycondensing a phosphorus-containing compound represented by the following formula with formaldehyde and monovalent or polyvalent phenols,

(2) The phosphorus-containing compound of the formula (1) and the following formula (2)

(In the formula (2), X is a single bond, an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, a sulfone group, a sulfoxide group, or a compound represented by the following formula (3) Represents one of the three groups described in _c

(In the formula (3), g. Represents an integer of 1 to 3. m, d and e each represent an integer of 0 to 6.)

R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group or a methylol group, but when R is 1, it is a methylol group, and when there are multiple values, it is independent. Each may be the same or different, and at least one is a methylol group. Q represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Multiple A's independently represent a carbon atom or a nitrogen atom. W represents an oxygen atom or a sulfur atom. When a plurality of X, Q and W are present in the structure represented by the formula (2), each X, each Q and each W are independently the same or different. You may. Also, when g, m, d and e are present in the structure represented by the formula (2), a plurality of g, m, d and e are different even if they are independently the same. May be. )

A plurality of Rs in the formula (2) independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group or a methylol group, and at least 1 The individual is a methylol group. h and i each independently represent an integer of 1 to 3. j and k independently represent an integer of 0-6. When a plurality of i and k exist in the structure represented by the formula (2), each i and each k may be independently the same or different. n represents an average value and represents a real number of 0 to 20. )

And a phenol compound obtained by polycondensing the phenols other than the methylol compound of the formula (2) if necessary as a polycondensation component, and (3) a phenol compound obtained by the polycondensation.

(In the formula (4), X is a single bond, an optionally substituted divalent hydrocarbon residue having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, a sulfone group, a sulfoxide group, or a compound represented by the following formula (5) ) Shows any one of the three groups described in the above.

(In the formula (5), g represents an integer of 1 to 3. m, d, and e each represent an integer of 0 to 6. A plurality of Zs independently represent a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms. Group, an alkoxy group, or one of the following formulas (6), at least one of which is represented by the following formula:

It is a group of (6). Q represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Multiple A's independently represent a carbon atom or a nitrogen. W represents an oxygen atom or a sulfur atom. When a plurality of X, Q and W are present in the structure represented by the formula (4), each X, each Q and each W may be independently the same or different. Is also good. Also, when g, m, d, and e exist in the structure represented by Equation (4), each g, each m, each d, and each e are independently the same. Or different. )

A plurality of Zs in the formula (4) are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or a compound represented by the following formula (6)

And at least one is a group of the formula (6). h and i each independently represent an integer of 1 to 3. j and k each independently represent an integer of 0-6. When a plurality of i and k exist in the structure represented by the formula (4), each i and each k may be independently the same or different. η indicates an average value, and indicates a real number of 0 to 20. )

A phenolic compound represented by

(4) The phenol compound according to the above (3), wherein h and i are 1 in the formula (4).

(5) The phosphorus-containing compound represented by the formula (1) and the formula (7)

(In the formula (7), represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, and when two or more are present, they may be the same or different independently. Y is 2 And X represents an integer of 1 to 5.) A phenolic compound obtained by condensing a methyl alcohol compound represented by

(6) Equation (8)

(In the formula (8), represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, and when two or more are present, they may be the same or different independently. Y is 2 And X represents an integer of 1 to 5.) A phenol compound represented by the following formula:

(7) A resin composition containing the polyvalent phenol compound according to any one of the above (1) to (6),

(8) The resin according to the above (7), which does not contain a halogen.

(9) The resin composition according to the above (8), wherein the resin composition is a curable resin composition,

(10) The resin composition according to the above (9), wherein the resin composition is an epoxy resin composition,

(11) A cured product of the resin composition according to any one of the above ('8) to (10),

(12) The cured product according to the above (11), which has flame retardancy.

(13) Flame-retardant thermoplastic containing the phenolic compound according to any one of the above (1) to (6)

About. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. In the following, “parts” means “parts by mass”.

The phenolic compound of the present invention includes, for example, a phosphorus-containing compound of the formula (1), formaldehyde, monovalent phenols and polyvalent phenols (hereinafter simply referred to as phenols include both monovalent and polyvalent). Or polycondensation in a single batch, or by first reacting formaldehyde with phenols, then reacting with the phosphorus-containing compound of formula (1) and, if necessary, further dehydrating condensation with phenols. or Can be obtained by reacting various aldehydes in the presence of phenols.

More specifically, the phenol compound of the present invention includes a phenol compound represented by the formula (4). The phenolic compound of the present invention represented by the formula (4) may be synthesized by any method. More preferably, the methylol derivative represented by the formula (2) is synthesized by the latter method or the like. It can be obtained by dehydration condensation of a methylol group with a phosphorus-containing compound of the formula (1), and, if necessary, further dehydration condensation with phenols or reaction of various aldehydes in the presence of phenols.

In the phenol compound of the formula (4), a compound in which n is 0 to 10, more preferably 0 to 5, and still more preferably 0 to 3 is one of preferred compounds. Further, a compound in which h and i are 1 in the formula (4) is also preferable. Therefore, a compound in which n is a preferred range and h and i are 1 is one of more preferred compounds. Further, the compound of the formula (4) preferably has two or more phosphorus-containing groups represented by the formula (6). It is more preferable when this is combined with the above preferred range. In the phenolic compound of the present invention, an example of a compound having a preferred range is a compound represented by the formula (8). The compound represented by the formula (8) can be further combined with the preferred range described above.

In the present invention, a simple hydrocarbon group or a monovalent hydrocarbon means a group obtained by removing one hydrogen atom from a hydrocarbon, and a divalent hydrocarbon group means two hydrogen atoms from a hydrocarbon. Excluding divalent.

In the present invention, the divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in the formula (2) may be a straight-chained, branched or cyclic divalent hydrocarbon group. It may be a divalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

When the divalent hydrocarbon group has a substituent, examples of the substituent include a carbon atom such as a halogen atom (a chlorine atom, a bromine atom, and a fluorine atom), a hydroxy group, and an alkoxy group (a methoxy group, an ethoxy group, and a propyl group). And alkyl groups of numbers 1 to 4). When the divalent hydrocarbon group is a cyclic group or includes a cyclic group, the ring is substituted with an alkyl group (eg, a methyl group, an ethyl group, a propyl group). And b) an alkyl group having 1 to 4 carbon atoms such as a group).

In the formula (2) and the like, the condensed ring portion described by a broken line indicates that it may or may not be present, and when present, the condensed ring portion is combined with the solid benzene ring to form a naphthalene ring. When there is no benzene ring, the benzene ring in the solid line is shown.

The methylol compound represented by the formula (2) can be obtained by a conventionally known method. For example, monovalent phenols or polyvalent phenols are usually converted to formaldehyde in the presence of an alkaline catalyst. A reaction method, a method of reducing an aldehyde group of a monovalent aromatic aldehyde compound or a polyvalent aromatic aldehyde compound, and the like can be adopted. Alkali catalysts used in the former method include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal alkoxides, di- or tri (hydroxy substituents). And C 1 -C 4 alkyl) amines which may be present. Specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, and carbonic acid. Sodium, potassium carbonate, magnesium carbonate, calcium carbonate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, triethylamine, trioctylamine, tetramethylethylenediamine, N, N-dimethylethanolamine, N, N— Getylmethanolamine, N, N-dibutylethanolamine, etc. However, the present invention is not limited to these.

The reaction between the phenols and formaldehyde is usually carried out in an aqueous solution at a reaction temperature of about room temperature to about 100 ° C. for about 1 to 10 hours using an equimolar amount or a slight excess of formaldehyde. Just do it.

Specific examples of the monovalent phenols that can be used in synthesizing the methyl alcohol of the formula (2) include alkenyl-substituted phenols such as phenol, cresol phenol phenol, butyl phenol, and octyl phenol, and phenyl phenol. Examples include aromatic-substituted phenols such as dimethylphenol, alkoxy-substituted phenols such as methoxyphenol and ethoxyphenol, naphthol, and alkyl-substituted naphthol.

Specific examples of polyvalent phenols that can be used in synthesizing the methyl ester of formula (2) include resorcin, hydroquinone, catechol, phloroglicinol, Droxynaphthalene, dihydroxyphenyl ether, thiodiphenol, dihydroxyphenylsulfone, bisphenols (bisphenol A, bisphenol-F, pisphenol, biphenol, bisphenol AD, etc.), phenols and various aldehydes (formaldehyde , Acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, pyridinecarboxaldehyde, thiophene carboxaldehyde, daltaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) With polyphenols, phenols and various gen compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornage , Vinylnorpolenene, tetrahydroindene, divinylbenzene, dipinylbiphenyl, diisoprobenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acedone, methylethylketone, methylisobutylketone, acetophenone) , Benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, a, a, a, monobenzenedimethanol, biphenyldimethanol, a, a, a, a, -biphenyldimethano) Polycondensates with phenols and aromatic dichloromethyls (a, —dichloroxylene, pschloromethylbiphenyl, etc.), polycondensates of bisphenols with various aldehydes, etc. Is mentioned.

The above monovalent and divalent phenols can be used as a mixture of two or more kinds, respectively, or monovalent and divalent phenols can be used in combination. It can also be used for one-batch (poly) condensation of the phosphorus-containing compound of the formula (1) with formaldehyde and monovalent or divalent phenols.

In the methylol form of the formula (2), one of preferred compounds is a compound in which n = 0. This n = 0 compound can be obtained by reacting with formaldehyde using only monovalent phenols as the phenols in the above-mentioned production method. As a typical compound of the compound of n = 0, a methylol compound represented by the following formula (7) is exemplified.

In the methylol compound of the formula (2), n is 0 to 20, preferably 0 to 10, more preferably 0 to 5, and still more preferably 0 to 3, and X is a single bond or a halogen atom. A divalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with, more preferably an alkylene group having 1 to 5 carbon atoms, which may be substituted by a halogen atom; Is a methyl group when there is one, and when there are a plurality of them, each R independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a methylol group, and at least one is a methylol group Wherein h and i are 1 or 2, more preferably 1, and compounds wherein j and k are each independently 1 to 5 are also preferred.

Hereinafter, a method for producing a phenol compound of the present invention using a methylol compound of the formula (2), which is a preferred embodiment of the present invention, will be described.

The dehydration-condensation reaction between the phosphorus-containing compound of the formula (1) and the methylol compound of the formula (2) usually proceeds by heating in a solvent solution if necessary without a catalyst.

Specific examples of solvents that can be used include toluene, xylene, dioxane, dimethylformamide, dimethylsulfoxide, methanol, ethanol, isopropanol, ethylene glycol, ethers, phenols, and the like. Ketone solvents such as aceton-methylethyl ketone are not suitable for use unless they are used as raw materials, because they themselves react with the phosphorus-containing compound of the formula (1).

The reaction between the phosphorus-containing compound of the formula (1) and the methylol derivative of the formula (2) proceeds without a catalyst. However, as described below, an excess methylol group reacts with a monovalent phenol or a polyvalent phenol. If necessary, an acidic or basic catalyst may be present. However, alkali metal hydroxides and alkaline earth metal hydroxides are not preferred for the basic corrosion medium since they hydrolyze the phosphorus-containing compound of the formula (1) and generate phosphoric acid. Specific examples of the acidic catalyst that can be used include, but are not limited to, p-toluenesulfonic acid, acetic acid, formic acid, and oxalic acid. Specific examples of the basic catalyst that can be used include triethylamine, trioctylamine, N, Ν, Ν ', N'-tetramethylethylenediamine, Ν, Ν-diethylethanolamine, Ν, Ν-dimethylethanol. Tertiary amines such as amine, Ν-methyl-Ν, Ν-jetanolamine, Ν, ジ -dibutylethanolamine, preferably those having about 1 to 10 carbon atoms in the alkyl or alkylene group on the Ν atom. (Which may be substituted by a hydroxy group, etc.) It is not specified.

The amount of the catalyst to be used is generally 0.01 to 500 parts, preferably 0.02 to 300 parts, per 100 parts of the methylol compound of the formula (2).

The reaction between the methylol compound of formula (1) and formula (2) is a dehydration reaction, and the phosphorus-containing compound of formula (1) easily generates phosphoric acid when reacted with water. It is preferable to discharge it out of the system.

The reaction temperature and time vary depending on the solvent used and the reactivity of the methylol group of the methylol compound of the formula (2), but are usually in the range of 50 to 200 ° C, preferably 70 to 180 ° C, and usually 5 to 100 ° C. Hours, preferably in the range of 6 to 30 hours.

Since the reaction between the phosphorus-containing compound of the formula (1) and the methylol group of the methylol compound of the formula (2) is a reaction at a ratio of 1 mol: 1 mol, usually both are equimolar or phosphorus of the formula (1). The compound contained may be used in a slight excess. However, in some cases, the ratio of the methylol group may be increased (using an excess of the methylol form such that the number of moles of the methylol group in the methylol form exceeds the number of moles of the phosphorus-containing compound of the formula (1)). After the phosphorus-containing compound of the formula (1) has completely reacted with the methylol group in the methylol compound of the formula (2), the remaining methylol group is dehydrated and condensed with monovalent phenols or polyvalent phenols. Can also.

Further, the polyvalent phenol compound obtained by reacting the phosphorus-containing compound of the formula (1) with a methylol group at a ratio of 1 mol: 1 mol may be used alone or in the monovalent phenol / polyhydric phenol. Further, in the presence of benzene, it may be allowed to polymerize (condensate) with each aldehyde, various gen compounds, ketones, aromatic dimethanols, aromatic dichloromethyls and the like.

Further, after reacting a monovalent phenolic methylol compound with a phosphorus-containing compound of the formula (1), if necessary, various aldehydes are further added in the presence of the above-mentioned monovalent phenol / polyvalent phenol. It may be polymerized with various gen compounds, ketones, aromatic dimethanols, aromatic dichloromethyls and the like. The phenolic compound of the present invention thus obtained is represented by the above formula (4). When the compound of the formula (7) is used, a compound represented by the formula (8) is obtained, and the phosphorous in one molecule is obtained. Compounds having two or more atoms are preferred. Hereinafter, the resin composition of the present invention will be described.

As long as the resin composition of the present invention contains the phenolic compound of the present invention, a curable resin composition (for example, a thermosetting resin composition, a radical-curable resin composition, a cation-curable resin composition) or a thermosetting resin composition Any of a plastic resin composition and the like may be used.

In the resin composition of the present invention, one or more resins selected from the group consisting of epoxy resins, cyanate ester resins, maleimide compounds and resole resins, and / or one or more of the other components other than the phenolic compound of the present invention. Contains a curing agent. The proportion of the phenol compound of the present invention in the total resin composition is not particularly limited as long as the intended effect is exhibited, but is at least 3% by mass, preferably at least 5% by mass, more preferably at least 1% by mass. It is at least 0% by mass and usually at most 80 '% by mass, preferably at most 60% by mass, more preferably at most 40% by mass.

When the phenolic compound of the present invention having only one phenolic hydroxyl group is blended in a resin composition, it mainly functions as a flame retardant and imparts excellent flame retardancy to a cured product of the resin composition. In addition, the cured product has low hygroscopicity and excellent water resistance. In addition, when the phenol compound of the present invention having two or more phenolic hydroxyl groups is incorporated into a resin composition, it has a function as a flame retardant and also as a curing agent such as an epoxy resin. The cured product of the resin composition having excellent flame retardancy, low hygroscopicity, and excellent water resistance as described above. In the case of the phenol compound of the present invention having two or more phenolic hydroxyl groups, it is possible to use it alone as a curing agent. It may be used in combination with other hardeners usually used depending on the resin. When another curing agent is used in combination, the ratio of the phenolic compound of the present invention, when added to the resin composition, is particularly preferable if the ratio of the phenolic compound of the present invention to the entire resin composition falls within the above range. Not limited. Usually, it may be 20% by mass or more based on the whole curing agent, and preferably about 30 to 70% by mass.

Examples of the curing agent for other resins that can be used in combination with the phenol compound of the present invention include, for example, amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, triethylenetetramine, diaminodiphenylsulfone, Polyamide resin synthesized from dimer of isophoronediamine, dicyandiamide, linolenic acid and ethylenediamin, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride , Methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, Alkyl-substituted phenols, aromatic-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthylene, etc.) and various aldehydes (formaldehyde) , Acetaldehyde, alkyl aldehyde, benzaldehyde, polycondensation products with alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, darthalaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc., phenols and various gen compounds Polymers with cyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, 'diisoprobenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones (α) Polycondensate with cetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenonone, benzophenone, etc., phenols and aromatic dimethanol (Benzene dimethanol,, a, a'-benzenedimethanol, biphenyldimethanol, α,, ',' —biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α, «'Dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, and modified products thereof, imidazole, BF ₃ -amine complex, guanidine derivative, dicyandiamide, etc. However, the present invention is not limited to these. When the resin composition contains an epoxy resin, the epoxy resin is used in a ratio of 0.5 to 1.5 equivalents per equivalent of the curing agent, and when the resin composition contains a cyanate ester resin, the curing agent is used. : Sine ester resin (mass ratio) = 20:80 to 80:20, and when a maleimide compound is contained, curing agent: maleimide compound (mass ratio) = 20: 80 to 80:20 It is preferable to use Good.

Specific examples of epoxy resins that can be used in the resin composition of the present invention include bisphenols (bisphenol 8, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols and various aldehydes (formaldehyde). Polycondensates with aldehydes, acetoaldehydes, alkyl aldehydes, benzaldehydes, alkyl-substituted benzaldehydes, hydroxybenzaldehydes, naphthaldehydes, daltalaldehydes, phthalaldehydes, crotonaldehydes, cinnamaldehydes, etc., phenols and various gen compounds Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisoprobe Polymers with dirubiphenyl, butadiene, isoprene, etc.), polycondensates with phenols and ketones (acetone, methylethylketone, methylisobutylketone, acetophenonone, benzophenone, etc.), phenols and aromatic dimethanol (Benzene,, a, a ',' -benzenedimethanol, biphenyldimethanol, a,, ', a'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyl Polycondensates with phenols (a, a'—dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols with various aldehydes, and dalicidyl ether epoxy resins obtained by converting alcohols, etc. to dalicidyl ether , Alicyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin The resin is not limited to these, as long as it is a commonly used epoxy resin. These may be used alone or in combination of two or more.

When the resin composition of the present invention contains an epoxy resin, if necessary, a resin composition generally used as a curing accelerator for an epoxy resin may be contained. Specific examples of the curing accelerator that can be used include imidazole compounds such as 2-methylimidazole and 2-edimidazole, boron trifluoride complex, triphenylphosphine, trioctylphosphine, tricyclohexylphosphine, and triflic. Enylphosphine • Triphenylphenylborane, phosphorus-based compounds such as tetraphenylphosphonium and tetraphenylporate, and tertiary amine compounds. The amount is usually 0.1 to 15 parts, preferably 0.1 to 10 parts per 100 parts of fat. Specific examples of the cyanate ester resin that can be used in the resin composition of the present invention include dicyantobenzene, tricyantobenzene, diciana-tonaphthalene, dicyan-to-biphenyl, 2,2,1-bis (4-cyanatophenyl). ) Bread, bis (4-cyanatophenyl) methane, bis (3,5-dimethyl-41-cyanatophenyl) methane, 2,2'-bis (3,5-dimethyl-4-cyana-tophenyl) propane, 2,2, —Bis (4-cyanatophenyl) ethane, 2, 2 '—bis (4-cyanatophenyl) hexafluoropropane, bis (4-cyanatophenyl) sulfone, bis (4-cyanatophenyl) thioether, phenol Examples include nopolakcyanate and phenol / dicyclopentadiene cocondensate obtained by converting a hydroxyl group into a cyanate group, but are not limited thereto. These may be used alone or in combination of two or more.

In the case where the thermosetting resin composition of the present invention contains a cyanate ester resin, zinc naphthenate and naphthenic acid are used in order to trimerize the cyanate group as needed to form a sym-triazine ring. A catalyst such as copal small, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetate acetate, dibutyltin maleate and the like can be contained. The catalyst is used in an amount of usually 0.0001 to 0.10 part, preferably 0.000015 to 0.0015 part, based on 100 parts of the resin component in the resin composition. These may be used alone or in combination of two or more. The maleimide compound that can be used in the resin composition of the present invention may be any compound having a maleimide group, and is a compound obtained by subjecting a compound having a secondary amine and maleic anhydride to a condensation and dehydration reaction, Specific examples that can be used include phenylmaleimide, hydroxyphenylmaleimide, N, N'-ethylenebismaleimide, N, N'-hexamethylenebismaleimide, N, N'-phenylenebismaleimide, 4,4 'Bismaleimidodiphenylmethane, 4, 4'-Bismaleimidediphenylpropane, 4, 4'Bismaleimidediphenylsulfone, Condensation and dehydration of amino groups of polycondensates of anilines and aldehydes with maleic anhydride Maleimide resin, condensation dehydration of maleic anhydride with amino group of aniline and aromatic dimethanol polycondensate Maleimide resin etc., but are not limited to these It is not something to be done. These may be used alone or in combination of two or more. When a maleimide compound is contained in the resin composition of the present invention, a curing accelerator such as a curing accelerator for epoxy resin / cyanate ester resin or a radical polymerization initiator such as an organic peroxide / diazo compound is used. Is also good. In this case, the curing accelerator or the polymerization initiator is usually used in a ratio of 0.01 to 10 parts with respect to 100 parts of the resin in the resin composition. These may be used alone or in combination of two or more. When the resin composition of the present invention contains an epoxy resin or a maleimide compound, the resin composition can be cured by light by using a photoradical initiator, a photodynamic thione initiator, or the like.

Further, the resin composition of the present invention may contain various additives as necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, indene resin, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, and silicone. Oil, silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, my strength, glass powder, glass fiber, glass nonwoven fabric or carbon fiber Examples include inorganic fillers such as fibers, surface treatment agents for fillers such as silane coupling agents, release agents, coloring agents such as carbon black, phthalocyanine blue, and phthalocyanine green, and flame retardants such as brominated epoxy resins.

When obtaining a flame-retardant cured product that does not contain halogen, do not mix a bromine-based or chlorine-based compound in the composition, and use only the polyvalent phenol compound of the present invention or other phosphorus-based flame retardants or nitrogen. Flame retardancy is exhibited by the combined use of such compounds.

The resin composition of the present invention can be obtained by uniformly mixing the above components at the above-described ratios. Mixing can be carried out by heating and melting at a temperature about 20 to 100 ° C. higher than the softening point of each of the above components, if necessary.

Alternatively, the components can be mixed by uniformly dispersing or dissolving the components of the resin composition in a solvent or the like. The solvent in this case is not particularly limited, but specific examples that can be used include toluene, xylene, methylethylketone, methylisobutylketone, dioxane, methylcellosolve, dimethylformamide and the like. these The solvent is used in an amount of usually 5 to 300 parts, preferably 10 to 150 parts, based on 100 parts of the resin.

The cured product of the present invention is obtained by treating the above resin composition at room temperature to 250 ° C. for 30 seconds to 50 hours.

Alternatively, the components of the resin composition may be uniformly dispersed or dissolved in a solvent or the like, and after the solvent is removed, the resin composition may be cured under the above-described conditions.

When the resin composition contains a photo-radical initiator, a photo-thion initiator, or the like, the resin composition can be cured mainly by irradiating ultraviolet rays. Thereafter, heat treatment is preferably performed under the above conditions.

Further, flame retardancy can be imparted by adding the phenolic compound of the present invention to a thermoplastic. When the phenolic compound of the present invention is used for this purpose, it may be used alone or in combination with other flame retardants and flame retardant auxiliaries. Other flame retardants include commonly used phosphorus-based flame retardants (mainly phosphate esters), halogen-based flame retardants, organic flame retardants such as nitrogen-based compounds, red phosphorus-based flame retardants, and trioxide. Examples include inorganic flame retardants such as antimony and aluminum hydroxide. However, considering recent environmental issues, it is preferable not to use halogen-based flame retardants or antimony trioxide.

The amount of the phenolic compound of the present invention used in the thermoplastic plastic of the present invention varies depending on the amount of other flame retardants and flame retardant aids used and the type of plastic, but usually the amount of phosphorus contained in the plastic is high. It is blended so as to be 0.1 to 15% by mass, preferably 0.3 to 10% by mass in terms of conversion. Example

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these examples. In Examples, the melt viscosity and the melting point were measured under the following conditions.

1) Melt viscosity

Melt viscosity in the cone-plate method at 200 ^

Measuring machine: cone plate (ICI) high temperature viscometer (RESEARCH EQUIPMENT) (LONDON) LTD.)

Cone No .: 3 (measurement range 0 to 2.0 Pa's; Examples A 1 to A4) Sample amount: 0.155 ± 0.005 (g) (Examples Α1 to Α4) Cone No .: 4 (measurement Range 0 to 4.O Pa's; Example B 1)

Sample amount: 0.100 ± 0.005 (g) (Example B 1)

2) Melting point

Measured by DSC.

3) Softening point

Conforms to ASTM D 1763

Synthesis example 1

o-Cresol 151 parts, paraformaldehyde 91.3 parts, water 280 parts, 30% sodium hydroxide aqueous solution 46 parts are charged into a reaction vessel, heated and stirred, and reacted at 60 ° C for 3.5 hours and at 50 ° C for 1.5 hours. Went. After completion of the reaction, 0 parts of water was charged, neutralized with hydrochloric acid, and the crystals were filtered and dried. A dinuclear dimethylol (Ml) of 0-cresol represented by the following formula (A1) was obtained. 169 parts were obtained.

Example A 1

A reaction vessel was charged with 21.6 parts of the phosphorus-containing compound of the formula (1), 14.4 parts of the compound of the formula (A1), and 100 parts of xylene. The mixture was heated and stirred, and reacted at 130 to 140 ° C. for 20 hours. went. At that time, xylene and water produced by azeotropic distillation were cooled and separated, and then the reaction was carried out while returning only xylene as an organic layer into the system. After completion of the reaction, the mixture was cooled, 5 parts of methanol was added, and the precipitate was separated by filtration and dried to obtain the following formula (A2)

33 parts of the phenolic compound (P1) of the present invention represented by the following formula: The melting point of the obtained compound (P1) was 217 ° C. Example A 2

21.6 parts of the phosphorus-containing compound of the formula (1), 21.4 parts of the compound of the formula (A1) and 100 parts of toluene are charged into a reaction vessel, heated and stirred, and reacted at 130 to 140 ° C for 20 hours. Was done. At that time, the xylene and water produced by azeotropic distillation were cooled and separated, and then the reaction was carried out while returning only the organic layer xylene into the system. Thereafter, 16.2 parts of 0-cresol and 0.5 part of p-toluenesulfonic acid were added, and the mixture was reacted at 100 to 110 ° C for 2 hours. After adding 70 parts of toluene, water washing was repeated several times. From toluene by heating under reduced pressure under heating to obtain the following formula (A 3)

(A plurality of r's in the formula independently represent a hydrogen atom or the above formula (6). N = l.3 (average value)) 44 parts of the phenolic compound (P 2) of the present invention represented by the following formula was obtained. . The obtained compound (P2) had a softening point of 143 ° C and a melt viscosity of 0.36 Pa's. Example A 3

In the same manner as in Example A2 except that the compound of the formula (Al) was changed to 28.8 parts and 0-cresol was changed to 32.4 parts, the same operation as in the above formula (A3) (n = l.7 ( (Average value)) 54 parts of the phenolic compound (P3) of the present invention represented by the following formula: The softening point of the obtained compound (P3) was 137 ° C, and the melt viscosity was 0.21 Pa · s. Example A 4

In the same manner as in Example A3 except that 0-cresol was changed to 38 parts of phenol, 50 parts of a phenol compound (P4) of the present invention were obtained. The obtained compound (P4) had a softening point of 157 ° C and a melt viscosity of 1.3 Pa · s. Examples A5 to A7

The mixture blended at the ratio shown in the column of “Composition of the blend” in Table 1 was kneaded with a twin-screw roll, crushed and tableted, and a resin molded body was prepared by transfer molding. And further cured at 180 ° C for 8 hours.

The results of measuring the physical properties of the cured product thus obtained are shown in Table 1 in the column of “Physical Properties of Cured Product”.

In addition, the measurement of the physical property value was performed by the following method.

• Moisture absorption: Weight increase rate after a disc-shaped test specimen with a diameter of 5 cm and a thickness of 4 mm is left for 24 hours under conditions of 12 l ° CZl and 100% RH;:)

'' Flame retardant: UL-94 compliant

• Glass transition temperature: TMA method (TM-7000, manufactured by Vacuum Riko Co., Ltd.)

Heating rate 2 ° C / min

In Table 1 (same in Table 2)

ECN: o-Cresol nopolak epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-1020, epoxy equivalent 199 g / eQ, softening point 63 ° C)

PN: Phenolnopolak (Meiwa Kasei Co., Ltd., H-1, hydroxyl equivalent 105 g / e α, softening point 84 ° C)

TPP: Trifenylphosphine Synthesis Example 2

108 parts of P-cresol, 65.2 parts of paraformaldehyde, 80 parts of water and 12 parts of sodium hydroxide were charged into a reaction vessel, heated and stirred, and reacted at 50 for 5 hours. After completion of the reaction, 230 parts of water was charged and neutralized with hydrochloric acid, and the crystals were filtered and dried to obtain 147 parts of a dimethylol derivative of p_cresol (M2). Example B 1

26 parts of the phosphorus-containing compound of the above formula (1), the compound (M 2) obtained in Synthesis Example 1 9. 2 parts and 20 parts of xylene were charged into a reaction vessel, heated and stirred, and reacted at 140 to 150 ° C for 20 hours. At that time, xylene and water produced by azeotropic distillation were cooled and separated, and then the reaction was carried out while returning only xylene, which is the organic layer, into the system. After completion of the reaction, xylene is distilled off under reduced pressure by heating to obtain the following formula (B 1)

The phenolic compound (P5) of the present invention, comprising as a main component, was obtained. The obtained phenol compound (P5) had a softening point of 142 ° C and a melt viscosity of 0.32 Pa's.

Note that in Synthesis Example 2! ) By changing 108 parts of cresol to 144 parts of 1-naphthol, a dimethylol form of 1-naphthol was synthesized. In Example B1, the dimethylol form of 1-naphthol was replaced with 0.55 in place of the compound (M2). When used in a molar amount, the phenol-containing compound of the present invention in which the p-cresol residue is a 1-naphthol residue in the above formula (B1) can be synthesized. Example B2

A cured product was obtained in the same manner as in Examples A5 to A7, except that the composition shown in the column of “composition of formulation” in Table 2 was used. The physical properties of the cured product thus obtained were measured in the same manner as in Examples A5 to A7, and the results are shown in the column of “Physical Properties of Cured Product” in Table 2. Table 2

Composition of Formulation Example B 2 (parts)

(a) Epoxy resin 54.9

(b) Curing agent: PN 25.1

(d) P 5 20.0

(e) Curing key: TPP 1.0

Physical properties of cured product

1.5

Flame retardant V-0 Industrial applicability

The phenolic compound of the present invention is used as a raw material for various resins, and a resin composition containing the same has excellent heat resistance (determined from a high glass transition temperature) in a cured product thereof, moisture resistance (moisture absorption rate) Is low) and has flame retardant properties, such as insulating materials for electric and electronic parts (such as highly reliable semiconductor encapsulation materials), laminates (such as printed wiring boards), and CFRP. It is extremely useful when used in various composite materials, adhesives, paints, etc.

Further, by using the phenolic compound of the present invention as a part of a raw material or as an additive in plastics, flame retardancy can be exhibited without using halogen or the like.

Claims

Equation (1)

A phenol compound obtained by subjecting a phosphorus-containing compound represented by the formula (1) to formaldehyde and monovalent or polyvalent phenols to a polycondensation component and subjecting them to polycondensation.

2. The phosphorus-containing compound of the formula (1) and the following formula (2)

Enclosure

(In the formula (2), a plurality of Xs are independently a single bond, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an oxygen atom, a sulfur atom, a sulfone group, a sulfoxide group, Represents any one of the three groups described in the following formula (3).

(In the formula (3), g represents an integer of 1 to 3. m, d, and e each represent an integer of 0 to 6. R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, Any one of methylol groups is shown, but when R is 1, it is a methylol group, and when two or more are present, they may be independently the same or different from each other, and at least one Is a methylol group. Q is a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms Represents a group. Multiple A's independently represent a carbon atom or a nitrogen atom. W represents an oxygen atom or a sulfur atom. When a plurality of X, Q and W are present in the structure represented by the formula (2), each X, each Q and each W are independently the same or different. You may. Also, when g, m, d and e are present in the structure represented by the formula (2) in plurals, each g, each m, each d and each e are different even if they are independently the same. May be. )

In addition, a plurality of Rs in the formula (2) independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group or a methyl group. At least one is a methylol group. h and i each independently represent an integer of 1 to 3. j and k independently represent an integer of 0-6. When a plurality of i and k are present in the structure represented by the formula (2), each i and each k may be independently the same or different. n represents an average value and represents a real number of 0 to 20. )

A phenolic compound obtained by polycondensing a methylol compound represented by the formula and optionally phenols other than the methylol compound of the formula (2), and 3. a phenol compound obtained by the polycondensation;

(In the formula (4), X is a single bond, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, a sulfone group, a sulfoxide group or a group represented by the following formula (5). Represents one of the three groups.

(In the formula (5), g represents an integer of 1 to 3. m, d, and e each represent an integer of 0 to 6. A plurality of Zs independently represent a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Represents a hydrogen group, an alkoxy group or one of the following formulas (6), at least one of which is represented by the following formula:

It is a group of (6). Q represents a hydrogen atom or a hydrocarbon group having 1 to 2.0 carbon atoms. Multiple A's independently represent a carbon atom or a nitrogen atom. W represents an oxygen atom or a sulfur atom. When a plurality of X, Q and W are present in the structure represented by the formula (4), each Q and each W may be independently the same or different. Is also good. When g, m, d, and e exist in the structure represented by the formula (4), each g, each m, each d, and each e are independently the same. Or different. )

A plurality of Zs in the formula (4) are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or the following formula (6)

And at least one is a group of the formula (6). h and i each independently represent an integer of 1 to 3. j and k each independently represent an integer of 0-6. When a plurality of i and k are present in the structure represented by the formula (4), each i and each k may be independently the same or different. n represents an average value and represents a real number of 0 to 20. )

A phenolic compound represented by

4. The phenol compound according to claim 3, wherein h and i in the formula (4) are 1.

5. The phosphorus-containing compound represented by the formula (1) and the formula (7)

(In the formula (7), represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, and when two or more exist, they may be independently the same or different. X represents an integer of 2 to 3, and X represents an integer of 1 to 5.) A phenol compound obtained by condensing a methyl alcohol compound represented by the following formula as a polycondensation component.

6. Equation (8)

(In the formula (8), represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, and when a plurality of groups are present, they may be independently the same or different. X represents an integer of 2 to 3, and X represents an integer of 1 to 5.)

7. A resin composition containing the polyhydric phenol compound according to any one of claims 1 to 6.

8. The resin composition according to claim 7, which contains no halogen. '

9. The resin composition according to claim 8, wherein the resin composition is a curable resin composition.

10. The resin set according to claim 9, wherein the resin composition is an epoxy resin composition. Adult.

1 1. A cured product of the resin composition according to any one of claims 8 to 10.

12. The cured product according to claim 11, which has flame retardancy.

13. A flame-retardant thermoplastic containing the phenolic compound according to any one of claims 1 to 6.