TW201226433A - Phosphorus-containing phenol resin, the resin composition and cured article - Google Patents

Abstract

Provided is a phosphorus-containing phenol resin having a good solubility to organic solvent and a good miscibility with epoxy resin etc., and having excellent workability, hardenability and formability. The phosphorus-containing phenol resin is represented by the following formula (10). Wherein, A represents an arylene group and/or a triyl having 6 to 20 carbon atoms, which are the same or different, R represents oxygen atom or sulfur atom, carbonyl group, sulfonyl group, hydrocarbon group or single bond, R2 and R3 represent a hydrocarbon group having 1 to 6 carbon atoms, which are the same or different, and may form a ring with phosphorus atoms, R4 represents oxygen atom or sulfur atom, carbonyl group, sulfonyl group, hydrocarbon group or single bond, the hydrocarbon group may contain a hetero atom.

Description

201226433 VI. [Technical Field] The present invention relates to a phosphorus-containing phenol resin having flame retardancy, a curable resin composition containing the ruthenium-containing resin, and a cured product thereof. [Prior Art] The phenol resin is widely used as a molding material for various substrates, a binder for abrasive materials, a binder for polishing materials, and an adhesive for wood, which are excellent in heat resistance, adhesion, mechanical properties, electrical properties, and the like. A binder for a mold, a binder for a laminate, a coating agent, an epoxy resin hardener, and the like. In particular, when it is used as a laminated material in electrical/electronic parts, it is required to impart flame retardancy in order to prevent combustion and suppress the generation of smoke during fire k. In the past, a resin-based resin and a fluorination method have been used, and the flame retardant, the gas-based flame retardant, and the squamous flame retardant have been separately or combined, and the flame retardant is used alone or in combination with the inorganic system. The flame retardant system used in combination with flame retardant additives is the mainstream. However, in recent years, due to environmental problems, (4) flame retardants are respectable. Further, when red phosphorus is used as an additive-type phosphorus-based flame retardant, its safety is insufficient, and when a phosphate-based compound is used, there is a problem that it is precipitated on the surface of the cured product. Further, if a phosphate ester is used, there is a problem that solder heat resistance and bathing property are lowered. Therefore, it is desired to develop a non-s-type reactive flame retardant which can obtain flame retardancy without using such an additive flame retardant. On the other hand, even the hardener of epoxy resin has the same problems as described above, for example, using 2-diphenyl-based hydrogen i (dlphenylph〇sphinyl hydr〇quin〇ne; abbreviated as PPQ) and 1〇_ (2 , 5-dihydroxyphenyl)-1〇h_9_oxa_1〇_phosphine phenanthrene-oxide 4 323617

S 201226433 (10-(2,5-Dihydroxyphenyl)-10H-9-〇xa-10- • phosphaPhenanthrene-10-oxide; Sanguang Co., Ltd., product, name HCA-HQ) and other phosphorus-containing phenol compounds A cured flame retardant having high flame retardancy. However, these phosphorus-containing phenol compounds are inferior in solvent solubility and compatibility with an epoxy resin, and when used as a curing agent alone, they are deposited without being dissolved in an epoxy resin varnish, so that they are used for laminated materials and the like. Insufficient practicality. In order to solve this problem, Patent Document No. 2 and 2 disclose a partially-containing oxime resin which is a pre-reaction in which an epoxy resin and a phosphine compound of 3 phosphorus are previously reacted in consideration of dispersibility. However, there is a problem of low adhesion. When this varnish/grain medium uses Shangfo point solvent, the solvent solubility of the resin is less than satisfactory. Patent Document 3 proposes to improve the phosphorus-containing phenol resin with an epoxy resin ruthenium phase/gluten. However, since cyclohexanone having a high boiling point is used as a reaction solvent, it is difficult to completely remove the solvent in the laminate production step. Continuation of the epoxy-cured material and the reliance on the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the invention. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a test resin containing a sarcophagus, which does not use a type; a type of resistance _he (four) is resistant to impurities, and is read by a dissolution history of a solvent of each machine and Each of the observation county tree materials has good compatibility, and is suitable for dense, formed materials, laminated sheets, injection molding materials, adhesives, insulating coatings, etc.; 323617 5 201226433 and provides a cured product which will contain the inclusion The resin composition of the phosphorus phenol resin is cured, and is excellent in flame retardancy, heat reliability, and adhesion. (Means for Solving the Problem) The present invention is: 1. A filled phenol resin which is represented by the following formula (1) and has an average number of molecular weights of 500 to 5,000. Y*YCH2CHCH2'Z\ V OH h /Z-CH2 9H CH2J γ' v OH Αι •a^Ri-a^i-a^y-Zchs-ch-chs-z ’ \ OH ,

A -Y-/CH2CHCH2-Z' \ OH / jp (1) (wherein A represents a aryl group and/or a triyl group having a carbon number of 6 to 20, which may be the same or different. γ represents an oxygen atom and/or a nitrogen atom 'which may be the same or different. wherein Z represents the general formula (2) and/or the general formula (3) and/or the general formula (4), but the phosphorus-containing phenol of the present invention The resin must have both the structures represented by the general formula (2) and the general formula (3) in one molecule. In the formula, R represents an oxygen atom or a sulfur atom, a carbonyl group, a sulfoxime group, a hydrocarbon group, The single chain, the hydrocarbon group may contain a hetero atom. The formula α is an integer from 〇 to 4, an integer not represented by 1 to 1 、, an integer representing 1 to 10, and 〇 indicates that the configuration in parentheses is A hydrogen atom, £ represents an integer from 0 to 2, and when Q, represents a structure in the parentheses as a hydrogen atom, 323617 6 201226433 represents 1 or 2.) * R2 . X 0) 73⁄4 (2) —O-A-O-X Formula (5^), the basin can be the same as the formula (1), and X represents a hydrogen atom and/or a hydrocarbon of 1 I 6 , IT or is different. Further, in the formula, 匕 and R3 represent a carbon number ring. "Working ', can be the same or different' and can be combined with the whole (3) (Χ-〇)δ (〇-χ)δ -OA-fR^Aj^F^-Aj^Ox) [Α^ °-Χ)δ]ε (wherein Α and α, /5, τ, Α· 〆, Ρ Ύ d, ε are respectively the same as the general formula (1) 'X is the same as the general formula (1). R4 represents a hydrogen atom or Sulfur, (county phase % mercapto, hydrocarbyl, single bond, hydrocarbyl group may contain heteroatoms.) r2 〇10 0) 73⁄4 (4) (wherein 7 and formula (1) (iv), and h represents the carbon number i to the nicotine' They may be the same or different, and may form a ring together with the chi and the sub-(Z-CH2g|CH2Guang)~^CH2gHCHrz) (5) -CH2 ~ Y~ ft(R 1~A -Υ -^〇η2ΌΗ- CH2-Z j

, A- -y-/ch2ch-ch2-z\ \ OH /η PJ 323617 7 201226433 (In the formula and 1, 丫, 2, 〇;, call, 7, (5, £, 7? 2. The phosphorus-containing phenol resin according to the above (1), which is represented by the following formula (6): R2 〇 = Ή〇 ^ (〇Η) H〇-A- 0-CH2CH-CH2-0-A^Rl-A)3〇-CH2-CH-CH2-0-A-(R4-A)jR4-Ah〇H (6)

◦H OH /A \ Y \6h)e (wherein A and ε are the same as in the formula (1), R2 and R3 are the same as in the formula (2), and R4 is the same as the formula (3). The middle 0 represents an integer from 0 to 5.) 3. The phosphorus-containing phenol resin according to the above (1) or (2), which reacts the phosphorus-containing phenol compound represented by the formula (7) and the difunctional or higher phosphorus-free phenol compound with an epoxy resin . R2 〇 ten C%R3 (7)

HO-A-OH (wherein A and r are the same as in the formula (1), and r2 and r3 are the same as in the formula (2), respectively). A resin composition containing the phosphorus-containing phenol resin according to any one of the above (A) to (3). 5. A flame retardant resin cured product which is cured by the resin composition described in the above (4). (Effects of the Invention) 8 323617 201226433 According to the present invention, it is possible to provide a phosphorus-containing phenol resin having a solubility in an organic solvent and a compatibility with an epoxy resin or the like and a composition thereof. A resin composition obtained by blending the phosphorus-containing phenol resin with an epoxy resin and other phenol resins can obtain a cured product having excellent flame retardancy, heat resistance reliability, and adhesion. [Embodiment] In the formula of the formula (丨) of the present invention, A represents a carbon number of 6 to 20 and/or a triyl group which may be the same or different. Specifically, it is a stupid base, a stretched base, a diphenyl group, a biphenyl group, a naphthyl group, a benzene-1,2,4-trianthene group, etc., which may have a substituent or may contain a hetero atom. In the formula (1), R1 is an oxygen atom or a sulfur atom, a carbonyl group, a sulfonium fluorenylene group, a methine group or the like, a single bond, and the hydrocarbon group may contain, for example, In the case of G, R1 is a hydrocarbon group such as an oxygen atom, a sulfur atom, a brewing group, a single bond, a methylene group, and a phenyl group. When ε is 1, a hydrocarbon group such as a 2 曱 2 group or a benzene-1,3,4-triyl group is used. ' £ is a 2-day temple Rl is a hydrocarbon group such as ethane and U'2-tetrayl. In the formula, α represents an integer of G to 4, preferably an integer of 嶋1 to 1〇 in the formula, preferably in the range of 1 to 3. Similarly, the formula occupies a range of two. :3: Preferably, it is in the range of 0 to 5, and it is more preferable that the solubility and the softening point are increased at 0, and the compatibility of the solvent and the other compounds is lowered.碟 _ (the average molecular weight of the target is preferably 500 to 2500, more preferably 5 〇〇 to π 〇〇 323617 9 201226433 If the molecular weight of the mesh exceeds _ then the viscosity of the resin is high, and the combination with the 禋 tree The compatibility and solvent solubility are reduced. In the formula (2), hydrazine and r3 represent a hydrocarbon group having a carbon number of 丨 to 6, which may be the same or different, and may form a ring together with the phosphorus atom. Further, in the formula In the formula of the formula (1), the formula (1) is a benzene group, a trisyl group, and an oxygen atom, and a hydrocarbon group having a carbon number of 6 and R3 are the same as the hydrocarbon group of the carbon number 6 and (1) are the same and the formula (1) The structure represented by the formula (8) is a structure represented by the formula (4) when ruthenium and R3 together with a dish atom form a ring shape and r is 1.

One zero

(8) (9) In the formula (6), α represents an integer of 〇 to 4, preferably in the range of 〇 to 2. e represents an integer from 〇 to 2. Further, 0 in the formula represents an integer from 〇 to 5, preferably in the range of 〇 to 2. When "and 0 exceeds 4 and 5, respectively, and ε exceeds 2, the softening point is increased and solvent solubility and compatibility with other resins are lowered, which is not preferable. The scaly phenol resin represented by the general formula (6) The structure is included in the structure represented by the general formula ()) 323617 10 201226433. For example, in the formula (1), γ is an oxygen atom, α is -0, yS, r, and π is a formula (2) Wherein X is a hydrogen atom and r is 1, wherein in the formula (3), x is a hydrogen atom, α and 5 are ruthenium, cold and r are 1, and α of the formula (6) is 〇, 7 and 0 represent At 1 o'clock, the formula (1) and the formula (6) have the same structure 'is a structure represented by the formula (10). R2 o=po-r3 (10)

HO-A -〇-CH2"C H-CH2-〇_A~RrA -〇-cH2-<pH-CH2-〇- A-R4-a - OH OH OH Formula (1) and/or The phosphorus-containing phenol resin represented by the formula (6) can be produced by reacting a phosphorus-containing compound and a difunctional or higher phosphorus-free phenol compound with an epoxy resin. However, the scope of the present invention is not limited to the production method. The epoxy resin used for the production of the phosphorus-containing phenol resin of the present invention is exemplified by: ΕΡ0Τ0ΗΤ0 YD-128, ΕΡ0Τ0ΗΤ0 YD-8125 (BPA made by Nippon Steel Chemical Co., Ltd.) Type epoxy resin), ΕΡ0Τ0ΗΤ0 YDF-170, EPOTOHTOYD-8170 (BPF type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), YSLV-80XY (tetrakisyl bisphenol f type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd. ),ΕΡ0Τ0ΗΤ0 YDC-1312 (hydrogen type epoxy resin), jER YX4000H (Mitsubishi Chemical Co., Ltd.), ΕΡ0Τ0ΗΤ0 YDPN-638 (Nippon Steel Chemical Co., Ltd. phenol novolac) Epoxy resin), ΕΡ0Τ0ΗΤ0 YDCN-701 (Nippon Steel Chemical Co., Ltd. armored varnish no var (cresol novo lac) type epoxy resin), ΕΡ0Τ0ΗΤ0 ZX-1201 (Nippon Steel Chemical Co., Ltd. Epoxy resin), TX-0710 (Nippon Steel Chemical Co., Ltd., Shuangpan 11 323617 201226433 S-type epoxy resin), EPICLONEXA-1515 (D-phenol S-type epoxy resin manufactured by Dainippon Chemical Industry Co., Ltd.) , NC-3000 (biphenyl aralkyl phenol epoxy resin manufactured by Nippon Kasei Co., Ltd.), ΕΡ0Τ0ΗΤ0 ZX-1355, ΕΡ0Τ0ΗΤ0 ZX-1711 (naphthalene diene epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ΕΡ0Τ0ΗΤ0 ESN-155 (manufactured by Nippon Steel Chemical Co., Ltd.; 5-naphthol aralkyl type epoxy resin), ΕΡ0Τ0ΗΤ0 ESN-355, ΕΡ0Τ0ΗΤ0 ESN-375 (Ninatron Chemical Co., Ltd. bisphthol aralkyl type epoxy Resin), ΕΡ0Τ0ΗΤ0 ESM75V, ΕΡ0Τ0ΗΤ0 ESN-485 (α-naphthol aralkyl type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), EPPN-501H (triphenylmethane type epoxy resin manufactured by Sakamoto Chemical Co., Ltd.) , SUMIEP0XY ΤΜΗ-574 (a triphenylmethane type epoxy resin manufactured by Sumitomo Chemical Co., Ltd.) and other multi-valent resin expectant compounds and epoxy resin produced by epihalohydrin; by Τ0Τ0ΗΤ0 YH-434 ( Epoxy resin produced by an amine compound such as diamine diphenyl decane diglycidylamine and epihalohydrin; jER 630 (amine phenol epoxy resin manufactured by Mitsubishi Chemical Corporation), ΕΡ0Τ0ΗΤ0 F X-289B, ΕΡ0Τ0ΗΤ0 FX-305, TX0932A (a phosphorus-containing epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), etc., a phosphorus-containing epoxy resin obtained by reacting an epoxy resin with a modifier such as a phosphorus-containing phenol compound; YSLV-120TE (disulfide type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ΕΡ0Τ0ΗΤ0 ZX-1684 (resorcinol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), DENAC0L EX-201 ( Nagase ChemteX Co., Ltd., styrene-based epoxy resin), EPICLONHP-7200H (dicyclopentadiene-type cycloolefin resin manufactured by DIC Corporation), urethane modified epoxy resin, sputum, etc. _

S 323617 12 201226433 (oxazolidone) epoxy resin of the ring, τχ„〇929, τχ_〇934 (the alkyl diol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), etc., but is not limited to the above. Further, these epoxy resins may be used singly or in combination of two or more kinds. The scaly desired compound used in the present invention is a structure represented by the formula (11). For example, 10-(2,5-dihydroxyl) Phenyl)-10H-9-oxa-10-phosphinophen-10-oxide (manufactured by Sanguang Co., Ltd., trade name hca_Hq), 1 〇1 (1,4-dihydroxynaphthyl)-10H-9-oxygen Hetero-10-phosphine- ίο-oxide (manufactured by Beixing Chemical Industry Co., Ltd., trade name PPQ), diphenylphosphinyl _丨4_dipyridyl, 1,4-cyclooctyl phosphinyl- 1,4-cyclooctylenephosphiny 1,4-phenyldi〇i (manufactured by Nippon Chemical Industry Co., Ltd., trade name CPH0-HQ), 1,5-cyclohexyl phosphinyl group- Phosphorus-containing phenols such as 1,4-dihydroxybenzene (manufactured by Sakamoto Chemical Industry Co., Ltd., trade name: CPH0-HQ) are not limited to the above. In addition, two kinds of phosphorus-containing phenol compounds may be used in combination. the above R2 0=Pf〇)yR3 〇1) ho-a-oh (wherein A and r are the same as in the general formula (1), and R2 and r3 are the same as the general formula (2), respectively.) The filler-containing compound may have an active hydrogen directly bonded to a phosphorus atom, such as 9, 10-dihydrooxa-10-phosphinophen-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA) and diphenylphosphine. The base disc compound is obtained by reacting with 1,4-benzoquinone and 1,4_ Cai Yukun 323617 13 201226433 (1,4-naphthoquinone), etc. HCA-HQ is based on B Bent Kaizhao 60-126293, HCA-NQ is issued in Japan, JP-A 61-23678^ PPQ is based on zh. Obshch. Khim, 42(11), pp. 2415-2418 (1972). The composition of the scaly resin used in the present invention is preferably 1,4-benzene and 1,4-naphthol with respect to the phosphorus compound such as HCA and diphenylphosphine. The range of from 0 moles to 1. moles is more preferably in the range of from 0.5 moles to 1.0 moles, and more preferably in the range of from 〇8 moles to 1.0 moles. If less than 0.5 mole, the hydroxyl group in the phenolic resin is less. Therefore, the crosslink density of the cured product is lowered, and the physical property is deteriorated. In addition, if it exceeds 1. 〇 Moole, there is unreacted brewing residue, which is not preferable. The compound containing no phosphorus in the resin containing the filler of the present invention is a compound having two or more hydrophobic groups in one molecule, and examples thereof include catechol and resorcin. Hydroxybenzenes such as hydroquinone; naphthalenes, hydrazines, trisphenols, diterpene A, bisphenol F, bisphenol S, and Shonol BRG-555 (Showa Electric Co., Ltd. ), cresol novolac resin, alkyl phenol novolac resin, aryl lacquer varnish resin, platin varnish resin containing triazine ring, biphenyl aralkyl phenol resin, RESITOPTPM-100 (group) It is a polyvalent phenol such as a trihydroxyphenyl nonane novolak resin manufactured by Rong Chemical Industry Co., Ltd. or an aryl naphthoquinone resin, but is not limited thereto. Further, these phosphorus-free phenol compounds may be used in combination of two or more types. In the present invention, the phosphorus-containing phenol compound and the phosphorus-free phenol compound are used in combination. 14 323617

S 201226433 is used, but the total ratio of the phosphorus-containing phenol compound and the phosphorus-free compound is such that the weight ratio of the phosphorus-containing phenol compound is 20% to 8〇%. 30% to 70% 'better than 40% to 65% is preferred. When the phosphorus-containing phenol compound is less than 20%, the flame retardancy of the cured product is insufficient. When more than 80% is used, the solvent solubility of the obtained resin containing the disk is deteriorated. The ruthenium-containing oxime resin of the present invention can be obtained by reacting the above epoxy resin, the above-mentioned phenol-containing compound, and phosphorus-free phenol compound. The total of the hetero group in the phosphorus-containing phenol compound and the phosphorus-free phenol compound is preferably in the range of 15 mol to 4 =, more preferably, relative to the epoxy group 1 mol in the epoxy resin. For 丨.8 mole to 2.2 moles. If the weaving is less than 5, the resin molecules will become higher and gelatinized, and the epoxy stability will deteriorate the storage stability, or the Tg of the Wei can be extremely reduced. The compatibility of the rail resin or the like is inferior to obtain the phosphorus-containing phenolic tree of the present invention to 20 (TC, preferably 140. (: to 16 曰〇. The reaction temperature is 100 ° C. The line is significantly slower, at 20 (TC) In the above C, the reaction time is preferably 2 to 6 hours at 100 ° C or less, and the resin may be partially decomposed. Further, the reaction catalyst may be used to obtain the phosphorus in the present invention. In the reaction, in order to promote the anti-tris(2,6-dimethoxyphenyl) Lin 1 catalyst, a tetrabasic phosphine, an ethyltriphenyl moth, etc. Phenyl evolution scale, imidazoles such as phenylimidazole; tetramethyl, 2~ethyl-4-methylimidazole, 2 ammonium monofluoride, tetraethylammonium bromide, etc. 4 323617 15 201226433 money salt; A primary amine such as ethylamine or benzyldimethylamine. The amount of these catalysts is preferably in the range of 0.01 to 1% by weight based on the total amount of the 22 compounds. The reaction between the tree month a and the resin can be carried out in the absence of a solvent, or it can be carried out in an aprotic solvent when it is carried out in a solvent, for example, propylene glycol alone (PGM), propylene glycol monomethyl acetate vinegar mm%, dicalcin, di(giyc〇iether), oxyethylene 1 and other reaction solvents can be used alone or in combination with 2 feeding anti-riding medium (four) Preferably, the weight of the reaction is less than 50% by weight. The composition of the present invention contains the phosphorus-containing fat, but in the case of the epoxy resin composition, the epoxy resin, the resin of the present invention may be used. A hardener, a hardening accelerator, a filler, etc. are mentioned. The epoxy resin used for the epoxy resin composition mentioned above can be mentioned as the same kind as the epoxy type which synthesizes the slave of this invention. Further, these epoxy resins may be used singly or in combination of two or more kinds. When the epoxy resin is used as the resin composition of the present invention, the phosphorus-containing resin of the present invention acts as an epoxy resin for hardening. The resin composition of the present invention is in addition to the present invention. The fat material can be used as a Wei agent. The phosphorus-free phenol compound used in the manufacture of the phosphorus-containing phenol resin can be mentioned; the adipicdihydrazide and the anthraquinone; Imidazole compounds and salts thereof; dicyandiamide, aminobenzoic acid esters, diethylidene triamine, three 16 323617 201226433 ethyltetramine, tetraethylamamine, isophthalic acid An aliphatic amine such as guanamine or isophorondiamine; an aromatic amine such as diaminodiphenylmethane, diaminodiphenyl sulfone or diaminoethyl benzene; orthophthalic acid Anhydride, trimelitate anhydride, pyromellitic acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, mercaptotetrahydrophthalic anhydride, hexahydrophthalic anhydride , such as mercapto hexahydrophthalic anhydride, methyl naphthalic anhydride, etc., can also be used together! A known epoxy resin hardener of a type or more. For the epoxy group 1 mole in the epoxy resin used, the epoxy resin hardener containing the phosphorus-containing phenol resin of the present invention is preferably used in an amount of from 0.3 mol to 1.5 mol, more preferably In 〇.4 莫 to 1.2 m. Further, when the phosphorus-containing phenol resin of the present invention is used in combination with other epoxy resin hardeners, the total amount of the phosphorus-containing phenol resin is 20% by weight or more, preferably 3% by weight, based on the total amount of the phosphorus-containing phenol resin. The above 'better than 40% of the way. If the resin containing less than 2% is filled, the flame retardancy of the cured product is liable to be insufficient. Further, when the fluidity and viscosity are adjusted, a reactive diluent can be used insofar as the physical properties of the resin composition of the present invention are not impaired. The diluent is preferably a reactive diluent, but a non-reactive diluent may also be used. The reaction diluent may, for example, be a monofunctional glycidyl ether such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether or phenyl glycidyl ether; resorcinol glycidol, neodecyl glycol glycidyl ether , 1,6-hexanediol diglycidyl ether, etc., two b Sb glycidyl bonds, glycerol polyglycidyl ether, trihydrocarbyl propane polyglycidyl ether, neopentyl 17 323617 201226433 A polyfunctional glycidyl ether such as glycidyl ether. Examples of the non-reactive diluent include decyl alcohol, butyi diglycol, and rosin oil (pine oi1). Further, the resin composition of the present invention may use a hardening accelerator as necessary. For example, phosphines, quaternary phosphonium salts, tertiary amines, quaternary ammonium compounds, imidazole compounds, boron trifluoride complexes, 3_(3 4_dichlorodiphenyl) ruthenium, propylene Base urea, 3-(4-phenylphenyl)-1, dibiguanyl urea, 3-phenyl-l-monomethyl urea, and the like. These hardening accelerators are preferably based on the type of epoxy resin, the molding method, and the curing temperature required characteristics of the epoxy resin used in combination, and the curing accelerator is preferably used in the weight of the epoxy resin. More than 0.01% to 20%, more preferably in the range of 〇. 1% to 10%. The resin composition of the present invention can be blended with other thermosetting resins and thermoplastic resins within a range that does not impair the properties. For example, resin, acrylic resin, petroleum resin, enamel resin, benzofuran-indene resin, phenoxy resin, polyurethane, polyester, polyamide, polyimine, poly Indoleamine-polyimine, polyetherimide, polyethersulfone, polyfluorene, polyfluorene, polyphenylene sulfide (P〇ly (phenylene sui f丨)), polyvinyl alcohol Aldehyde, but is not limited to these. The resin composition of the present invention can be formulated with an inorganic filler or an organic filler as necessary. Examples of the filler include: molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, aluminum hydroxide, talc, mica, calcium carbonate, calcium citrate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, and nitriding. Boron, carbon, carbon fiber, glass fiber, alumina fiber, cerium oxide-alumina fiber, carbon fiber, polyester fiber, cellulose fiber, linaloamide fiber, and the like. The ^ filling

323617 S 18 201226433 The agent is preferably 丨〇% to 7〇% of the total weight of the resin composition. The resin composition of the present invention can be formulated with a coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant, and a pigment according to the necessity thereof. Such as nuclear additives. 01%至二十百分比的范围内。 These additions are preferably in the range of 0.01% to 20% of the total resin composition. The resin composition of the present invention can be formed by the same method as the known brewed resin composition, and is a cured product. The Chengfa method and the Wei method are the same as the well-known method, and do not require the method unique to the invention tree. 4, I% of the fat hardened can be a laminate film, film and other types. The present invention is excellent in workability in the flame retardancy of the scaly resin and the compatibility with the epoxy resin, and the workability is excellent, and the resin is cured and the residue is good, and the seal for the rabbit's gas electronic parts is known. Materials, copper-clad laminates, insulating coatings, electrical materials, insulation _ follow-up money zero (four) A, coating (example) Leaf 1 糸 is useful. The present invention is not limited to the embodiment of the present invention, but "part" means a part by weight unless otherwise specified. Further, the analysis method and measurement method are as follows. The heart indicates the weight %. Light basis weight: The solvent is acetylated with 14-dioxane, and the excess acetic acid gas U.5m〇1/L·°·5 is oxidized and discharged using potentiometric titration=19 323617 201226433 Epoxy equivalent: based on JIS K7236. Nonvolatile component: JIS K7235-1986 Number average molecular weight: The molecular weight distribution was determined by colloidal permeation chromatography and converted by a calibration curve obtained from standard polystyrene. In this case, the peak derived from the remaining unreacted raw materials and impurities was removed and calculated. Specifically, the main body (HLC-8220GPC manufactured by TOSOH Co., Ltd.) was used by connecting a column (TSKgel G4000HXL, TSKgel G3000HXL, TSKgel G2000HXL manufactured by TOSOH Co., Ltd.) in series, and the column temperature was 40 °C. Further, the washing liquid used tetrahydrofuran to have a flow rate of 1 ml/min, and the detector used an RI detector. Phosphorus content: sulfuric acid, hydrochloric acid, and peroxyacid are added to the sample, followed by hot wet ashing, so that all the lining atoms become orthophosphor i c acid. And reacting with metavanadate and molybdate in an acidic solution of sulfuric acid, and measuring the absorbance of the resulting Ammonium phosphomolybdate (n-hydrate) complex at 420 nm, and using a pre-made calibration curve The phosphorus atom content is obtained and expressed in % by weight. The phosphorus content of the laminate indicates the content of the resin portion relative to the laminate. Infrared absorption spectrum: A Fourier transform infrared spectrometer (Spectum One manufactured by PerkinElmer Co., Ltd.) was used and measured by a tablet method (KBr). Gluing time · Take 〇.. 2ιη 1 resin composition, drip to 16 〇. The stirring was performed on a hot plate to measure the time until the resin composition was gelatinized. Copper foil peel strength and interlayer peel strength: based on JISC6481. Flammability. Based on UL94 (Underwirters Laboratories Inc. 20 323617 s 201226433 safety certification specification). The test was carried out in five test pieces, and the total time of the flame burning time was expressed in seconds after the first and second combustions (five pieces of the two pieces were fed twice in total for 10 times). T-288 test: based on ipc TM-650.

Glass Transfer Temperature: Differential Scanning Thermal Analyzer (SII

The temperature of the DSC extrapolated value indicates the glass transition temperature when the temperature is measured at a temperature rise of 10 °C/min. by the NanoTechnology Co., Ltd. EXSTAR6000 DSC6200. Thermal decomposition temperature: The differential heat-thermal weight simultaneous measurement device (EXSTAR6000 TG/DSC62® manufactured by SII NanoTechnology Co., Ltd.) was measured at a temperature rise condition of 10 C /min, and its thermal weight was reduced by a small amount. (Example 1) A bisphenol F-type epoxy resin was added to a four-port detachable flask experimental apparatus equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction tube (manufactured by Nippon Steel Chemical Co., Ltd., a product Name YDF-17〇, epoxy equivalent 170g/eq·) 84. 9 parts, and add 1〇-( 2, 5-dihydroxyphenyl)-l〇u, 9, oxa-10-phosphinophen-10 - Oxide (manufactured by Sanguang Co., Ltd., trade name HCA-HQ, melting point 256 Ό, phosphorus content 9.6%, hydroxyl equivalent 162 g/eq) 78. 3 parts, trishydroxyphenylmethane novolak resin (Rong Chemical Industry Co., Ltd. The company's product name, RESITOP TPM-100, hydroxyl equivalent of 97·5g/eq), 50.4 parts, and propylene glycol monoterpene ether acetate (PMA), 53 parts. At this time, the ratio of the phenol compound contained in the entire phenol compound was 61%, and the functional group ratio of the cycloolefin resin, the phosphorus-containing phenol compound, and the phosphorus-free phenol compound was 323617 21 201226433 1. 00 : 0. 96 : 1. 04. After adding a triphenylphosphine as a catalyst and reacting at 160 ° C for 3 hours ', a mixed solvent of propylene glycol monoterpene ether (PGM) and methyl ethyl ketone (MEK) (1:1) was added to dilute the obtained content. The phosphorus phenol resin solution is red and transparent, and has a nonvolatile content of 6% by mole, a phosphorus content of 3.5%, a number average molecular weight of 2077, and a hydroxyl equivalent of 427 g/eq. Table 1 shows the amount of addition, the ratio of addition, the properties of the resin, and the like. (Example 2) The reaction was carried out in the same manner as in Example 1 except that the TPM-100 of Example 1 was changed to bisphenol F (manufactured by Honshu Chemical Co., Ltd., hydroxyl group equivalent: 100 g/eq.), 51.6 parts. At this time, the proportion of the phenanthrene compound in all the compounds was 60%, and the functional group ratio of the epoxy resin, the compound containing the compound, and the phosphorus-free phenol compound was 1.00 : 〇 96 : 1〇4. After the reaction was completed, it was diluted with a PGM/MEK mixed solvent. The resulting resin-containing solution was light yellow and transparent, and had a nonvolatile content of 60%, a phosphorus content of 3.5%, a number average molecular weight of 1,620, and a hydroxyl equivalent of 430 g/eq. Table 1 shows the amount of addition, the ratio of addition, the properties of the resin, and the like. (Example 3) In addition, the YDF-170 of Example 1 was changed to an alkylene glycol type epoxy resin. The purpose of the test was Τχ-0929, and EOg/eq. 70. The reaction was carried out in the same manner as in Example 1 except for 3 parts. At this time, the ratio of the phosphorus-containing phenol compound in the total phenolic compound is 58 ^, the oxy-alkali resin, the phosphorus-containing compound, and the compound containing no compound are 1. 〇〇: 〇. 92 : 1. 08. After the end of the reaction, it was diluted with pgm/MEK mixture/troreal. The obtained phenol resin solution is light yellow transparent, which does not wave 323617

S 201226433 Hair composition 60%, phosphorus content 3.6%, number average molecular weight 1943, hydroxyl - when the guest '393g / eq. Table 1 shows the amount of addition, the proportion of addition, the properties of the resin, and the like. (Example 4) 9,1 〇-dihydro-9-oxa-10-phosphinophen-10 was added to a four-port glass separable flask experimental apparatus equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction tube. - Oxide (manufactured by Sanko Co., Ltd., trade name HCA, scale content 14.2%) 55.5 parts, and 1,4-naphthoquinone (3.4% by weight of Kawasaki Chemical Industry Co., Ltd.) 40. 7 parts, toluene After 17 minutes of disruption at 75 ° C for 30 minutes, the reaction was carried out at 11 ° C for 9 minutes while removing moisture from the system. At this time, the molar ratio of HCA to 1,4-naphthoquinone is ι.00: 〇 98. Thereafter, toluene was removed, and 85.0 parts of YDF-170, 49.6 parts of BPF, and 20 parts of PMA were added, and the reaction was carried out in the same manner as in Example 1. 00 : 1. 00 : 1, 00 : 1. 00 : 1, 00: 1. 00: 1, phenol: phenol compound 00. After the reaction was completed, it was diluted with a PGM/MEK mixed solvent. The obtained phosphorus-containing phenol resin solution was dark brown transparent, and a resin solution containing 60% of a nonvolatile matter, a 3.4% phosphorus content, a number average molecular weight of 1914, and a hydroxyl equivalent weight of 460 g/eq. was obtained. Table 1 shows the amount of addition, the properties of the resin, and the like. (Example 5) In the resin containing the dish obtained in Example 1, the phenolic novolac type epoxy resin was prepared in the amount of the solid content shown in Table 2 (Nippon Steel Chemical Co., Ltd., product name YDPN-638, ring equivalent 175 g /e(1) and hardening accelerator, and 323617 23 201226433 resin composition. Dissolve it in MEK to become resin varnish (varn i sh). Impregnate the obtained epoxy resin into glass cloth (WEA 116E106S136 Nitto Textile Co., Ltd. The company has a thickness of 1. 1 leg) and is dried in a 150 ° C hot air circulating oven for 10 minutes to obtain a prepreg. Overlap 4 sheets of prepreg and copper foil (3EC-IH, thickness by Mitsui Mining Co., Ltd.) 35/zm), a vacuum pressing of 2 MPa was carried out at a temperature of 130 ° C x 15 minutes + 190 ° C x 80 minutes to obtain a laminated board having a thickness of 5 Å. Table 2 shows the blending ratio and the evaluation result of the laminate. Example 6) An epoxy resin cured product was obtained by using the phosphorus-containing phenol resin obtained in Example 2 and YDPN-638 in the same manner as in Example 5. Table 2 shows the blending ratio and the evaluation result of the laminate. (Example 7) Example 5 in the same manner 'using the scaled tree obtained in Example 3 An epoxy resin cured product was obtained from YDPN-638. Table 2 shows the blending ratio and the evaluation results of the laminate. (Example 8) In the same manner as in Example 5, the filled resin and YDPN- obtained in Example 4 were used. An epoxy resin cured product was obtained as 638. Table 2 shows the blending ratio and the evaluation result of the laminate. (Example 9) In the same manner as in Example 5, the obtained 1:1 resin and bisphenol F-type epoxy resin were obtained. Nippon Steel Chemical Co., Ltd. YDF-ΠΟ, epoxy equivalent 17Gg/eg) Obtained epoxy resin. 2 323617 24 201226433 % Indicates the blending ratio and laminate evaluation results. - (Example 10) • Implementation In the same manner as in Example 5, the phosphorus-containing phenol resin obtained in Example 1 and the cresol novolac type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name YDCN-700-7, epoxy equivalent 209 g/eg) were used. Epoxy resin cured product. Table 2 shows the blending ratio and laminate evaluation results. (Example 11) In the same manner as in Example 5, the phosphorus-containing phenol resin obtained in Example 1 and the phosphorus-containing epoxy resin (Nippon Steel) were used. 0% by the chemical company, the trade name FX-289B, phosphorus content 2. 0% Epoxy resin cured product was obtained by the epoxy equivalent of 300 g/eg. Table 2 shows the blending ratio and the evaluation result of the laminate. (Comparative Example 1) In the same manner as in Example 1, 84. 9 parts of YDF-170 and 162 parts of HCA- were added. HQ, 62 parts of cyclohexene, and reacted in the same manner as in Example 1. At this time, the proportion of the phosphorus-containing phenol compound in all the phenol compounds was 1%, epoxy resin, filled phenol compound, The functional group ratio of the phosphorus-free phenol compound is 1. 00 : 1. 〇〇: 〇. 00. After the reaction, it was diluted with a DMF/methyl cellosolve mixed solvent. The resulting phosphorus-containing phenol resin solution was light yellow transparent, having a nonvolatile content of 6% by weight, a phosphorus content of 6.3%, a number average molecular weight of 602, and a basis weight of 484 g/eq. Table 1 shows the amount of addition, the ratio of addition, the properties of the resin, and the like. (Comparative Example 2) 84.9 parts of YDF-170, 162 parts of HCA-HQ, and 61 parts of cyclohexanone were added in the same manner as in Example 1 and reacted in the same manner as in Example 1. 25 323617 201226433 After cooling to 60 ° C, 196 parts of BPF, 50 parts of PMA were added and scrambled. At this time, the ratio of the phosphorus-containing phenol compound in all the phenol compounds is 45%, and the functional group ratio of the epoxy resin, the phosphorus-containing phenol compound, and the phosphorus-free phenol compound is 1.00:2·00:1· 98. The obtained phenol-containing phenol resin solution was white semi-solid, and had a nonvolatile content of 80%, a phosphorus content of 3.5%, and a hydroxyl group equivalent of 180 g/eq. It was diluted with a pgm / hydrazine mixed solvent and made to have a non-volatile content of 60%, only a white solid precipitate. Since the obtained resin was partially insoluble in THF, it could not be measured by GPC. Table 1 shows the amount of addition, the ratio of addition, the properties of the resin, and the like. (Comparative Example 3) In the phosphorus-containing phenol resin obtained in Comparative Example 1, a phenol novolac type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name YDPN-638, epoxy) was prepared according to the solid content shown in Table 3. Equivalent to 175 g/eq) and a hardening accelerator to obtain a resin composition. After the resin composition was dissolved in a DMF/MEK mixed solvent to obtain a resin varnish, an epoxy resin cured product was obtained in the same manner as in Example 5. Table 3 shows the proportion of the unmixed and the evaluation of the laminate. (Comparative Example 4) In YDPN-638, mixed according to the amount shown in Table 1 (2,5-diphenyl)-10-H-9-oxa-10-phosphinophen-10-oxide (Sanguang Co., Ltd.) A resin composition was obtained by the product name: HCA-HQ, melting point 256 ° C, phosphorus content 9.6%, hydroxyl equivalent 162 g/eq.) 94·8 parts and curing accelerator. This was added to the DMF/MEK mixed solvent because the resin varnish could not be obtained because it was not dissolved. Therefore, the evaluation of the laminate cannot be performed. (Comparative Example 5)

323617 S 26 201226433 In the same manner as in Example 5, a phenol novolak type resin (Shonol BRG-555, phenolic hydroxyl equivalent i〇5 g/eq, manufactured by Showa Shoji Co., Ltd.) and YDPN-638 were used to harden the epoxy resin. Things. Table 3 shows the blending ratio and the evaluation results of the laminate. (Comparative Example 6) In the same manner as in Example 5, BRG-555 and a phosphorus-containing epoxy resin (testing name TX-0932A manufactured by Nippon Steel Chemical Co., Ltd., phosphorus content 3.5%, epoxy equivalent 390 g/) were used. Eq) gives an epoxy cured product. Table 3 shows the blending ratio and the evaluation results of the laminate. (Comparative Example 7) TX-0932A and a curing accelerator were blended in a solid amount shown in Table 3 in dicyandiamide (DICY, active hydrogen equivalent 21 g/eq) to obtain a resin composition. This resin composition was dissolved in a DMF / methicone mixed solvent to obtain a resin varnish, and then an epoxy resin cured product was obtained in the same manner as in Example 5. Table 3 shows the blending ratio and the evaluation results of the laminate. 323617 27 201226433 [5 Comparative Example 2 84.9 | 162 196 LO [1.00 2.00 1.98 I 0.358 S white in co 180 1 Comparative Example 1 84.9 162 100 1.00 2.00 0.00 0.162 〇CM <Light yellow transparent CO CD 484 2530 Example 4 85,0 ! 55.5 39,9 49.6 CD CO 1.00 〇q 1.00 0,146 〇 Dark brown transparent inch CO 460 1914 Example 3 69.7 73.8 53.2 CO ! 1.00 0.92 0.127 〇 light yellow transparent CO c*i 393 1943 Example 2 84.9 | 787—! 51.6 S 1.00 0.96 inch q 0,130 〇 light yellow transparent u> ca 430 1620 Example 1 84.9 | 78.3 50.4 CD 1.00 0.96 1.04 0.129 S Blush transparent in CO I 427 2077 I epoxy resin phosphorus-containing phenolic compound Phosphorus-containing compound g/eq YDF-170 | TX-0929 HCA-HQ HCA 1.4-NQ TPM-100 BPF ΤΡΡ ΡΜΑ | Cyclohexanone Epoxy Resin Filled Compounds Do not contain phenolic compounds ♦l 5- S ΦΦ 湓翕^•<0 Functional ratio of raw material reaction catalyst reaction solvent resin varnish appearance phosphorus content in resin hydroxy equivalent number average molecular weight 28 323617 201226433 3] 00- 6ICS I 010

SI evjl 0-Λ 1S00 seo 081-< η inch-one 0- oo t s s 05 ιηει 9r 0-> sco oi-oole 0〇〇!.< η inch ‘one οοι

Si sozo § CSIL 0-> l'? 0600 εοεε

SIX S6.1 § 00_· odol 00_·

Oos-Ndcu r--οοί-ΝοαΛ bTTiu-ipiA— m6oo3-xd s 060 601 ioL 0-> 06CO οιηε(093

OSK 0_·1.1

CO s 80.0 szzo llnlcsl woo uxa m coin 〇o !§01>ττ0->01> 09(0 ιοοε ιη9ε —9«! «ο inchi^,eosα>εέ II inch 900C 6εε !y ίυίαοο!. 081 &lt ; 0~< oootc

UJE

9V ε·ι ®t τϊ. ε/iE/i 寸f#鸯驷丨!:1!-#丨esIMi 驷zwsz inch m—ΊΠ fl2to S,sSRl narrow s®? hN umbrella swallow icf/domain And Bao oseMl si Li twisted 85-1 29 323617 201226433 [ε omnibus] Comparative Example 7 100 〇〇csi 0.50 inch CO inch CJ Τ - Ο > 〇 0 309 343 359 S CO cp Ο Comparative Example 6 100 0.10 00 Csi 104 V-0 σ> 325 354 367 > 180 Ο r - Comparative Example 5 100 CD 0.10 q ό 110 Combustion I 266 i: — 344 — 378 m CD 0.92 0.88 Comparative Example 4 100 〇> 0.10 卜 — 1 I 1 1 1 ϊ 1 1 1 Comparative Example 3 100 283 0.10 100 Ο > s CM *r- ~r-~ 178 194 W) 0.34 0.31 Umbrella SZ α Ρ 1 i sec 1 __ PPP min kN/m kN/m YDPN -638 ΤΧ-0932Α Comparative Example 1 HCA-HQ BRG-555 DICY 2Ε4ΜΖ UL-94 Total time 1% reduction 3% reduction 5% reduction copper foil interlayer epoxy resin epoxy resin hardener hardening accelerator composition filling content Tg ( DSC) Flame Retardant Thermal Decomposition Temperature T-288 Test Stripping Strength 30 323617 201226433 Example 1 to Real _ Resin Lines _ and = (4), the present invention contains 酴Reacts, therefore, compared with Comparative Example 22: No (4) Compound: Reactant), tBu#i Only % Oxygen Resin Combined with Phosphorus Containing Phenol, and then Combined with Non-Epoxy Resin and Phosphorus Containing Bismuth Compound The phenolic phenolic ruthenium of the present invention is superior in solvent solubility as compared with the phenolic compound. As shown in Fig. 1G, compared with the conventional use of hard test, the use of the phosphorus-containing heterolipid of the present invention as the epoxy tree θ%, oxygen; the heat-reliability and adhesion of the W-hardened product Excellent. ★ In the case of Example 11, the curing of the phosphorus-containing epoxy resin is compared with the conventional curing (4). The curing with the combination of the epoxy resin is excellent in heat resistance, adhesion, and Tg. (Industrial Applicability) The phosphorus-containing phenol resin of the present invention is excellent in workability, hardenability, and moldability because of its solubility in an organic solvent and compatibility with an epoxy resin. The resin composition of the phosphorus phenol resin can have sufficient flame retardancy without using an additive flame retardant. Further, when the phosphorus-containing phenol resin of the present invention is used as a curing agent such as an epoxy resin, a cured product excellent in heat resistance and adhesion can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing gel permeation chromatography of a phosphorus-containing phenol resin obtained in Example 2. The horizontal axis represents the retention time (minutes) and the left axis represents the detection intensity (mV). The right axis shows the molecular weight (M) of the decrement line in logarithm. The residence time from the start of the test 31 323617 201226433 17.8 points to the end of the peak detection, the range of 26.1 points is the peak derived from the phosphorus-containing phenol resin component. Others are peaks from unreacted starting materials and impurities. Fig. 2 is a view showing the infrared absorption spectrum of the phosphorus-containing phenol resin obtained in Example 2. [Main component symbol description] None 0 32 323617

Claims (1)

201226433 VII. Scope of application: • I. A new type of filled resin, as expressed by the general formula (1) and 'number average molecular weight is 500 to 5000, CHfZ' y-^ch2ch \ OH A -(Ri-A^RrA^- -Y ^z-ch2chch2Vy- , 0H A 卞H2(pH-CH2-Z \ OH ' (1) AY -/ch2chch2-z' \ OH · (wherein A represents carbon number 6 to 20 of an extended aryl group and/or a triyl group, which may be the same or different, wherein γ represents an oxygen atom and/or a nitrogen atom, and the like may be the same or different, wherein Ζ represents a general formula. (2) and/or the general formula (3) and/or the general formula (4), but the phosphorus-containing phenol resin of the present invention must have the structures represented by the general formula (2) and the general formula (3) in one molecule. In the formula, 匕 represents an oxygen atom or a sulfur atom, a carbonyl group, a sulfonyl gro叩, a hydrocarbon group, a single bond, and the hydrocarbon group may contain a hetero atom, wherein α represents an integer of 〇 to 4, and a point represents 丨 to 1〇. The integer, r table is not 0 or 1, the integer representing 丨 to 1〇, when 〇, the structure in parentheses is a hydrogen atom, ε is an integer representing 〇 to 2, and when it is 〇, the structure in parentheses is a hydrogen atom. , β means 1 or 2) r2 (2) 0 〇 VR3 ——Ο—Α-〇~χ (wherein A and r are the same as in general formula (1), χ represents a hydrogen atom and/or 323617 1 201226433 :(5), which may be the same or different Further, in the formula, and R3 represents a hydrocarbon group of carbon to 6, which may be the same or different from each other to form a cyclic group. Atomic total (Χ-〇)δ (〇-χ)δ [Vx)s]e P (3) phase m = X is the same as the general formula (2), R4 represents an oxygen atom or a sulfur atom, a group, a fluorenyl group, a hydrocarbon group, a single bond, and a hydrocarbon group may contain a hetero atom) r2 0 (0) 73⁄4 (4) (wherein 7 and The phase (m) of the formula (1) represents a hydrocarbon group having a carbon number of j to 6, which may be the same or different, and may form a ring together with the phosphorus atom) '~CH2'?^'CH2~Y~A--(Ri-A)ir(RrA; (5) ^--Υγ〇Η2·ΟΗ·〇ΐ2-Ζ' \ OH , a--y-/ch2chch2 -z' \ OH / (wherein A and RrY'z'a, stone, and " are respectively the same as in the formula (1)). η • The phosphorus-containing phenol resin as described in claim 1 of the patent application, It is represented by the general formula (6) 323617 2 201226433 r... ride. ,.^〇_Α, 55ν兮. H (6) (U (wherein A and Rl, α, 7, 5, ε are the same as in the formula (1), Rz and R3 are the same as in the formula (2), I is the same as the formula (3), and 9 shows an integer from 0 to 5.) 3. The patented _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The phenanthrene-containing compound is reacted; r2 ... 〇10 C% R3 (7) HO-A-OH (wherein A and γ are the same as in the formula (1), respectively, and mR3 is the same as in the formula (2), respectively). A resin composition comprising the phosphorus-containing phenol resin according to any one of claims 3 to 5. 5. A flame retardant resin cured product, which is described in claim 4 The resin composition is hardened. 323617 3