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WO2019065552A1 - Résine phénoxy contenant du phosphore, composition de résine correspondante et produit durci - Google Patents

Résine phénoxy contenant du phosphore, composition de résine correspondante et produit durci Download PDF

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Publication number
WO2019065552A1
WO2019065552A1 PCT/JP2018/035256 JP2018035256W WO2019065552A1 WO 2019065552 A1 WO2019065552 A1 WO 2019065552A1 JP 2018035256 W JP2018035256 W JP 2018035256W WO 2019065552 A1 WO2019065552 A1 WO 2019065552A1
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Prior art keywords
group
resin
carbon atoms
phosphorus
independently
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Japanese (ja)
Inventor
佐藤　洋
雅男 軍司
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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Priority to JP2019545088A priority Critical patent/JP7244427B2/ja
Publication of WO2019065552A1 publication Critical patent/WO2019065552A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a phosphorus-containing phenoxy resin excellent in flame retardancy, high in heat resistance, and excellent in tracking resistance.
  • the present invention also relates to a resin composition containing the phosphorus-containing phenoxy resin and a curable resin component, and a cured product thereof.
  • Resin compositions are widely used mainly in electrical insulating materials due to their excellent electrical insulating properties, electrical properties, adhesiveness, mechanical properties of cured products, and the like. These electrical insulating materials are required to have high flame retardancy from the viewpoint of safety, and are made flame retardant by using a halogen-based flame retardant, an antimony compound or a phosphorus-based flame retardant in combination.
  • regulations on materials used for these have been increased in terms of environmental pollution and toxicity. Among them, the toxicity and carcinogenicity of organic halogen substances such as dioxins are a problem, and reduction and elimination of halogen-containing substances are strongly demanded.
  • the demand for reduction and elimination of antimony compounds is also increasing. Under these circumstances, substitution with phosphorus flame retardants has been proposed and studied.
  • epoxy resins are given film forming properties by high molecular weight polymerization by various methods, and are used as phenoxy resins.
  • the performance required for a phenoxy resin for electrical insulating material applications includes flame retardancy, high heat resistance and solvent solubility.
  • a phosphorus atom-containing phenoxy resin is disclosed in order to develop flame resistance without using a halogen from environmental problems, but the solvent solubility is poor such that the solvent for dissolving this is limited (patent document 1, 2).
  • a method of improving solvent solubility is also disclosed, flame resistance can not be secured unless the phosphorus content is increased because a large amount of aliphatic skeleton is used (Patent Documents 3 and 4).
  • a general-purpose phosphorus-based flame retardant is used as a main agent to make a flame retardant
  • a conductive track is easily formed under high voltage because of heat resistance, property deterioration due to moisture absorption, and a flame retardant action due to carbonization.
  • the tracking resistance decreases.
  • the inorganic hydrate is used as the main agent to make the flame retardant, high loading of the inorganic hydrate to an extreme extent is required, which causes problems such as the processability of the laminate, the heat resistance and the like being remarkably reduced.
  • the properties of the flame retardant phenoxy resin serving as the binder are greatly affected, and it is difficult to improve the tracking resistance.
  • the present invention solves these problems, and is a heat-resistant, tracking-resistant, highly safe, and highly flame-retardant, processable, heat-resistant, phosphorus-containing phenoxy resin, a resin composition using the same, and a circuit board It is an object of the present invention to provide a material and a cured product thereof.
  • the present invention is a phosphorus-containing phenoxy resin represented by the following formula (1) and having a weight average molecular weight Mw of 10,000 to 200,000.
  • X is a divalent group, but at least two of X are a group (X 1 ) and a heterocyclic structure-containing group (X 2 ) represented by the following Formula (2).
  • Y each independently represents a hydrogen atom or glycidyl group.
  • n is the number of repetitions, and its average value is 25 to 500.
  • A is an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring, and these aromatic ring groups are alkyl groups having 1 to 8 carbon atoms, 1 carbon atoms Alkoxy group of ⁇ 8, cycloalkyl group of 5 to 8 carbon atoms, aryl group of 6 to 10 carbon atoms, aralkyl group of 7 to 11 carbon atoms, aryloxy group of 6 to 10 carbon atoms, or 7 to 11 carbon atoms And any of the aralkyloxy groups may be possessed as a substituent.
  • Z is a phosphorus-containing group represented by the following formula (3).
  • R 1 and R 2 each represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, which may be different or identical, and may be linear, branched or cyclic It may be Further, R 1 and R 2 may be bonded to form a cyclic structure site.
  • k1 and k2 are independently 0 or 1.
  • the divalent group that may exist as X is the group (X 1 ) represented by the formula (2), the heterocyclic structure-containing group (X 2 ) and the other group (X 3 ), and the respective abundances thereof are
  • the phosphorus-containing group represented by the above formula (3) is preferably a phosphorus-containing group represented by the following formula (3a) or (3b).
  • R 3 and R 4 are each independently a hydrocarbon group having 1 to 11 carbon atoms, m 1 is each independently an integer of 0 to 4 and m 2 is independently 0 It is an integer of ⁇ 5.
  • the number of moles of the heterocyclic structure-containing group (X 2 ) is 12.5 to 75 mole%, and the number of moles of the other group (X 3 ) is 0 to 12 with respect to the total number of moles of X above. It is preferable that it is 5 mol%.
  • the heterocyclic structure-containing group (X 2 ) preferably contains at least one of divalent groups represented by the following formulas (4a) to (4f).
  • each R 5 independently represents an alkyl group having 1 to 6 carbon atoms, or an aromatic ring group having either a benzene ring or a naphthalene ring, and these aromatic rings each have 1 to 6 carbon atoms With any of an alkyl group of 8, an alkoxy group of 1 to 8 carbon atoms, a cycloalkyl group of 5 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms and an aralkyl group of 7 to 11 carbon atoms as a substituent May be
  • each R 6 independently represents a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms.
  • R 7 is each independently a hydrocarbon group having 1 to 11 carbon atoms, and m 3 is each independently an integer of 0 to 3.
  • the other group (X 3 ) preferably contains at least one of the divalent groups represented by the following formulas (5a) to (5c).
  • R 8 is a direct bond or a hydrocarbon group having 1 to 20 carbon atoms, —CO—, —O—, —S—, —SO 2 —, —C (CF 3 ) 2 — It is a divalent group to be selected.
  • R 9 , R 10 and R 11 each independently represent a hydrocarbon group having 1 to 11 carbon atoms
  • m 4 and m 5 each independently represent an integer of 0 to 4
  • this invention is a resin composition formed by mix
  • the curable resin component is preferably at least one selected from an epoxy resin, an acrylic ester resin, a melanin resin, an isocyanate resin, and a phenol resin.
  • this invention is a circuit board material obtained from the said resin composition, and is the hardened
  • the phosphorus-containing phenoxy resin of the present invention is represented by the above formula (1), and has a weight average molecular weight (Mw) of 10,000 to 200,000 as measured by gel permeation chromatography (GPC), 20,000 to 150,000 is preferable, 25,000 to 100,000 is more preferable, 30,000 to 80,000 is more preferable.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • X is a divalent group, and the group (X 1 ) represented by the formula (2) and the group (X 2 ) having a heterocyclic structure are essential, and the other groups (X 3) May be included.
  • Y each independently represents a hydrogen atom or glycidyl group.
  • n is the number of repetitions, and the average value thereof is 25 to 500, preferably 40 to 400, more preferably 50 to 350, and still more preferably 70 to 300.
  • n is related to the above Mw.
  • A represents an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring.
  • aromatic ring groups are an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 carbon atoms. Any of an aralkyl group of to 11 groups, an aryloxy group of 6 to 10 carbon atoms, or an aralkyloxy group of 7 to 11 carbon atoms may be possessed as a substituent.
  • examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group and the like, and cycloalkyl groups having 5 to 8 carbon atoms
  • examples of the group include a cyclohexyl group and the like
  • examples of the aryl group having 6 to 10 carbon atoms and the aryloxy group include a phenyl group, a naphthyl group, a phenoxy group, a naphthyloxy group and the like, and an aralkyl having 7 to 11 carbon atoms
  • Examples of the group or aralkyloxy group include benzyl group, phenethyl group, 1-phenylethyl group, benzyloxy group and naphthylmethyloxy group.
  • Preferred examples of A include a benzene ring, a methyl-substituted benzene ring, a 1-phenylethyl-substituted benzene ring, a naphthalene ring, a methyl-substituted naphthalene ring, and a 1-phenylethyl-substituted naphthalene ring. is there.
  • Z is a phosphorus-containing group represented by the above formula (3).
  • R 1 and R 2 each represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, which may be different or identical, and may be linear, branched or cyclic. It may be Further, R 1 and R 2 may be bonded to form a cyclic structure site. In particular, aromatic ring groups are preferred.
  • R 1 and R 2 are an aromatic ring group, as a substituent, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, 6 to 10 carbon atoms Or an aralkyl group having 7 to 11 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an aralkyloxy group having 7 to 11 carbon atoms.
  • a hetero atom an oxygen atom etc. are illustrated and this can be contained between carbon which comprises a hydrocarbon chain or a hydrocarbon ring.
  • R 3 and R 4 are each independently a hydrocarbon group having 1 to 11 carbon atoms, and specifically, methyl group, ethyl group, t-butyl group, cyclohexyl And a methyl group, a cyclohexyl group, a phenyl group, a tolyl group and a benzyl group are mentioned, and a methyl group, a phenyl group and a benzyl group are preferable.
  • m1 is each independently an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1.
  • m2 is each independently an integer of 0 to 5, preferably 0 to 2, and more preferably 0 or 1.
  • Another preferred embodiment of the above formula (3) is any one of the following formulas (a1) to (a10).
  • X is a heterocyclic structure-containing group (X 2 ), it is not particularly limited as long as it is a divalent group having a heterocyclic structure inside, and may have a plurality of heterocyclic structures, and -E-Het- It may be a group such as E-.
  • Het is a heterocyclic structure
  • E is a single bond or a linking group, but a preferred linking group is an oxygen atom.
  • the heterocyclic structure is preferably composed of a 5- to 16-membered heterocyclic ring, and is, for example, an oxygen-containing heterocyclic such as furan, tetrahydrofuran, oxane (tetrahydropyran), dioxolane, dioxane, benzopyran, xanthene compound, etc.
  • an oxygen-containing heterocyclic such as furan, tetrahydrofuran, oxane (tetrahydropyran), dioxolane, dioxane, benzopyran, xanthene compound, etc.
  • Heterocycles derived from compounds heterocycles derived from sulfur-containing heterocyclic compounds such as thiophene, tetrahydrothiophene, thiane (tetrahydrothiopyran) and dithiane compounds, pyrrolidine, piperidine, piperazine, pyrrole, pyridine, pyrazine, Examples thereof include heterocycles derived from nitrogen-containing heterocyclic compounds such as pyrimidine, triazole, pyrazole, imidazole, indole, oxazole, oxazoline, oxazolidine, and thiazole compound.
  • heterocyclic rings of aliphatic rings such as tetrahydrofuran, oxane, dioxolane, dioxane, tetrahydrothiophene, thiane, dithiane, piperidine, pyrrolidine, piperazine, oxazolidine and the like are preferable, and tetrahydrofuran, dioxane, and piperazine are more preferable.
  • Preferred embodiments of the heterocyclic structure-containing group (X 2 ) include groups represented by the above formulas (4a) to (4f).
  • each R 5 independently represents an alkyl group having 1 to 6 carbon atoms, or an aromatic ring group having either a benzene ring or a naphthalene ring, and these aromatic rings each have 1 to 6 carbon atoms
  • an alkyl group of 8 an alkoxy group of 1 to 8 carbon atoms
  • a cycloalkyl group of 5 to 8 carbon atoms an aryl group of 6 to 10 carbon atoms and an aralkyl group of 7 to 11 carbon atoms
  • the substituent illustrated by Formula (2) is preferable.
  • R 5 is an aromatic ring group similar to A of the formula (2), and is a benzene ring, a methyl group substituent of a benzene ring, a 1-phenylethyl group substituent of a benzene ring, a naphthalene ring or a naphthalene ring It is a methyl-substituted or 1-phenylethyl-substituted naphthalene ring.
  • R 6 s are each independently a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and adjacent R 6 s may be bonded to form a cyclic structure. Specific examples thereof include a hydrogen atom, a methyl group, an ethyl group, an iso-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group and a phenyl group. A methyl group or an ethyl group is preferable, and a methyl group is more preferable.
  • Each R 7 is independently a hydrocarbon group having 1 to 11 carbon atoms, and the same group as R 6 is preferable.
  • m3 is each independently an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
  • any structure may be used as long as it is a divalent group other than (X 1 ) and (X 2 ), but having a ring structure in terms of heat resistance Is preferable, and in view of tracking resistance, an aliphatic type is preferable, and one having an aliphatic ring structure is more preferable. More preferably, they are groups represented by the above formulas (5a) to (5c).
  • R 8 is a direct bond, or a hydrocarbon group having 1 to 20 carbon atoms, selected from —CO—, —O—, —S—, —SO 2 —, and —C (CF 3 ) 2 — Is a bivalent group.
  • Preferred R 8 is a direct bond, -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -CO-, -O-, -S-, -SO 2- , cyclohexylidene Group, trimethylcyclohexylidene group, cyclooctylidene group, cyclododecylidene group, bicyclohexylidene group, 9H-fluoren-9-ylidene group, and divalent groups having a tetrahydrodicyclopentadiene structure, Bond, -CH 2- , -C (CH 3 ) 2- , -CO-, -SO 2- , trimethylcyclohexylidene group, 9H-fluoren-9-ylidene group, or a bivalent having a tetrahydrodicyclopentadiene structure Are more preferred.
  • R 8 When R 8 is a direct bond, it is a biphenyl skeleton, but its bonding position is 2, 2 ', 2, 3', 2, 4 ', 3, 3', 3, 3 ', or Although it may be any of the 4,4'-positions, it is preferably the 4,4'-position.
  • the bonding position of the benzene ring is 2,2 ′, 2,3 ′, 2,4 ′, 3,3 ′, 3,4 ′, or 4 , 4 'may be used, but preferably it is 4,4'.
  • R 9 is each independently a hydrocarbon group having 1 to 11 carbon atoms, and is preferably the same group as R 3 in formula (3a).
  • m4 is each independently an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1.
  • each R 10 independently represents a hydrocarbon group having 1 to 11 carbon atoms, and a group similar to R 3 in the formula (3a) is preferable.
  • m5 is an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1.
  • R 11 is each independently a hydrocarbon group having 1 to 11 carbon atoms, and is preferably the same group as R 3 in formula (3a).
  • m6 is an integer of 0 to 6, preferably 0 to 2, and more preferably 0 or 1.
  • the respective abundance ratios are as follows: It is. 1/99 to 99/1 is preferable, 5/95 to 90/10 is more preferable, 10/90 to 80/20 is further preferable, and 20/80 to 70/30 is particularly preferable. 30/70 to 50/50 are most preferred. If X1 is small, there is a risk that the flame retardancy caused by the phosphorus atom in (X 1 ) may be insufficient.
  • X2 / X3 is preferably 50/50 to 100/0, more preferably 65/35 to 100/0, and still more preferably 80/20 to 100/0.
  • (X 2 ) is necessary to improve the flame retardancy without increasing the residual carbon ratio, but if the amount of (X 3 ) is large, the effect may not be exhibited, and (X 3 ) is present Preferably not.
  • (X 3 ) may serve to improve other properties, such as solvent solubility, dielectric properties, etc., it is preferable to determine the amount according to the purpose.
  • the phenoxy resin of the present invention can be in the form of epoxy group terminal, phenolic hydroxyl group terminal, or a mixture thereof. Since the phenoxy resin does not generally consider the reaction at the epoxy group, the epoxy equivalent does not have to be particularly specified, but it is not necessary to specify 5,000 g / eq. It is sufficient if it is the above. 5,000 g / eq. If it is less than this, the film formability and the extensibility are inferior and it is not preferable. In addition, when it comes to a phenolic hydroxyl group terminal, the epoxy group concentration becomes 0, so the epoxy equivalent becomes an infinite value. Therefore, defining the upper limit of the epoxy equivalent has virtually no critical meaning.
  • the one-step method essentially comprises an epihalohydrin such as epichlorohydrin or epibromohydrin, a phosphorus-containing bifunctional phenol compound represented by the following formula (6a), and a bifunctional compound having a heterocyclic structure represented by the following formula (6b)
  • the bifunctional compound to be reacted is reacted in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
  • X 1 is a group represented by the formula (2)
  • X 2 is a heterocyclic structure-containing group, represented by the above formulas (4a) to (4f) Preferred is a divalent group.
  • the functional group in the said bifunctional compound is a group reactive with an epoxy group, and OH group is preferable.
  • the two-stage process generally reacts a difunctional compound with a bifunctional epoxy resin in the presence of a catalyst.
  • a bifunctional compound a bifunctional compound having a group (X 1 ) represented by Formula (2), a heterocyclic structure-containing group (X 2 ), or both of them is used.
  • a bifunctional epoxy resin a bifunctional epoxy resin having the group (X 1 ), the group (X 2 ), or both of them is used. Then, the reaction is carried out by using the group (X 1 ) and the group (X 2 ) in such a manner that they have one or both of the bifunctional compound and the bifunctional epoxy resin.
  • the phosphorus-containing phenoxy resin of the present invention may be obtained by any production method, but in general, the two-step method is easier to obtain since the phenoxy resin is easier to obtain than the one-step method. preferable.
  • the weight average molecular weight and epoxy equivalent of the phosphorus-containing phenoxy resin are adjusted by adjusting the preparation molar ratio of the epihalohydrin and the bifunctional phenol compound in the one-step method and the preparation molar ratio of the bifunctional epoxy resin and the bifunctional phenol compound in the two-stage method A range of interest can be manufactured.
  • the phosphorus-containing bifunctional phenol compound represented by the above formula (6a) can be obtained by reacting an organic phosphorus compound represented by the following formula (7) with a quinone compound using a known synthesis method.
  • a synthesis method for example, JP-A-60-126293, JP-A-61-263787, zh. Obshch. Khim, 42 (11), pp. 2415-2418 (1972).
  • R 1, R 2, k1, and k2 are respectively synonymous with R 1, R 2, k1, and k2 in Formula (3).
  • a in the formula (2) is a benzene ring
  • benzoquinone methyl-benzoquinone, ethyl-benzoquinone, butyl-benzoquinone, dimethyl-benzoquinone, diethyl-benzoquinone, dibutyl-benzoquinone, methyl-isopropyl-benzoquinone, diethoxy And -benzoquinone, trimethyl-benzoquinone, methyl-dimethoxy-benzoquinone, methyl-methoxy-benzoquinone, phenyl-benzoquinone, tolyl-benzoquinone, ethoxyphenyl-benzoquinone, diphenyl-benzoquinone and the like.
  • a in the formula (2) is a naphthalene ring, for example, naphthoquinone, methyl-naphthoquinone, cyclohexyl-naphthoquinone, methoxy-naphthoquinone, ethoxy-naphthoquinone, dimethyl-naphthoquinone, dimethyl-isopropyl-naphthoquinone, methyl-methoxy-naphthoquinone Etc.
  • a in the formula (2) is an anthracene ring
  • examples thereof include anthraquinone, methyl-anthraquinone, ethyl-anthraquinone, methoxy-anthraquinone, dimethoxy-anthraquinone, diphenoxy-anthraquinone and the like.
  • a in the formula (2) is a phenanthrene ring
  • examples thereof include phenanthrenequinone, methyl-phenanthrenequinone, isopropyl-phenanthrenequinone, methoxy-phenanthrenequinone, butoxy-naphthoquinone, dimethoxy-phenanthrenequinone and the like.
  • These quinone compounds may be used alone or in combination of two or more.
  • Examples of the organic phosphorus compound represented by the formula (7) include dimethyl phosphine oxide, diethyl phosphine oxide, dibutyl phosphine oxide, diphenyl phosphine oxide, dibenzyl phosphine oxide, cyclooctylene phosphine oxide, tolyl phosphine oxide, bis (methoxy) (Phenyl) phosphine oxide, etc., phenyl phenyl phosphinate, ethyl phenyl phosphinate, tolyl tolyl phosphinate, benzyl benzyl phosphinate, etc., 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , DOPO), 8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-benzyl-9,10-dihydro-9-oxa-10-phos
  • Examples of the bifunctional compound having a heterocyclic structure represented by the formula (6b) include isosorbide, 1,5,7,11-tetraoxaspiro [5.5] undecane-3,9-diol, 1,3 5,7,7-tetraoxadecalin-4,8-dimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] Dihydric alcohols such as undecane, diamines such as piperazine, 3,9-bis (4-hydroxyphenyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 7,7'-dihydroxy And difunctional phenol compounds such as -4,4,4 ', 4'-tetramethyl-2,2'-spirobichroman.
  • the compound in which X 2 of formula (6b) is represented by formula (4d) can be synthesized by a known method.
  • a compound having pentaerythritol, and one hydroxy group and one aldehyde group is provided.
  • the compound represented by Formula (4e) in which X 2 of Formula (6b) is represented by Formula (4e) can be synthesized by a known method.
  • a compound having a carbonyl group such as acetone and an aromatic compound having a plurality of phenolic hydroxyl groups such as resorcinol And a condensation reaction in the presence of an acid catalyst.
  • the bifunctional compound used in the production of the one-step method and the two-step method includes a phosphorus-containing bifunctional phenol compound represented by the formula (6a) and a bifunctional compound having a heterocyclic structure represented by the formula (6b) Although it is a compound, other bifunctional phenol compounds may be used in combination as long as the object of the present invention is not impaired.
  • difunctional phenol compounds which may be used in combination include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol E, bisphenol C, bisphenol Z such as bisphenol acetophenone and bisphenol fluorenone, biphenols, catechol, Monocyclic bifunctional phenols, such as resorcinol and hydroquinone, dihydroxy naphthalenes, etc. are mentioned. Moreover, these may be substituted by the substituent which does not have a bad influence, such as an alkyl group and an aryl group. These bifunctional phenol compounds may be used in combination of two or more.
  • a phosphorus-containing phenoxy resin can be obtained by reacting in a non-reactive solvent in the presence of an alkali metal hydroxide, consuming epihalohydrin, and performing a condensation reaction so that the weight average molecular weight becomes 10,000 or more. .
  • the content of the phosphorus-containing bifunctional phenol compound represented by the formula (6a) used as the raw material is preferably 1 to 99% by mol, more preferably 5 to 90% by mol, and more preferably 10 to 80% by mol. 20 to 70 mol% is particularly preferable, and 30 to 50 mol% is most preferable.
  • the difunctional compound having a heterocyclic structure represented by the formula (6b) is preferably 1 to 99 mol%, more preferably 10 to 95 mol%, still more preferably 20 to 90 mol% in the raw material difunctional compound. 30 to 80 mol% is particularly preferable, and 50 to 70 mol% is most preferable.
  • the effect of the present invention is affected. 50 mol% or less is preferable with respect to the sum total with the bifunctional compound which has a heterocyclic structure represented by Formula (6b) so that it is not, 35 mol% or less is more preferable, and 20 mol% or less is more preferable.
  • the reaction can be carried out under normal pressure or under reduced pressure.
  • the reaction temperature is usually preferably 20 to 200 ° C., more preferably 30 to 170 ° C., still more preferably 40 to 150 ° C., and particularly preferably 50 to 100 ° C. in the case of reaction under normal pressure.
  • 20 to 100 ° C. is preferable, 30 to 90 ° C. is more preferable, and 35 to 80 ° C. is more preferable. If the reaction temperature is within this range, side reactions are unlikely to occur and the reaction is likely to proceed.
  • the reaction pressure is usually normal pressure. When it is necessary to remove the heat of reaction, the reaction is usually carried out by the evaporation / condensation / reflux method of the solvent used, the indirect cooling method, or a combination of these.
  • non-reactive solvents include aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as dibutyl ether, dioxane and tetrahydrofuran, ethanol and isopropyl alcohol Alcohols such as butyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, glycol ethers such as ethylene glycol dimethyl ether, etc. may be mentioned, but it is not particularly limited thereto, and these solvents may be used alone. You may mix and use two or more types.
  • catalysts can be used.
  • quaternary ammonium salts such as tetramethyl ammonium chloride and tetraethyl ammonium bromide
  • tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol
  • examples thereof include imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole, phosphonium salts such as ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine.
  • These catalysts may be used alone or in combination of two or more.
  • the bifunctional epoxy resin to be the raw material epoxy resin of the two-step method is preferably represented by the following formula (8) obtained by reacting a bifunctional compound having a heterocyclic structure represented by the above formula (6b) with epihalohydrin. It is a bifunctional epoxy resin represented.
  • X 2 in the formula (8) is replaced by X 1
  • X 2 is replaced by X 3.
  • X 2 is a divalent group having a heterocyclic structure, and divalent groups represented by the above formulas (4a) to (4f) are preferable.
  • G is a glycidyl group.
  • j is the number of repetitions, and the average value thereof is 0 to 6, preferably 0 to 3, and more preferably 0 to 1.
  • the amount is 0.80 to 1.20 moles, preferably 0.85 to 1., times the molar groups in the bifunctional compound.
  • Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like of 05 times mol are used. If the amount is smaller than this range, the amount of hydrolyzable chlorine remaining is large, which is not preferable.
  • the metal hydroxide is used in the form of an aqueous solution, an alcohol solution or a solid.
  • an excess of epihalohydrin is used for the bifunctional compound.
  • 1.5 to 15 times mol of epihalohydrin is used with respect to 1 mol of functional groups in the bifunctional compound, preferably 2 to 10 times mol, more preferably 5 to 8 times mol.
  • the production efficiency is lowered, and when it is less than this, the amount of the polymer of the epoxy resin to be produced is increased, and it is not suitable as a raw material of the phosphorus-containing phenoxy resin.
  • the epoxidation reaction is usually performed at a temperature of 120 ° C. or less. At the time of reaction, if the temperature is high, the amount of so-called poorly hydrolyzable chlorine increases and it becomes difficult to achieve high purification. Preferably it is 100 degrees C or less, More preferably, it is the temperature of 85 degrees C or less.
  • bifunctional epoxy resin to be a raw material of the two-stage method a bifunctional epoxy resin represented by the formula (8) is preferable, but other bifunctional epoxy resins may be used in combination as long as the object of the present invention is not impaired.
  • bifunctional epoxy resin which can be used together for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol acetophenone type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, bisphenol fluorenone type epoxy Resins etc.
  • epoxy resins bisphenol type epoxy resin, biphenol type epoxy resin, monocyclic bifunctional phenol diglycidyl ether such as hydroquinone type epoxy resin, dihydroxynaphthalene type epoxy resin, diphenyldicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, fat Group cyclic epoxy resin and the like.
  • These epoxy resins may be substituted with a non-defective substituent such as an alkyl group or an aryl group.
  • These epoxy resins may be used in combination of two or more. Among these, epoxy resins having divalent groups of the above formulas (5a) to (5c) are preferable.
  • a catalyst can be used, and any compound can be used as long as it has a catalytic ability to promote the reaction of the epoxy group with the phenolic hydroxyl group.
  • alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like can be mentioned.
  • These catalysts may be used alone or in combination of two or more.
  • alkali metal compound examples include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, sodium carbonate, sodium bicarbonate, alkali metal salts such as sodium chloride, lithium chloride and potassium chloride, sodium methoxy Alkali metal alkoxides such as sodium hydroxide and sodium ethoxide, alkali metal phenoxides, sodium hydride, lithium hydride and the like, and alkali metal salts of organic acids such as sodium acetate and sodium stearate and the like.
  • alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide
  • sodium carbonate sodium bicarbonate
  • alkali metal salts such as sodium chloride, lithium chloride and potassium chloride
  • sodium methoxy Alkali metal alkoxides such as sodium hydroxide and sodium ethoxide
  • alkali metal phenoxides sodium hydride, lithium hydride and the like
  • alkali metal salts of organic acids such
  • organic phosphorus compounds include tri-n-propyl phosphine, tri-n-butyl phosphine, triphenyl phosphine, tetramethyl phosphonium bromide, tetramethyl phosphonium iodide, tetramethyl phosphonium hydroxide, and trimethyl.
  • tertiary amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine and the like.
  • quaternary ammonium salts include tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium hydroxide, triethyl methyl ammonium chloride, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetraethyl ammonium iodide, tetrapropyl ammonium bromide, and tetrapropyl ammonium bromide.
  • imidazoles for example, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- And phenylimidazole.
  • cyclic amines for example, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), 1,5-diazabicyclo [4,3,0] -5-nonene (DBN), tetrahydro-1,4-oxazine (morpholine), N-methylmorpholine, N, N-dimethylaminopyridine (DMAP) and the like can be mentioned.
  • DABCO 1,4-diazabicyclo [2,2,2] octane
  • DBU 1,8-diazabicyclo [5,4,0] -7-undecene
  • DBN 1,5-diazabicyclo [4,3,0] -5-nonene
  • morpholine tetrahydro-1,4-oxazine
  • N-methylmorpholine N, N-dimethylaminopyridine (DMAP)
  • the amount of catalyst used is 0.001 to 1% by mass with respect to the reaction solid content.
  • the alkali metal component remains in the phosphorus-containing phenoxy resin, and the insulating properties of the electronic / electrical parts and printed wiring boards using it are deteriorated, so lithium in the phosphorus-containing phenoxy resin 100 ppm or less is preferable, as for the sum total of alkali metal content, such as sodium and potassium, 60 ppm or less is more preferable, and 50 ppm or less is more preferable.
  • the content of phosphorus atoms or nitrogen atoms in the phosphorus-containing phenoxy resin is preferably 300 ppm or less, more preferably 200 ppm or less, and still more preferably 100 ppm or less, because the insulation properties of electronic / electrical parts and printed wiring boards are deteriorated.
  • a solvent may be used, and any solvent may be used as long as it dissolves a phosphorus-containing phenoxy resin and does not adversely affect the reaction.
  • aromatic hydrocarbons, ketones, ester solvents, ether solvents, amide solvents, glycol ether solvents and the like can be mentioned. These solvents may be used alone or in combination of two or more.
  • aromatic hydrocarbons include benzene, toluene, xylene and the like.
  • ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, acetylacetone and the like.
  • ester solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, valerolactone, butyrolactone and the like.
  • ether solvents include diethyl ether, dibutyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane and the like.
  • amide solvents include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like.
  • glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether And-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate and the like.
  • the amount of the solvent to be used can be appropriately selected depending on the reaction conditions, but for example, in the case of the two-step production, the solid content concentration is preferably 35 to 95% by mass. If a highly viscous product is generated during the reaction, the reaction can be continued by adding a solvent during the reaction. After completion of the reaction, the solvent can be removed by distillation or the like as required, and can be further added.
  • the reaction temperature is such that the catalyst used does not decompose. If the reaction temperature is too high, the resulting phosphorus-containing phenoxy resin may be degraded. If it is too low, the reaction may not proceed and the target molecular weight may not be achieved. Therefore, the reaction temperature is preferably 50 to 230 ° C., and more preferably 120 to 200 ° C.
  • the reaction time is usually 1 to 12 hours, preferably 3 to 10 hours.
  • a low boiling point solvent such as acetone or methyl ethyl ketone
  • the reaction temperature can be secured by conducting the reaction under high pressure using an autoclave. When it is necessary to remove the heat of reaction, it is usually carried out by the evaporation / condensation / reflux method of the solvent used by the heat of reaction, the indirect cooling method, or a combination of these.
  • the phosphorus-containing phenoxy resin of the present invention is a thermoplastic resin which is flame retardant by itself and is flexible and can be used alone, but it can be used as a thermosetting resin by blending a curable resin component. It can be made a resin composition.
  • the curable resin component include epoxy resin, acrylic ester resin, phenol resin, melanin resin, urea resin, unsaturated polyester resin, isocyanate resin, alkyd resin, thermosetting polyimide resin and the like.
  • an epoxy resin, a phenol resin, a melanin resin and an isocyanate resin are preferable, and an epoxy resin is more preferable.
  • These curable resin components may be used alone or in combination of two or more.
  • the curable resin component for example, a resin composition which cures an epoxy resin with a curing agent, a resin composition which cures an acrylic ester resin with a radical polymerization initiator, a phenol resin, a melanin resin, an isocyanate resin, etc. Resin components and the like.
  • the compounding amount of the curable resin component is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, as phosphorus-containing phenoxy resin / curable resin component (mass ratio), and 25/75 to 75 / 25 is more preferable.
  • the curable resin component is an epoxy resin
  • conventionally known epoxy resins can be used.
  • an epoxy resin refers to the epoxy resin which has at least 1 piece of epoxy group, the epoxy resin which has 2 or more epoxy groups is preferable, and the epoxy resin which has 3 or more epoxy groups is more preferable.
  • Specific examples thereof include polyglycidyl ether compounds, polyglycidyl amine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone, or two or more of the same epoxy resins may be used in combination, or epoxy resins of different systems may be used in combination.
  • polyglycidyl ether compounds include bisphenol A epoxy resin, bisphenol F epoxy resin, tetramethyl bisphenol F epoxy resin, biphenol epoxy resin, hydroquinone epoxy resin, bisphenol fluorene epoxy resin, naphthalene diol Epoxy resin, bisphenol S epoxy resin, diphenyl sulfide epoxy resin, diphenyl ether epoxy resin, resorcinol epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, alkyl novolac epoxy resin, styrenated phenol novolac epoxy Resin, bisphenol novolac epoxy resin, naphthol novolac epoxy resin, ⁇ -naphthol ala Kill type epoxy resin, naphthalenediol aralkyl type epoxy resin, ⁇ -naphthol aralkyl type epoxy resin, biphenylaralkylphenol type epoxy resin, trihydroxyphenylmethane type epoxy resin, tetrahydroxyphenylethane type epoxy resin, dicycl
  • polyglycidyl amine compounds include diaminodiphenylmethane type epoxy resin, metaxylene diamine type epoxy resin, 1,3-bisaminomethylcyclohexane type epoxy resin, isocyanurate type epoxy resin, aniline type epoxy resin, hydantoin type epoxy resin An epoxy resin, an aminophenol type epoxy resin, etc. are mentioned.
  • polyglycidyl ester compounds include dimer acid type epoxy resins, hexahydrophthalic acid type epoxy resins, trimellitic acid type epoxy resins, and the like.
  • an alicyclic epoxy compound aliphatic cyclic epoxy resins, such as Celoxide 2021 (made by Daicel Chemical Industries, Ltd.), etc. are mentioned.
  • modified epoxy resin specifically, urethane modified epoxy resin, oxazolidone ring containing epoxy resin, epoxy modified polybutadiene rubber derivative, carboxyl group-terminated butadiene nitrile rubber (CTBN) modified epoxy resin, polyvinylarene polyoxide (eg, divinyl) Benzene dioxide, trivinyl naphthalene trioxide, etc.), a phosphorus containing epoxy resin, etc. are mentioned.
  • CBN carboxyl group-terminated butadiene nitrile rubber
  • the curing agent is a substance that contributes to the crosslinking reaction and / or the chain extension reaction between epoxy groups of the epoxy resin.
  • the compounding amount of the curing agent is 0.1 to 100 parts by mass as needed, preferably 1 to 80 parts by mass, more preferably 5 to 60 parts by mass, with respect to 100 parts by mass of the epoxy resin. 60 parts by mass is more preferred.
  • the curing agent is not particularly limited, and any of those generally known as epoxy resin curing agents can be used.
  • curing agent, and imidazole are mentioned.
  • an active ester type hardening agent is mentioned as a preferable thing.
  • amine curing agents In addition, amine curing agents, acid anhydride curing agents, organic phosphines, phosphonium salts, benzoxazine compounds, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan curing agents, isocyanate curing And blocked isocyanate curing agents.
  • amine curing agents may be used alone, or two or more of the same type may be used in combination, or other types may be used in combination.
  • phenolic curing agents include bisphenol A, bisphenol F, dihydroxydiphenylmethane, dihydroxydiphenyl ether, bis (hydroxyphenoxy) benzene, dihydroxydiphenyl sulfide, dihydroxydiphenyl ketone, dihydroxydiphenyl sulfone, fluorene bisphenol, hydroquinone, resorcine, catechol, t.
  • -Difunctional phenolic compounds such as -butyl catechol, t-butyl hydroquinone, dihydroxynaphthalene and dihydroxymethylnaphthalene, phenol novolac, bisphenol A novolac, cresol novolac, xylenol novolac, trishydroxyphenylmethane novolac, dicyclopentadiene phenol, naphthol novolac , Styrenated fe Trivalent compounds such as ol novolac, terpene phenol, heavy oil modified phenol, phenol aralkyl, naphthol aralkyl, polyhydroxystyrene, fluoroglycinol, pyrogallol, t-butyl pyrogallol, benzenetriol, trihydroxynaphthalene, trihydroxybenzophenone, trihydroxyacetophenone, etc.
  • the above-mentioned phenol compounds and phosphorus-containing phenol compounds such as 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide may be mentioned. Those obtained by reacting these phenol compounds with indene or styrene may be used as a curing agent.
  • the phenolic curing agent is preferably used at a molar ratio of active hydroxyl groups in the curing agent to epoxy groups in the epoxy resin in the range of 0.8 to 1.5.
  • Examples of the amide-based curing agent include dicyandiamide and derivatives thereof, and polyamide resins.
  • the amide curing agent is preferably used in the range of 0.1 to 25 parts by mass with respect to 100 parts by mass of the total epoxy resin component.
  • the imidazoles include 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2'-Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]
  • the imidazole is preferably used in the range of 0.1 to 25 parts by mass with respect to 100 parts by mass of the total epoxy resin component.
  • imidazoles since imidazoles have catalytic ability, they are generally classified as curing accelerators described later, but in the present invention, they are classified as curing agents.
  • active ester curing agents compounds having two or more reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. Among them, phenol esters obtained by reacting a polyfunctional phenol compound and an aromatic carboxylic acid as described in Japanese Patent No. 5152445 are preferable.
  • Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid.
  • Examples of the aromatic compound having a phenolic hydroxyl group include catechol, dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, phenol novolac and the like.
  • Commercially available products include Epiclon HPC-8000-65T (manufactured by DIC Corporation) and the like, but are not limited thereto.
  • the active ester curing agent is preferably used in a molar ratio of 0.2 to 2.0 in terms of the molar ratio of the active ester group in the curing agent to the epoxy group in the resin composition.
  • the amine-based curing agent include diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl ether, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, Examples thereof include amine compounds such as polyamidoamine which is a condensation product of an acid such as dicyandiamide or dimer acid and a polyamine.
  • the amine curing agent is preferably used in a molar ratio of 0.5 to 1.5 in terms of a molar ratio of active hydrogen groups in the curing agent to epoxy groups in the resin composition.
  • the acid anhydride curing agent for example, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, methyl anhydride Nadic acid, maleic anhydride and the like can be mentioned.
  • the acid anhydride curing agent is preferably used in a molar ratio of 0.5 to 1.5 in terms of the molar ratio of the acid anhydride group in the curing agent to the epoxy group in the resin composition.
  • the active hydrogen group includes a functional group having active hydrogen reactive with an epoxy group (a functional group having latent active hydrogen which generates active hydrogen upon hydrolysis etc., and a functional group having an equivalent curing action.
  • an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group etc. are mentioned.
  • the number of carboxyl groups (—COOH) and phenolic hydroxyl groups (—OH) is 1 mole, and that of amino groups (—NH 2 ) is 2 moles, with respect to the active hydrogen group.
  • an active hydrogen equivalent can be calculated
  • the active hydrogen equivalent of the used curing agent is obtained by reacting a monoepoxy resin having a known epoxy equivalent such as phenyl glycidyl ether with a curing agent having an unknown active hydrogen equivalent and measuring the amount of the monoepoxy resin consumed.
  • a hardening accelerator when mix
  • the curing accelerator include imidazole derivatives, tertiary amines, phosphorus compounds such as phosphines, metal compounds, Lewis acids, amine complex salts and the like. These curing accelerators may be used alone or in combination of two or more.
  • the imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton.
  • a ring structure such as And an imidazole compound substituted with a hydrocarbon group.
  • tertiary amines for example, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo [5.4.0] -7-undecene ( DBU etc. are mentioned.
  • phosphines include triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphine triphenyl borane and the like.
  • metal compounds include tin octylate and the like.
  • amine complex salt for example, boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenylamine complex, boron trifluoride benzylamine complex, boron trifluoride An aniline complex or boron trifluoride complexes, such as mixtures thereof, etc. are mentioned.
  • curing accelerators when used as a build-up material application or circuit board application, 2-dimethylaminopyridine, 4-dimethylaminopyridine or the like from the viewpoint of being excellent in heat resistance, dielectric properties, solder resistance, etc. Imidazoles are preferred. Moreover, when using it as a semiconductor sealing material use, a triphenyl phosphine and DBU are preferable from the point which is excellent in curability, heat resistance, an electrical property, moisture-reliability etc.
  • the compounding amount of the curing accelerator may be appropriately selected according to the purpose of use, 0.01 to 15 parts by mass is used as needed with respect to 100 parts by mass of the epoxy resin component in the resin composition, The amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.1 to 5 parts by mass.
  • a curing accelerator By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.
  • the resin composition which hardens the acrylic acid ester resin as a curable resin component with a radical polymerization initiator includes a thermosetting resin composition of a (meth) acrylate compound and a photocurable resin composition.
  • the (meth) acrylate compound is an acrylate having at least one or more (meth) acryloyl group in a molecule used as a viscosity adjusting or curing component. It is desirable that part of the (meth) acrylate compound has two or more (meth) acryloyl groups.
  • the resin composition in this case contains a (meth) acrylate compound, a thermal polymerization initiator, a photo polymerization initiator, or both as essential components.
  • Examples of these (meth) acrylate compounds include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, and dicyclopentanyl Meta) acrylate, acryloyl morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl polyester X- (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate
  • a compound which can be used as a polymerization initiator of a (meth) acrylate type compound if it is what generate
  • the polymerization initiator for example, in the case of curing by heating, any of those which can be used for ordinary radical thermal polymerization such as azo type isobutyro nitrile, azo type such as benzoyl peroxide, peroxide type initiator etc. It can be used.
  • radical polymerization is carried out by photo radical polymerization
  • any of those which can be used for ordinary photo radical polymerization such as benzoins, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, phosphine oxides, etc. should be used.
  • These polymerization photoinitiators may be used alone or as a mixture of two or more.
  • the radical photopolymerization initiator may be used in combination with an accelerator such as a tertiary amine compound or ethyl ester of N, N-dimethylaminobenzoic acid.
  • an organic solvent or reactive diluent can be used for viscosity adjustment.
  • These organic solvents or reactive diluents may be used alone or in combination of two or more.
  • organic solvent examples include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol Ethers such as dimethyl ether, Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol , Alcohols such as butyl diglycol and pine oil, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl Acetoates such as cellosolve acetate, cellosolve acetate, e
  • reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether , Difunctional glycidyl ethers such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane Polyglycidyl ether, trimethylolethane polyglycidyl ether, pentaerythrito
  • organic solvents or reactive diluents at 90 mass% or less as a non volatile matter
  • the appropriate kind and the usage-amount are suitably selected by a use.
  • polar solvents such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol and the like having a boiling point of 160 ° C. or less are preferable, and the amount thereof used is preferably 40 to 80% by mass in nonvolatile matter.
  • non-halogen flame retardants substantially containing no halogen atom may be used together with the object of improving the flame retardancy of the cured product to be obtained, as long as the reliability is not reduced. it can.
  • non-halogen flame retardants examples include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants and the like. These non-halogen flame retardants are not limited at all when used, and may be used alone, or two or more of the same flame retardants may be used in combination, and different flame retardants may be used. It may be used in combination. Since the phosphorus-containing phenoxy resin of the present invention is excellent in flame retardancy, the blending of the flame retardant can be unnecessary or greatly reduced.
  • any of inorganic phosphorus-based compounds and organic phosphorus-based compounds can be used.
  • inorganic phosphorus compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, ammonium phosphates such as ammonium triphosphate and ammonium polyphosphate, and nitrogen-containing inorganic phosphorus compounds such as phosphoric acid amide.
  • red phosphorus is subjected to surface treatment for the purpose of preventing hydrolysis and the like, and as the surface treatment method, for example, (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, hydroxide Method of coating with an inorganic compound such as titanium, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof, (2) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and phenol Method of coating with a mixture of thermosetting resin such as resin, (3) Thermosetting resin such as phenol resin on a film of inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide And the like.
  • the surface treatment method for example, (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, hydroxide Method of coating with an inorganic compound such as titanium, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof, (2) inorganic compounds such as
  • organic phosphorus compounds examples include general-purpose organic phosphorus compounds such as phosphoric acid ester compounds, condensed phosphoric acid esters, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, and phosphorane compounds, nitrogen-containing organic phosphorus compounds,
  • phosphorus compounds having an active hydrogen group directly linked to a phosphorus atom eg, DOPO, diphenyl phosphine oxide etc.
  • phosphorus-containing phenol compounds eg, 10- (2,5-dihydroxyphenyl)- 10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO-HQ), 10- (2,7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10 Oxide (hereinafter referred to as DOPO-NQ), diphenyl phosphini Hydroquinone,
  • DOPO-HQ 10- (2,5-dihydroxypheny
  • part represented by Formula (3) are preferable.
  • the phosphorus-containing epoxy resin include Epototh FX-305, FX-289B, TX-1320A, TX-1328 (all manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) and the like.
  • the epoxy equivalent (g / eq.) Of the phosphorus-containing epoxy resin is preferably 200 to 800, more preferably 300 to 780, and still more preferably 400 to 760.
  • the phosphorus content is preferably 0.5 to 6% by mass, more preferably 2 to 5.5% by mass, and still more preferably 3 to 5% by mass.
  • the phosphorus-containing curing agent in addition to the above-mentioned phosphorus-containing bifunctional phenol compound, a structural part represented by the formula (3) by a production method as shown in JP-A-2008-501063 or JP-A- 4548547.
  • a phosphorus-containing phenol compound can be obtained by reacting an aldehyde compound with a phenol compound.
  • the phosphorus compound having the structural unit represented by the formula (3) is incorporated into the molecule by condensation addition to the aromatic ring of the phenol compound via aldehydes.
  • phosphorus-containing active ester is obtained from a phosphorus compound phenol compound having a structural part represented by the formula (3) by further reacting an aromatic carboxylic acid according to a production method as shown in JP-A-2013-185002.
  • Compounds can be obtained.
  • the phosphorus-containing benzoxazine compound which has a structure part represented by Formula (3) can be obtained with a manufacturing method as shown to the back table 2008/010429 gazette.
  • the compounding quantity of the phosphorus compound used together is suitably selected by the kind of phosphorus compound, phosphorus content, the component of a resin composition, and the extent of desired flame retardance.
  • a phosphorus compound in which a phosphorus compound is reactive that is, a phosphorus-containing epoxy resin or a phosphorus-containing curing agent, a resin composition containing all of a phosphorus-containing phenoxy resin, a curable resin component, a flame retardant and other fillers, additives, etc.
  • the phosphorus content is 0.2 to 6% by mass with respect to the total solid content in the resin (generally, the total solid content in the resin composition means the total of components excluding the solvent in the resin composition) Is preferable, 0.4 to 4% by mass is more preferable, 0.5 to 3.5% by mass is more preferable, and 0.6 to 3.0% by mass is particularly preferable. If the phosphorus content is low, it may be difficult to ensure flame retardancy, and if it is too high, the heat resistance and solvent solubility may be adversely affected.
  • the actual blending amount is preferably in the range of 0.1 to 2% by mass when using red phosphorus with respect to the total solid content in the resin composition, and 0.1 when using an organophosphorus compound
  • the range of -10% by mass is preferable, and the range of 0.5-6% by mass is more preferable.
  • hydrotalcite magnesium hydroxide
  • a boron compound zirconium oxide
  • calcium carbonate calcium carbonate
  • zinc molybdate zinc molybdate
  • a flame retardant when used in combination, it is preferable to use a phosphorus-based flame retardant, but the flame retardants described below can also be used in combination.
  • nitrogen-based flame retardant examples include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine and the like, and triazine compounds, cyanuric acid compounds and isocyanuric acid compounds are preferable.
  • the compounding quantity of a nitrogen-type flame retardant is suitably selected by the kind of nitrogen-type flame retardant, the other component of a resin composition, and the extent of the desired flame retardance, for example, the total solid in a resin composition It is preferable to mix
  • the silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber and silicone resin.
  • the compounding quantity of a silicone type flame retardant is suitably selected by the kind of silicone type flame retardant, the other component of a resin composition, and the extent of the desired flame retardance, for example, the total solid in a resin composition It is preferable to mix
  • an inorganic type flame retardant a metal hydroxide, a metal oxide, a metal carbonate compound, a metal powder, a boron compound, low melting glass, etc. are mentioned, for example.
  • the compounding quantity of an inorganic type flame retardant is suitably selected by the kind of inorganic type flame retardant, the other component of a resin composition, and the extent of desired flame retardance, a phenoxy resin, curable resin component, for example It is preferable to blend it in the range of 0.05 to 20% by mass with respect to the total solid content in the resin composition in which all of the flame retardant and other fillers, additives and the like are blended, particularly 0.5 to 15 It is preferable to mix
  • organic metal salt flame retardant for example, ferrocene, acetylacetonato metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound are ionically bonded or arranged And the like.
  • the compounding amount of the organic metal salt-based flame retardant is appropriately selected according to the type of the organic metal salt-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. It is preferable to blend in the range of 0.005 to 10% by mass with respect to the total solid content of the resin composition in which all of the curable resin component, the flame retardant and other fillers, additives and the like are blended.
  • a filler if necessary, a filler, a thermoplastic resin, a thermosetting resin other than an epoxy resin, a coupling agent, an antioxidant, a mold release agent, an extinction agent, as long as the properties are not impaired.
  • Other additives such as a foaming agent, an emulsifying agent, a thixotropic agent, a leveling agent, and a pigment can be blended.
  • the filler for example, fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, Inorganic fillers such as barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide Fibrous fillers such as fibers, polyester fibers, cellulose fibers, aramid fibers, ceramic fibers and the like, fine particle rubbers and the like can be mentioned.
  • fused silica when making the compounding quantity of a filler especially large.
  • fused silica can be used either in a crushed or spherical shape, it is more preferable to use mainly spherical ones in order to suppress the increase in melt viscosity of the molding material while increasing the blending amount of fused silica. .
  • the filler may be treated with a silane coupling agent or an organic acid such as stearic acid.
  • a silane coupling agent or an organic acid such as stearic acid.
  • the reason for using a filler is the effect of improving the impact resistance of the cured product, and the low linear expansion of the cured product.
  • a metal hydroxide such as aluminum hydroxide, boehmite or magnesium hydroxide is used, it acts as a flame retardant auxiliary and has an effect of improving the flame retardancy.
  • alumina, silicon nitride, boron nitride, aluminum nitride, fused silica and crystalline silica are preferable, and alumina, boron nitride, fused silica and crystalline silica are more preferable.
  • conductive fillers such as silver powder and copper powder can be used.
  • the blending amount of the filler is preferably high in consideration of the low linear expansion of the cured product and the flame retardancy.
  • the amount is preferably 1 to 98% by mass, more preferably 3 to 90% by mass, still more preferably 5 to 80% by mass, and particularly preferably 10 to 60% by mass, with respect to the total solid content in the resin composition. If the compounding amount is too large, the adhesion required for laminate applications may be reduced, and the cured product may be brittle, and sufficient mechanical properties may not be obtained. Moreover, when the compounding amount is small, there is a possibility that the compounding effect of the filler, such as improvement of impact resistance of the cured product, may not be obtained.
  • the average particle size is preferably 0.01 to 5 ⁇ m, more preferably 0.05 to 1.5 ⁇ m, and still more preferably 0.1 to 1 ⁇ m. If the average particle size of the inorganic filler is in this range, the flowability of the resin composition can be maintained well.
  • the average particle size can be measured by a particle size distribution measuring apparatus.
  • thermoplastic resin other than the phosphorus-containing phenoxy resin of the present invention may be used in combination.
  • the thermoplastic resin includes, for example, phenoxy resin, polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate resin, polycarbonate resin, Polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether sulfone resin, polysulfone resin, polyether ether resin Ketone resin, polyphenylene sulfide resin, polyvinyl formal resin, etc. may be mentioned. From the viewpoint of compatibility, phenoxy resins are preferred, and from the viewpoint of low dielectric properties, polyphenylene ether
  • a coupling agent may be blended in the resin composition of the present invention.
  • By blending the coupling agent it is possible to improve the adhesion to the substrate and the adhesion to the matrix resin and the inorganic filler.
  • a coupling agent a silane coupling agent, a titanate coupling agent, etc. are mentioned. These coupling agents may be used alone or in combination of two or more.
  • the compounding amount of the coupling agent is preferably about 0.1 to 2.0% by mass with respect to the total solid content in the resin composition. If the blending amount of the coupling agent is too small, the effect of improving the adhesion between the matrix resin and the inorganic filler can not be sufficiently obtained by blending the coupling agent, while the blending amount of the coupling agent is large. If it is too much, the coupling agent may bleed out from the resulting cured product.
  • silane coupling agent for example, epoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - Aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane Aminosilanes such as silane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane,
  • titanate coupling agent for example, isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, etc.
  • isopropyl triisostearoyl titanate isopropyl tri (N-aminoethyl aminoethyl) titanate
  • additives include organic pigments such as quinacridone, azo and phthalocyanine pigments, inorganic pigments such as titanium oxide, metal foil pigments and rust preventive pigments, and UV light such as hindered amine, benzotriazole and benzophenone pigments Absorbents, antioxidants such as hindered phenols, phosphorus, sulfur and hydrazides, release agents such as stearic acid, palmitic acid, zinc stearate and calcium stearate, leveling agents, rheology control agents, pigments Additives, such as a dispersing agent, a repelling inhibitor, an antifoamer, etc. are mentioned.
  • the compounding amount of these other additives is preferably in the range of 0.01 to 20% by mass with respect to the total solid content in the resin composition.
  • the resin composition of the present invention is obtained by uniformly mixing the above-mentioned components.
  • the resin composition containing a phosphorus-containing phenoxy resin, a curable resin component, and, if necessary, various additives, can be easily made into a cured product by the same method as conventionally known.
  • the cured product include molded and cured products such as laminates, cast products, molded products, adhesive layers, insulating layers and films.
  • the same method as a known resin composition can be used, and casting, pouring, potting, dipping, drip coating, transfer molding, compression molding, resin sheet, copper with resin, etc.
  • a method of forming a laminate by laminating in the form of a foil, a prepreg or the like and heating and pressure curing is suitably used.
  • the curing method of the resin composition varies depending on the blending components and the blending amount in the resin composition, but the curing temperature is usually 80 to 300 ° C., and the curing time is 10 to 360 minutes.
  • This heating is preferably performed in a two-step process of primary heating at 80 to 180 ° C. for 10 to 90 minutes and secondary heating at 120 to 200 ° C. for 60 to 150 minutes, and the glass transition temperature (Tg) is In a compounding system in which the temperature of the secondary heating is exceeded, it is preferable to further perform tertiary heating at 150 to 280 ° C. for 60 to 120 minutes.
  • Curing defects can be reduced by performing such secondary heating and tertiary heating.
  • a resin semi-cured product such as a resin sheet, a copper foil with resin, a prepreg, etc.
  • the curing reaction of the resin composition is usually advanced to such an extent that the shape can be maintained by heating or the like.
  • the resin composition contains a solvent, usually, the majority of the solvent is removed by a method such as heating, reduced pressure, air drying, etc., but a residual solvent of 5% by mass or less is left in the semi-cured resin It is also good.
  • the resin composition can be used in various fields such as circuit board materials, sealing materials, casting materials, conductive pastes, adhesives, insulating materials, etc., and in particular, the electric and electronic fields It is useful as an insulation casting, a lamination material, a sealing material etc.
  • Examples of applications include printed wiring boards, flexible wiring boards, laminates for electric and electronic circuits such as capacitors, metal foils with resin, film-like adhesives, adhesives such as liquid adhesives, semiconductor sealing materials, and under Examples thereof include, but are not limited to, fill materials, interchip fills for 3D-LSI, insulating materials for circuit boards, insulating sheets, prepregs, heat dissipation boards, and resist inks.
  • so-called electronic component embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded in a substrate for printed wiring board materials, insulating materials for circuit boards, and adhesive films for buildup It can be used as an insulating material for Among these, for circuit boards (laminated boards) such as printed wiring board materials, resin compositions for flexible wiring boards, and interlayer insulation materials for buildup boards because of their properties such as high flame retardancy, high heat resistance, and solvent solubility. It is preferable to use for material and semiconductor sealing material.
  • a fibrous thing is preferable at points, such as dimensional stability and flexural strength, and glass cloth, glass mat, glass roving cloth are More preferable.
  • the resin composition can be impregnated into a fibrous reinforcing substrate to make a prepreg used in a printed wiring board or the like.
  • a fibrous reinforcing substrate for example, woven or non-woven fabric of inorganic fibers such as glass, or organic fibers such as polyester resin, etc., polyamine resin, polyacrylic resin, polyimide resin, aromatic polyamide resin, etc. Although it can be done, it is not limited to this.
  • a prepreg from a resin composition
  • it is the resin varnish which mix
  • the resin varnish is prepared, and the resinous varnish is impregnated into the above-mentioned fibrous base material, followed by heating and drying to semi-cure (B-stage) the resin component.
  • the heating temperature is preferably 50 to 200 ° C., more preferably 100 to 170 ° C., depending on the type of the organic solvent used.
  • the heating time is adjusted depending on the type of the organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, and more preferably 3 to 20 minutes.
  • the mass ratio of the resin composition to be used and the reinforcing substrate is not particularly limited, but in general, it is preferable to adjust the resin content in the prepreg to be 20 to 80 mass%.
  • the resin composition of the present invention can be used after being formed into a sheet or film. In this case, it is possible to form a sheet or a film using a conventionally known method.
  • the method for producing the resin sheet is not particularly limited, but, for example, (a) extruding after kneading the resin composition with an extruder and extruding it into a sheet using a T die, a circular die, etc. Molding methods, (ii) casting methods in which a resin composition is dissolved or dispersed in a solvent such as an organic solvent and then casting to form a sheet, and (iii) other sheet forming methods known in the prior art, etc. .
  • the thickness of the resin sheet is not particularly limited, but is, for example, 10 to 300 ⁇ m, preferably 25 to 200 ⁇ m, and more preferably 40 to 180 ⁇ m. When used in a build-up method, 40 to 90 ⁇ m is most preferable. If the film thickness is 10 ⁇ m or more, insulation can be obtained, and if it is 300 ⁇ m or less, the circuit distance between the electrodes does not become longer than necessary.
  • the content of the solvent in the resin sheet is not particularly limited, it is preferably 0.01 to 5% by mass with respect to the entire resin composition.
  • the content of the solvent in the film is 0.01% by mass or more with respect to the entire resin composition, adhesion and adhesiveness are easily obtained when laminating on a circuit board, and if it is 5% by mass or less, heating is performed. Flatness after curing can be easily obtained.
  • a coating machine such as a reverse roll coater, a comma coater, a die coater or the like is used on a supporting base film in which the varnish-like resin composition containing the above organic solvent is not dissolved in the organic solvent. It is obtained by heat-drying and B-staging the resin component after coating.
  • another supporting base film is overlaid on the coated surface (adhesive layer) as a protective film, and drying is performed to obtain an adhesive sheet having a release layer on both sides of the adhesive layer.
  • supporting base films include metal foils such as copper foils, polyolefin films such as polyethylene films and polypropylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, silicon films, polyimide films, and the like.
  • metal foils particularly copper foils, in which multilayering of the laminate is easy are preferable.
  • the thickness of the supporting base film is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 25 to 50 ⁇ m, because it has strength as a support and is less likely to cause lamination failure.
  • the thickness of the protective film is not particularly limited, but generally 5 to 50 ⁇ m.
  • the thickness of the resin varnish applied is preferably 5 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, as the thickness after drying.
  • the heating temperature is preferably 50 to 200 ° C., more preferably 100 to 170 ° C., depending on the type of the organic solvent used.
  • the heating time is adjusted depending on the type of the organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes.
  • the resin sheet thus obtained is usually an insulating adhesive sheet having an insulating property, but a conductive adhesive sheet is obtained by mixing a conductive metal and metal-coated fine particles with the resin composition. It can also be done.
  • the support base film is peeled off after laminating on a circuit board or after heat curing to form an insulating layer. If the support base film is peeled off after the adhesive sheet is heated and cured, it is possible to prevent the adhesion of dust and the like in the curing step.
  • the insulating adhesive sheet is also an insulating sheet.
  • the metal foil with resin obtained by the resin composition of the present invention will be described.
  • the metal foil a single, alloy, or composite metal foil of copper, aluminum, brass, nickel and the like can be used. It is preferable to use a metal foil of 9 to 70 ⁇ m in thickness. It does not specifically limit as a flame retardant resin composition which comprises a phosphorus containing epoxy resin, and a method of manufacturing metal foil with resin from metal foil, For example, the said phosphorus containing resin composition is carried out to one surface of the said metal foil
  • the resin varnish whose viscosity is adjusted with a solvent is applied using a roll coater or the like, and then dried by heating to semi-cure the resin component (B-staging) to form a resin layer. When semi-curing the resin component, for example, it can be dried by heating at 100 to 200 ° C. for 1 to 40 minutes.
  • the thickness of the resin portion of the resin-attached metal foil is desirably 5 to 110 ⁇ m.
  • the prepreg and the insulating adhesive sheet it is possible to use a method of curing a laminate in general when producing a printed wiring board, but it is not limited thereto.
  • a method of curing a laminate in general when producing a printed wiring board, but it is not limited thereto.
  • a metal foil is disposed on one side or both sides to construct a laminate, and the laminate is pressurized and heated.
  • the prepreg can be cured and integrated to obtain a laminate.
  • the metal foil a metal foil of copper, aluminum, brass, nickel, etc. alone, an alloy, or a composite can be used.
  • the conditions for heating and pressing the laminate may be appropriately adjusted under the conditions for curing of the resin composition, and heating and pressing may be carried out, but if the amount of pressure applied is too low, bubbles will remain inside the resulting laminate. Since the electrical characteristics may be reduced, it is desirable to apply pressure under conditions that satisfy moldability.
  • the heating temperature is preferably 160 to 250 ° C., and more preferably 170 to 220 ° C.
  • the pressure applied is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa.
  • the heating and pressurizing time is preferably 10 minutes to 4 hours, and more preferably 40 minutes to 3 hours. If the heating temperature is low, the curing reaction may not proceed sufficiently, and if the temperature is high, thermal decomposition of the cured product may occur.
  • the applied pressure is low, air bubbles may remain inside the obtained laminate, and the electrical properties may be degraded. If the applied pressure is high, the resin may flow before curing, and a laminate having a desired thickness may not be obtained. There is a fear. In addition, if the heating and pressing time is short, the curing reaction may not proceed sufficiently, and if it is long, thermal decomposition of the cured product may occur.
  • a multilayer board can be created by using the single-layer laminated board obtained in this manner as an inner layer material.
  • the laminated board is subjected to circuit formation by an additive method or a subtractive method, and the formed circuit surface is treated with an acid solution and subjected to a blackening treatment to obtain an inner layer material.
  • An insulating layer is formed of a prepreg, a resin sheet, an insulating adhesive sheet, or a metal foil with resin on one side or both sides of a circuit forming surface of this inner layer material, and a conductor layer is formed on the surface of the insulating layer. It forms.
  • metal foil is arrange
  • metal foil the thing similar to what was used for the laminated board used as an inner-layer board can be used. The heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.
  • the printed wiring board can be molded by forming via holes and forming circuits on the surface of the multilayer laminate molded in this manner by the additive method or the subtractive method. Further, by repeating the above-described method using the printed wiring board as an inner layer material, a multilayer board of further layers can be formed.
  • an insulation adhesion sheet is arrange
  • an insulating adhesive sheet is disposed between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressurized to be integrally molded, thereby forming a cured product of the insulating adhesive sheet as an insulating layer and forming a multilayer of the inner layer material.
  • a metal foil that is an inner layer material and a conductor layer is formed as a cured product of the insulating adhesive sheet.
  • metal foil the thing similar to what was used for the laminated board used as an inner-layer material can be used. The heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.
  • the resin composition When a resin composition is applied to a laminate to form an insulating layer, the resin composition is preferably applied to a thickness of 5 to 100 ⁇ m and then 100 to 200 ° C., preferably 150 to 200 ° C.
  • the sheet is dried by heating and drying for about 120 minutes, preferably for about 30 to 90 minutes. It is generally formed by a method called casting method.
  • the thickness after drying is desirably 5 to 150 ⁇ m, preferably 5 to 80 ⁇ m.
  • the viscosity of the resin composition is preferably 10 to 40000 mPa ⁇ s at 25 ° C., and more preferably 200 to 30000 mPa ⁇ s, because a sufficient film thickness can be obtained and coating unevenness and streaks are hardly generated.
  • a printed wiring board can be formed by further forming via holes or forming circuits by the additive method or the subtractive method on the surface of the multilayer laminate thus formed. Further, by repeating the above-described method using the printed wiring board as an inner layer material, it is possible to form a multilayer board in a further multilayer.
  • Sealing materials obtained using the resin composition of the present invention include tape-like semiconductor chips, potting-type liquid seals, underfills, semiconductor interlayer insulation films, etc. It can be used.
  • a resin composition is cast or molded using a transfer molding machine, an injection molding machine, etc., and a molded article is obtained by heating at 50 to 200 ° C. for 2 to 10 hours. The method is mentioned.
  • a compounding agent such as an inorganic filler and an additive such as a coupling agent and a mold release agent, which are compounded as necessary, are added to the resin composition.
  • an extruder, a kneader, a roll or the like may be used to sufficiently melt and mix until uniform.
  • silica is generally used as the inorganic filler, but in that case, it is preferable to blend the inorganic filler in a proportion of 70 to 95% by mass in the resin composition.
  • the resin composition thus obtained is used as a tape-like sealing material, it is heated to prepare a semi-cured sheet, which is made into a sealing material tape, and then this sealing material tape is used.
  • a method of placing on a semiconductor chip, heating at 100 to 150 ° C. to soften and shape, and curing completely at 170 to 250 ° C. can be mentioned.
  • a potting type liquid sealing material after melt
  • the resin composition of the present invention can also be used as a resist ink.
  • a vinyl monomer having an ethylenically unsaturated double bond, a cationic polymerization catalyst as a curing agent, and a pigment, talc, and a filler are further added to the resin composition to prepare a composition for resist ink.
  • the composition is applied onto a print substrate by a screen printing method, and then a method of forming a cured resist ink is mentioned.
  • the curing temperature at this time is preferably in the range of about 20 to 250.degree.
  • the resin composition of the present invention was prepared, and the cured product was evaluated by heat curing. As a result, the flame retardancy is good despite the low residual carbon ratio. This indicates that the material is excellent in tracking resistance. Therefore, it is useful as a material of the board
  • Epoxy equivalent The measurement is performed according to JIS K7236 standard, and the unit is g / eq. It is.
  • Epoxy equivalent weight It measured by the method of JISK-7236, and computed the numerical value as solid content conversion value from the non volatile matter.
  • Weight average molecular weight (Mw) It calculated
  • 0.1 g of a solid sample was dissolved in 10 mL of N, N-dimethylformamide, and 20 ⁇ L of a 0.45 ⁇ m microfilter filtered solid was used as a measurement sample.
  • Mw is calculated from the calibration curve calculated from standard polyethylene oxide (manufactured by Tosoh Corporation, SE-2, SE-5, SE-8, SE-15, SE-30, SE-70, SE-150).
  • GPC-8020 model II version 6.00 manufactured by Tosoh Corporation was used.
  • Phosphorus content rate Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample and heated to wet ashing to convert all phosphorus atoms into orthophosphoric acid. The metavanadate and molybdate were reacted in a sulfuric acid solution, and the absorbance at 420 nm of the resulting phosphovanad molybdate complex was measured, and the phosphorus atom content determined by a calibration curve prepared in advance was expressed as%.
  • Tig extrapolated glass transition start temperature
  • As a measurement sample a resin film was punched, laminated, and packed in an aluminum capsule for use. The measurement was performed twice from room temperature to 240 ° C. at a temperature rising rate of 10 ° C./min.
  • Water absorption rate The measurement was performed using five test pieces obtained by cutting a resin film into 50 mm ⁇ 50 mm squares. The test piece is dried for 10 minutes at 100 ° C. in an air atmosphere using a hot-air circulating oven, and the mass is measured immediately, and the test piece is immersed in water at 25 ° C. I asked for.
  • Synthesis Example 1 (Synthesis of Heterocycle-Containing Epoxy Resin) At a room temperature, 73 parts of isosorbide, 1388 parts of epichlorohydrin, and 278 parts of ethylene glycol dimethyl ether are charged into a reactor equipped with a stirrer, thermometer, nitrogen gas introduction device, cooling pipe and water separator, and nitrogen gas The temperature was raised to 50.degree. C. while stirring. While maintaining the same temperature and vigorously stirring, 60.6 parts of 99% sodium hydroxide was added over 1 hour, and the reaction was further performed at the same temperature for 6 hours. The salt formed by filtration was removed and epichlorohydrin was distilled off and then dissolved in 300 parts of toluene.
  • Synthesis Example 2 Synthesis of Heterocyclic-Containing Phenolic Compound
  • DMF N, N-dimethylformamide
  • Synthesis Example 3 Synthesis of Heterocycle-Containing Epoxy Resin
  • 172 parts of the phenol compound B obtained in Synthesis Example 2 925 parts of epichlorohydrin, and 185 parts of ethylene glycol dimethyl ether were charged at room temperature and flowed with nitrogen gas and stirred while stirring 64 It heated up to ° C. Thereafter, the pressure was reduced to the extent that reflux of water occurred, and 81.6 parts of a 49% aqueous solution of sodium hydroxide was added dropwise over 3 hours.
  • Methyl isobutyl ketone was added and washing was repeated several times to remove ionic impurities.
  • the resin solution was filtered by dehydration, and methyl isobutyl ketone was distilled off under reduced pressure to obtain an epoxy resin B.
  • A-1) Epoxy Resin A Obtained in Synthesis Example 1 (Epoxy Equivalent: 133, jj0.04)
  • A-2) Epoxy resin B obtained in Synthesis Example 3 (epoxy equivalent weight: 236, j0.040.04)
  • A-3) Epoxy resin of 4,4 '-(3,3,5-trimethylcyclohexylidene) bisphenol (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., TX-1468, epoxy equivalent: 218, jj0.04)
  • A-4) Bisphenol A liquid epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., YD-8125, epoxy equivalent: 172, j 0.01 0.01)
  • A-5) Epoxy resin of 3,3 ', 5,5'-tetramethyl-4,4'-biphenol (Mitsubishi Chemical Corporation, YX-4000, epoxy equivalent: 186, j ⁇ 0.06)
  • A-6) Bisphenol A liquid epoxy resin (man
  • B-1 DOPO-HQ (manufactured by Sanko Chemical Co., Ltd., HCA-HQ, hydroxyl equivalent: 162, phosphorus content 9.5%)
  • B-2) DOPO-NQ (manufactured by Sanko Chemical Co., Ltd., HCA-NQ, hydroxyl equivalent: 187, phosphorus content 8.2%)
  • B-3) Diphenylphosphinyl hydroquinone (manufactured by Hokuko Chemical Co., Ltd., PPQ, hydroxyl equivalent: 155, phosphorus content 10.0%)
  • B-4) Phenolic compound B obtained in Synthesis Example 2 (hydroxy group equivalent: 172)
  • B-5) piperazine (reagent, active hydrogen equivalent: 86)
  • B-6) 4,4 ′-(3,3,5-trimethylcyclohexylidene) bisphenol (Honshu Chemical Industry Co., Ltd., BisP-TMC, hydroxyl equivalent: 155)
  • B-7) Bisphenol A
  • Catalyst (C-1): 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., Cuazole 2E4MZ)
  • C-2 triphenylphosphine (reagent)
  • C-3 tris (2,6-dimethoxyphenyl) phosphine (reagent)
  • Example 1 At room temperature, 319 parts of (A-1), 381 parts of (B-1), 300 parts of diethylene glycol dimethyl ether are charged into a reaction apparatus equipped with a stirrer, thermometer, nitrogen gas introduction device and cooling pipe, and nitrogen gas is added. The temperature was raised to 145 ° C. while flowing and stirring, and after adding 0.07 part of (C-1), the temperature was raised to 165 ° C. and reaction was carried out at the same temperature for 10 hours. Diluted and mixed with 500 parts of methyl cellosolve and 500 parts of cyclopentanone to obtain a resin varnish of phosphorus-containing phenoxy resin having a nonvolatile content of 35%.
  • the resin varnish is applied to a release film (made of polyimide film) by a roller coater so that the thickness after solvent drying becomes 60 ⁇ m, and after drying at 150 ° C. for 10 minutes, the dry film obtained from the release film is It peeled off. Two pieces of this dried film were stacked, and pressed using a vacuum press under the conditions of a vacuum degree of 0.5 kPa, a drying temperature of 180 ° C., and a press pressure of 2 MPa for 60 minutes to obtain a resin film with a thickness of 100 ⁇ m.
  • the epoxy equivalent and Mw of the phosphorus-containing phenoxy resin were measured using a resin film, and the phosphorus content, Tg, water absorption, residual carbon ratio, and flammability were each measured.
  • the results are shown in Table 1.
  • the molar ratio represents the ratio of (epoxy group of epoxy resin) / (active hydrogen group of bifunctional compound).
  • (Mol%) of X 1 , X 2 and X 3 is a group (X 1 ) represented by the formula (2) in X of the formula ( 1 ), a heterocyclic structure containing group (X 2 ) and other groups (X 3) Indicates the existence rate of).
  • Example 9 Using the same apparatus as in Example 1, 447 parts of (A-2) and 32 parts of (B-5) were charged at room temperature, and the temperature was raised to 130 ° C. while flowing nitrogen gas and stirring, and the temperature was the same. The reaction was performed for 5 hours. Thereafter, 221 parts of (B-1) and 300 parts of diethylene glycol dimethyl ether are charged, the temperature is raised to 145 ° C. while flowing nitrogen gas and stirring, 0.07 parts of (C-1) is added, and then the temperature is raised to 165 ° C. The reaction was carried out at the same temperature for 10 hours. Diluted and mixed with 500 parts of methyl cellosolve and 500 parts of cyclopentanone to obtain a resin varnish of a phosphorus-containing phenoxy resin. Thereafter, the same operation as in Example 1 was performed to obtain a resin film.
  • Example 10 Resin varnish and a resin film were obtained by the same operation using the apparatus similar to Example 9 by the compounding ratio (part) as described in Table 2.
  • Comparative Examples 1 to 5 Resin varnish and a resin film were obtained by the same operation using the apparatus similar to Example 1 according to the compounding ratio (part) as described in Table 2.
  • Table 2 summarizes the measurement results of epoxy equivalent, Mw, phosphorus content, Tg, water absorption, residual carbon ratio, and flame retardancy.
  • Example 11 285.7 parts of resin varnish 1 obtained in Example 1, 100 parts of (A-6) as an epoxy resin, 6.2 parts of DICY as a curing agent, 0.2 parts of a curing accelerator, and 0. (C-1).
  • a resin composition varnish was obtained by adding 2 parts, 50 parts of methyl cellosolve as a solvent, and 50 parts of DMF and uniformly stirring and mixing.
  • the resin composition varnish was applied to a mold release film by a roller coater so that the thickness after solvent drying was 60 ⁇ m, dried at 150 ° C. for 10 minutes, and then the dry film obtained from the mold release film was peeled off. .
  • the Tg, the water absorption, the residual carbon ratio, and the flame retardance of the resin film were measured, and the results are shown in Table 3.
  • the numeral attached to the resin composition varnish corresponds to the example number, which means that it is the resin composition varnish obtained in the example, and the resin composition varnish H2 and H4 are comparative examples 2 respectively. This means that the resin composition varnish obtained in Comparative Example 4 is used.
  • the phosphorus-containing phenoxy resin of the present invention is halogen-free, exhibits good flame retardancy and high heat resistance, and can be expected to have a low residual carbon ratio and high CTI (Comparative Tracking Index), so the resin composition is Useful for printed wiring board applications.
  • the present invention is useful for a substrate on which a heat-generating component such as an LED or the like having a high demand for tracking resistance is mounted.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne : une résine phénoxy contenant du phosphore présentant une résistance à la chaleur, une résistance au cheminement, une sécurité, une ininflammabilité, une aptitude au traitement et une résistance à la chaleur excellentes ; et une composition de résine utilisant ladite résine phénoxy. La résine phénoxy contenant du phosphore est représentée par la formule (1) et présente une masse moléculaire (MW) de 10 000 à 200 000, X étant un groupe divalent comprenant un groupe (X1) représenté par la formule (2) et un groupe (X2) contenant une structure hétérocyclique, Y étant chaque H ou un groupe glycidyle, n étant de 25 à 500, A étant un cycle benzène, un cycle naphtalène, un cycle anthracène ou un cycle phénanthrène, et Z étant un groupe contenant du phosphore représenté par la formule (3).
PCT/JP2018/035256 2017-09-26 2018-09-25 Résine phénoxy contenant du phosphore, composition de résine correspondante et produit durci Ceased WO2019065552A1 (fr)

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WO2020045150A1 (fr) * 2018-08-27 2020-03-05 日鉄ケミカル＆マテリアル株式会社 Résine époxy contenant du phosphore, composition de résine époxy, préimprégné, plaque stratifiée, matériau pour carte de circuit imprimé et produit durci
JP2021066805A (ja) * 2019-10-23 2021-04-30 日鉄ケミカル＆マテリアル株式会社 フェノキシ樹脂及びその製造方法、その樹脂組成物及び硬化物
WO2021193273A1 (fr) * 2020-03-27 2021-09-30 日鉄ケミカル＆マテリアル株式会社 Résine phénoxy à teneur en phosphore ainsi que procédé de fabrication de celle-ci, composition de résine, objet durci, et carte stratifiée pour circuit électrique/électronique
JP2023500516A (ja) * 2019-11-08 2023-01-06 ロケット フレール イソソルビドエポキシドを含むエポキシド樹脂組成物、及び繊維質又は多孔質材料の安定化におけるその使用
CN119242251A (zh) * 2024-12-04 2025-01-03 淮安凯悦科技开发有限公司 一种本征型阻燃水性聚氨酯胶黏剂及其制备方法和应用

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WO2020045150A1 (fr) * 2018-08-27 2020-03-05 日鉄ケミカル＆マテリアル株式会社 Résine époxy contenant du phosphore, composition de résine époxy, préimprégné, plaque stratifiée, matériau pour carte de circuit imprimé et produit durci
JPWO2020045150A1 (ja) * 2018-08-27 2021-08-26 日鉄ケミカル＆マテリアル株式会社 リン含有エポキシ樹脂、エポキシ樹脂組成物、プリプレグ、積層板、回路基板用材料および硬化物
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JP7405751B2 (ja) 2018-08-27 2023-12-26 日鉄ケミカル＆マテリアル株式会社 リン含有エポキシ樹脂、エポキシ樹脂組成物、プリプレグ、積層板、回路基板用材料および硬化物
JP2021066805A (ja) * 2019-10-23 2021-04-30 日鉄ケミカル＆マテリアル株式会社 フェノキシ樹脂及びその製造方法、その樹脂組成物及び硬化物
JP7359639B2 (ja) 2019-10-23 2023-10-11 日鉄ケミカル＆マテリアル株式会社 フェノキシ樹脂及びその製造方法、その樹脂組成物及び硬化物
JP2023500516A (ja) * 2019-11-08 2023-01-06 ロケット フレール イソソルビドエポキシドを含むエポキシド樹脂組成物、及び繊維質又は多孔質材料の安定化におけるその使用
JP7749553B2 (ja) 2019-11-08 2025-10-06 ロケット フレール イソソルビドエポキシドを含むエポキシド樹脂組成物、及び繊維質又は多孔質材料の安定化におけるその使用
WO2021193273A1 (fr) * 2020-03-27 2021-09-30 日鉄ケミカル＆マテリアル株式会社 Résine phénoxy à teneur en phosphore ainsi que procédé de fabrication de celle-ci, composition de résine, objet durci, et carte stratifiée pour circuit électrique/électronique
JPWO2021193273A1 (fr) * 2020-03-27 2021-09-30
JP7762140B2 (ja) 2020-03-27 2025-10-29 日鉄ケミカル＆マテリアル株式会社 リン含有フェノキシ樹脂、樹脂組成物、硬化物、電気・電子回路用積層板、及びリン含有フェノキシ樹脂の製造方法
CN119242251A (zh) * 2024-12-04 2025-01-03 淮安凯悦科技开发有限公司 一种本征型阻燃水性聚氨酯胶黏剂及其制备方法和应用

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