CN107446120A - Phosphorous epoxy resin and the resin combination, solidfied material - Google Patents
Phosphorous epoxy resin and the resin combination, solidfied material Download PDFInfo
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- CN107446120A CN107446120A CN201710674822.1A CN201710674822A CN107446120A CN 107446120 A CN107446120 A CN 107446120A CN 201710674822 A CN201710674822 A CN 201710674822A CN 107446120 A CN107446120 A CN 107446120A
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- epoxy resin
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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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention is phosphorous epoxy resin, it is reacted to obtain by making epoxy resin (a) and having with the compounds (b) of the reactive functional groups of the epoxy reaction of epoxy resin (a), it is characterized in that, phosphorous phenolic compound shown in compounds (b) using formula (1) is as essential component, and the epoxide equivalent of resulting phosphorous epoxy resin is 60% to 95% scope of the theoretical epoxy equivalent weight tried to achieve by formula 1.Chemical formula 1Formula 1Formula 2Formula 3
Description
It is on 2 22nd, 2012 the applying date that the application, which is, Chinese Patent Application No. 201210042752.5, denomination of invention
For the divisional application of the patent of invention of " phosphorous epoxy resin and the resin combination, solidfied material ".
Technical field
The present invention relates to the phosphorous epoxy resin of anti-flammability and the phosphorous epoxy resin composition, its solidfied material.
Background technology
Because the cementability of epoxy resin, heat resistance, mouldability are excellent, therefore it is widely used in the electric, layer of electronic equipment
Lamination, sealant, automobile component, FRP, sporting goods etc..
Particularly when for electric, electronic equipment plywood, in order to prevent smoke of burning and control in fire, by force
It is strong to require to assign anti-flammability.As the fire retardantization method of plywood resin, conventional bromine system incombustible agent, nitrogen system incombustible agent and phosphorus system
Incombustible agent alone or in combination, the incombustible agent alone or in combination in and with it is inorganic be that the fire retardant system of fire retardant auxiliary agent is main flow.
But in recent years, from environmental problem, avoiding using bromine system incombustible agent always.In addition, red phosphorus is being used as addition type
During phosphorus flame-retardant agent, security is insufficient, when using phosphoric acid based compound, has and oozes out (bleed on solidfied material surface
Out) the problem of.In addition, when using phosphoric acid ester, there is the problem of solder flux heat resistance, solvent resistance reduce.
For described problem, disclosed in patent document 1,2 makes 10- (2,5- dihydroxy benzenes with defined mol ratio
Base) -10H-9- oxa- -10- phospho hetero phenanthrene -10- oxides (Sanko Co., Ltd.'s system, the entitled HCA-HQ of product) and epoxy resin
Thermosetting resin obtained from reaction and composition.In addition, Patent Document 3 discloses make more than two functions to have ring
The phosphorous epoxy resin that the resin of epoxide forms with two phenenyl phosphinyl (phosphinyl) reacted with hydroquinone.But by so
Phosphorus compound and epoxy resin react obtained from phosphorous epoxy resin as phosphorus content increases, molecular weight increase, therefore can
To obtain the viscosity of the resin varnish of sufficient anti-flammability height, so as to have workability and the immersion variation to base materials such as glass cloth
The problem of.Further, since the molecular weight of phosphorous epoxy resin increases, the crosslink density of solidfied material reduces, and therefore, it is difficult to obtain height
Glass transition temperature.
In addition, Patent Document 4 discloses due to only cannot get sufficient anti-flammability by phosphorous epoxy resin, therefore
Phosphorus compound is dissolved in phosphorous epoxy resin varnish, improves phosphorus content, but solvent must use DMF
Deng high boiling solvent, so as to which also phosphorus compound easily separates out the problem of such.Patent Document 5 discloses following method：
By the way that HCA-HQ micro mists are broken into the size that average grain diameter is 10 μm, maximum particle diameter is 40 μm, it is set to be dispersed in resin varnish,
But compared with when dissolving phosphorus compound using high boiling solvent, viscosity easily increases, if reducing varnish viscosity, have not
The problem of to sufficient anti-flammability.
Prior art literature
Patent document
Patent document 1：Japan Patent -3092009
Patent document 2：Japanese Unexamined Patent Publication 11-279258
Patent document 3：Japanese Unexamined Patent Publication 5-214070
Patent document 4：Japanese Unexamined Patent Publication 2002-249540
Patent document 5：Japanese Unexamined Patent Publication 2003-011269
The content of the invention
Invent problem to be solved
It is an object of the present invention to by remaining phenolic hydroxyl group in end after the reaction and reducing molecular weight, there is provided varnish
The phosphorous epoxy resin that viscosity is low, workability is excellent.In addition, by solidifying the phosphorous epoxy resin composition, there is provided solidification
The excellent solidfied material of property, anti-flammability, heat resistance, cementability.
The means used to solve the problem
That is, the present invention is (1) phosphorous epoxy resin, and it is by making epoxy resin (a) and having and epoxy resin
(a) compounds (b) of the reactive functional groups of epoxy reaction react and obtained, it is characterised in that have reactive official
Phosphorous phenolic compound that can be shown in the compounds (b) using formula (1) of group is as essential component, and resulting phosphorous ring
The epoxide equivalent of oxygen tree fat is 60% to 95% scope of the theoretical epoxy equivalent weight tried to achieve by formula 1.
Chemical formula 1
(in formula, A represents the arlydene and/or three-level aryl (triyl) that carbon number is 6 to 20, and n represents 0 or 1.Separately
Outside, in formula, R1And R2The alkyl that carbon number is 1 to 6 is represented, can be the same or different, can also be together with phosphorus atoms
Form ring-type).
Formula 1
Formula 2
Formula 3
(2) according to the phosphorous epoxy resin described in (1), it is with having reaction by the epoxy resin (a) shown in formula 2
Property functional group compounds (b) reaction obtained from, wherein, relative to the equivalent of epoxy radicals 1 of (a), the reactive functional of (b)
Group is the scope of 0.10 equivalent to 0.94 equivalent.
(3) phosphorous epoxy resin composition, it is to contain phosphorous epoxy resin described in claim 1 or 2 as necessary
The phosphorous epoxy resin class (c) of composition coordinates what is formed with epoxy curing agent, wherein, work as relative to the epoxy radicals 1 of (c)
Amount, the reactive functional groups of epoxy curing agent are the scope of 0.1 equivalent to 1.3 equivalents.
(4) phosphorous epoxy resin solidfied material, its be by solidify the phosphorous epoxy resin composition described in (3) and
The solidfied material of formation.
Invention effect
The phosphorous epoxy resin of the present invention is by making the epoxy radicals of epoxy resin (a) and the phosphorous phenol shown in formula (1)
The phenolic hydroxyl group of class compound is reacted and obtained, but is reacted all phenolic hydroxyl group and remained a part, in epoxy
Resin epoxy group and phenolic hydroxyl group coexist.Coexisted by epoxy radicals and phenolic hydroxyl group, when all phenolic hydroxyl group are reacted compared with,
The molecular weight of resulting epoxy resin reduces, and viscosity when forming epoxy resin varnish also reduces.Thus, obtain to glass cloth
Immersion raising etc., the good phosphorous epoxy resin of workability.In addition, the solidfied material physical property of this epoxy resin is commented
Valency, as a result find compared with without the phenolic hydroxyl group and only known phosphorous epoxy resin with epoxy radicals, heat resistance and resistance
Combustion property etc. improves, so as to complete the present invention.
Brief description of the drawings
Fig. 1 is the GPC figures of the phosphorous epoxy resin obtained in embodiment 3.
Fig. 2 is the IR figures of the phosphorous epoxy resin obtained in embodiment 3.
Embodiment
Hereinafter, embodiments of the present invention are described in detail.
As the epoxy resin (a) of the phosphorous epoxy resin for manufacturing the present invention, can include：By Epototo
YD-128, Epototo YD-8125 (bisphenol A type epoxy resin of Nippon Steel Chemical Co., Ltd's production), Epototo YDF-
170th, Epototo YDF-8170 (bisphenol f type epoxy resin of Nippon Steel Chemical Co., Ltd's production), YSLV-80XY (new days
Iron KCC production tetramethyl bisphenol f type epoxy resin), Epototo YDC-1312 (hydroquinone type epoxy resin),
JER YX4000H (biphenyl type epoxy resin of Mitsubishi chemical Co., Ltd's production), Epototo YDPN-638 (Nippon Steel's strain formulas
Commercial firm production phenol novolak type epoxy resin), Epototo YDCN-701 (Nippon Steel Chemical Co., Ltd production first
Phenol phenolic resin varnish type epoxy resin), Epototo ZX-1201 (Nippon Steel Chemical Co., Ltd production bisphenol fluorene type ring oxygen tree
Fat), the TX-0710 bisphenol-s epoxy resin of production (Nippon Steel Chemical Co., Ltd), Epiclon EXA-1515 (big Japan
Chemical industry Co., Ltd. production bisphenol-s epoxy resin), NC-3000 (Nippon Kayaku K. K production biphenyl aralkyl
Base phenol type epoxy resin), Epototo ZX-1355, Epototo ZX-1711 (Nippon Steel Chemical Co., Ltd production naphthalene
Two phenol-type epoxy resins), Epototo ESN-155 (Nippon Steel Chemical Co., Ltd production betanaphthol aralkyl type epoxy tree
Fat), Epototo ESN-355, Epototo ESN-375 (Nippon Steel Chemical Co., Ltd production bisnaphthol aralkyl type ring
Oxygen tree fat), Epototo ESN475V, Epototo ESN-485 (Nippon Steel Chemical Co., Ltd production alpha-Naphthol aralkyl
Type epoxy resin), the EPPN-501H triphenylmethane type epoxy resin of production (Nippon Kayaku K. K), Sumiepoxy
TMH-574 (the triphenylmethane type epoxy resin of Sumitomo Chemical Co's production), YSLV-120TE (Nippon Steel's chemistry strain formulas
Commercial firm production double thioether type epoxy resin), Epototo ZX-1684 (Nippon Steel Chemical Co., Ltd production resorcinol
Type epoxy resin), the Denacol EX-201 resorcinol type epoxy resin of production (Nagase ChemteX Co., Ltd.),
The phenolic compounds of the polynary phenol resin such as Epiclon HP-7200H (dicyclopentadiene-type epoxy resin of Dainippon Ink Chemicals's production)
With epihalohydrin (epihalohydrin) manufacture epoxy resin, by TX-0929, TX-0934, TX-1032 (Nippon Steel chemistry
The alkylene glycol type epoxy resin of Co., Ltd.'s production) etc. the epoxy resin of alcoholic compound and epihalohydrin manufacture, by
Celloxide 2021 (aliphatic cyclic epoxy resin of Daicel chemical industry Co., Ltd. production), Epototo YH-434
Amines and epihalohydrins such as (the diaminodiphenyl-methane four glycidyl group amine of Nippon Steel Chemical Co., Ltd's production)
The epoxy resin of manufacture, make jER 630 (the aminobenzene phenol-type epoxy resin of Mitsubishi chemical Co., Ltd's production), Epototo
The asphalt mixtures modified by epoxy resin such as FX-289B, Epototo FX-305, TX-0932A (phosphorous epoxy resin of Nippon Steel Chemical Co., Ltd's production)
Phosphorous epoxy resin, polyurethane modified epoxy resin, Han oxazoles obtained from the reaction of the modifying agent such as fat and phosphorous phenolic compound
Epoxy resin of alkanone ring etc., but it is not limited to these.In addition, these epoxy resin can be used alone, can also and with 2 kinds
More than.
For the functional equivalent of the reactive functional groups of the epoxy reaction with epoxy resin (a), in phenolic compounds
When represent hydroxyl equivalent, anhydride equivalent is represented in acid anhydrides, in amines or with phosphorus with the hydrogen of phosphorus atoms Direct Bonding
Compound isochronous graph shows Ahew.
Phosphorous phenolic compound shown in compounds (b) with reactive functional groups using formula (1) is as must be into
Point.As the specific example of phosphorous phenolic compound, can include：10- (2,5- dihydroxy phenyls) -10H-9- oxa-s -10-
Phospho hetero phenanthrene -10- oxides (Sanko Co., Ltd. produces, the entitled HCA-HQ of product), 10- (the epoxide naphthalenes of Isosorbide-5-Nitrae-two
(dioxynaphthalene)) -10H-9- oxa-s -10- phospho hetero phenanthrene -10- oxides (being designated as HCA-NQ below), diphenyl phosphine oxide
Base quinhydrones (Hokko Chemical Industry Co., Ltd. produces, the entitled PPQ of product), the two phenenyl phosphinyl-epoxide of Isosorbide-5-Nitrae-two naphthalene, Isosorbide-5-Nitrae-Asia
Cyclooctyl (cyclooctylene) phosphinyl -1, 4-benzenediol (phenyldiol) (Nippon Chemical Ind produces,
The entitled CPHO-HQ of product), 1,5- cyclooctylenes phosphinyl -1, 4-benzenediol (Nippon Chemical Ind produce, product
Entitled CPHO-HQ) etc. phosphorous phenols, but be not limited to these.In addition, these phosphorous phenolic compounds can also and with 2 kinds with
On.
Chemical formula 2
(in formula, A represents the arlydene and/or three-level aryl that carbon number is 6 to 20, and n represents 0 or 1.In addition, in formula,
R1And R2The alkyl that carbon number is 1 to 6 is represented, can be the same or different, ring can also be formed together with phosphorus atoms
Shape).
In addition, these phosphorous phenolic compounds can pass through 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
(Sanko Co., Ltd. produces, the entitled HCA of product) or diphenylphosphine etc. have the phosphorus with the active hydrogen-based of phosphorus atoms Direct Bonding
Compound, react and obtain with the quinones such as 1,4- benzoquinones or 1,4- naphthoquinones.For HCA-HQ, in Japanese Unexamined Patent Application 60-126293
In show synthetic method, for HCA-NQ, synthetic method is shown in Japanese Unexamined Patent Application 61-236787, for PPQ,
Zh.Obshch.Khim, 42 (11), synthetic method is shown in the 2415-2418 pages (1972), but be not limited to this, can adopted
With known conventional method.
As the compounds (b) with reactive functional groups beyond the phosphorous phenolic compound, such as can arrange
Enumerate：The Hydroxybenzenes such as catechol, resorcinol, quinhydrones, bisphenols, dinaphthalene phenols, three phenols, bisphenol-A, Bisphenol F, bis-phenol
S, Shonol BRG-555 (phenol resol resins of Showa Denko K. K's production), cresol novolac resin, alkane
Base phenol resol resins, aralkylphenol novolac resin, the phenol resol resins containing triazine ring, biphenyl aralkyl
Base phenolic resin, Resitop TPM-100 (the trihydroxy benzene methylmethane type novolaks of Gunsaka Chem. Industry Co., Ltd.'s production
Resin), aralkyl naphthalenediol resin etc. have in a molecule compounds of more than 2 phenolic hydroxyl group, 9,10- dihydros-
9- oxa- -10- phospho hetero phenanthrene -10- oxides (Sanko Co., Ltd. produces, the entitled HCA of product) or diphenylphosphine etc. have and phosphorus
Hydrazides class, the imidazoles chemical combination such as the phosphorus compound class of the active hydrogen-based of atom Direct Bonding, adipic dihydrazide, sebacic dihydrazide
Species and its esters, dicyandiamide, aminobenzoic acid esters, diethylenetriamines, trien, tetren,
The aliphatic such as m-xylene diamine, IPD amine, diaminodiphenyl-methane, diamino diphenyl sulfone, diaminourea
The aromatic amines such as ethylo benzene, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic acid
Acid anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride
Etc. anhydrides etc., two or more in them can be used.The usage amount of these compounds is relative in used epoxy resin
The equivalent of epoxy radicals 1, preferably using the equivalent of functional group 0.5 below, more preferably below 0.2 equivalent.
The epoxide equivalent of the phosphorous epoxy resin of the present invention is the 60% to 95% of the theoretical epoxy equivalent weight tried to achieve by formula 1
Scope, preferably 70% to 95% scope, more preferably 75% to 90% scope.It is if less than 60%, then a large amount of to remain
The phosphorous phenolic compound of slightly solubility, solvent solubility lack.If greater than 95%, then viscosity during epoxy resin varnish is formed
Reducing effect diminishes.
In addition, the phosphorous epoxy resin of the present invention is by the epoxy resin (a) shown in formula 2 and has reactive functional
Obtained from compounds (b) reaction of group, wherein, relative to the equivalent of epoxy radicals 1 of (a), the reactive functional groups of (b) are
The scope of 0.10 equivalent to 0.94 equivalent, but preferably 0.20 equivalent to the scope of 0.70 equivalent, more preferably 0.20 equivalent extremely
The scope of 0.60 equivalent.If being less than 0.10 equivalent, anti-flammability becomes insufficient (b), if it exceeds 0.94 equivalent makes its anti-
Should, then the varnish viscosity of resulting phosphorous epoxy resin increases.
The reaction temperature for obtaining the reaction of the phosphorous epoxy resin of the present invention is 100 DEG C to 250 DEG C, more preferably 130 DEG C
To 180 DEG C, the progress reacted below 100 DEG C is substantially slack-off, is difficult to control more than 250 DEG C for obtaining theoretical epoxy equivalent weight
60% to 95% scope reaction.
In addition, in the reaction of phosphorous epoxy resin of the present invention is obtained, in order to promote reaction to use as needed
Catalysts.As the catalyst that can be used, can include：Triphenylphosphine, three (2,6- Dimethoxyphenyls) phosphines etc.
Quaternary phosphine salt, the 2- ethyl -4- methyl such as phosphine, the phenyl-bromide Phosphonium (phosphonium) of normal-butyl three, ethyl triphenyl phosphonium iodide
The quaternary ammonium salts such as imidazoles, tetramethyl ammonium chloride, the tetraethylammonium bromides such as imidazoles, 2- phenylimidazoles, triethylamine, benzyl diformazan
Tertiary amines such as amine etc., known conventional catalyst, but it is not limited to these.The usage amount of these catalyst is relative to phenolic compounds
Total amount, preferably 0.005% to 1% scope.
The reaction of epoxy resin and phosphorous phenolic compound can also be carried out in a solvent with solvent-free, but in a solvent
During progress, carried out preferably in non-protonic solvent, for example, can include：Toluene, dimethylbenzene, methanol, ethanol, 2- fourth oxygen
Base ethanol, dialkyl ether, glycol ether, propylene glycol monomethyl ether, dioxanes etc..These reaction dissolvents can be used alone, Huo Zheye
Two or more can be used simultaneously.The usage amount of these reaction dissolvents is preferably less than 50% in reactant gross weight.
In addition, the reaction of the phosphorous epoxy resin of the present invention can make the resin epoxy equivalent weight be by adjusting catalytic amount
The scope of the 60% to 95% of theoretical epoxy equivalent weight, but regulation reaction temperature can also be used or periodically reacted etc.
Known conventional manufacture method, and it is not limited to these.
In the phosphorous epoxy resin composition of the present invention, described phosphorous epoxy resin is essential component, but can root
According to needing containing other epoxy resin, epoxy curing agent, curing accelerator, filler etc..
The epoxy resin that can be used for the phosphorous epoxy resin composition contains as essential component, but except this hair
Outside bright phosphorous epoxy resin, the scope of physical property is not being damaged, can used and the phosphorous epoxy resin for the present invention
The same kind of epoxy resin of epoxy resin of synthesis, but it is not limited to these.In addition, these epoxy resin can also and with 2
More than kind.
As the epoxy curing agent for the phosphorous epoxy resin composition that can be used for the present invention, can include：It is adjacent
The Hydroxybenzenes such as benzenediol, resorcinol, quinhydrones, dinaphthalene phenols, bisphenols, three phenols, bisphenol-A, Bisphenol F, bisphenol S, three hydroxyls
Base phenylmethane, trihydroxy diphenylphosphino ethane, Shonol BRG-555 (the phenol novolacs trees of Showa Denko K. K's production
Fat), cresol novolac resin, alkylphenol novolac resin, aralkylphenol novolac resin, the benzene containing triazine ring
Phenol novolac resin, biphenyl aralkyl phenolic resin, Resitop TPM-100 be (Gunsaka Chem. Industry Co., Ltd.'s production
Trihydroxy benzene methylmethane type novolac resin), aralkyl naphthalenediol resin etc. there are more than 2 phenolic hydroxyl group in a molecule
Compounds, adipic dihydrazide, hydrazides class, imidazolium compounds class and its esters, dicyandiamide, the ammonia such as sebacic dihydrazide
Yl benzoic acid esters, diethylenetriamines, trien, tetren, m-xylene diamine, IPD
Etc. the aromatic amines such as aliphatic amine, diaminodiphenyl-methane, diamino diphenyl sulfone, diamino ethyl benzene, adjacent benzene two
Formic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride,
Anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride etc., can also and use known in
More than a kind of conventional epoxy curing agent.The usage amount of epoxy curing agent is relative to the phosphorous asphalt mixtures modified by epoxy resin of the present invention
Epoxy radicals 1 equivalent of the fat as the phosphorous epoxy resin class (c) of essential component, the functional group of epoxy curing agent are preferably
The scope of 0.1 equivalent to 1.3 equivalents, more preferably 0.2 equivalent are to 0.9 equivalent.
In addition, in influence liquidity and viscosity etc., in the physical property for the phosphorous epoxy resin composition for not damaging the present invention
Scope, reactive diluent can be used.Diluent preferred reactive diluent, or non-reactive diluent.Make
For reactive diluent, can include：Allyl glycidyl ether, 2- hexyl glycidyl ethers, phenyl glycidyl
The monofunctional glycidyl such as ether ethers, resorcinolformaldehyde resin, neopentylglycol diglycidyl ether, 1,6- hexane diols
The function glycidol ethers of diglycidyl ether etc. two, glycerol polyglycidyl ether, trimethylolpropane polyglycidylether, season
Polyfunctional glycidyl ether's classes such as penta tetrol polyglycidyl ether.As non-reactive diluent, can include：Benzylalcohol, fourth
Base diethylene glycol (DEG), pine-tree oil etc..
In addition, in the phosphorous epoxy resin composition of the present invention, curing accelerator can be used as needed.For example,
It can include：Phosphine, quaternary phosphine salt, tertiary amines, quaternary ammonium salt, imidazolium compounds class, boron trifluoride complex class, 3- (3,
4- dichlorophenyls) -1,1- dimethyl ureas, 3- (4- chlorphenyls) -1,1- dimethyl ureas, 3- phenyl -1,1- dimethyl ureas etc..These solidifications
Accelerator used in epoxy resin and the species of epoxy curing agent, forming method, solidification temperature, requirement
Characteristic and it is different, its relative to epoxy resin with weight ratio meter, preferably 0.01% to 20% scope, more preferably 0.1% to
10%.
The phosphorous epoxy resin composition of the present invention can coordinate thermosetting resin, thermoplasticity in the scope for not damaging characteristic
Resin.Such as it can include：Phenolic resin, acrylic resin, Petropols, indene resin, coumarone indeneresin, phenoxy
Fat, polyurethane, polyester, polyamide, polyimides, polyamidoimide, PEI, polyether sulfone, polysulfones, polyether-ether-ketone,
Polyphenylene sulfide, polyvinyl formal etc., but it is not limited to these.
The phosphorous epoxy resin composition of the present invention can coordinate inorganic filler, organic filler as needed.As
The example of filler, it can include：Fused silica, crystalline silica, aluminum oxide, silicon nitride, aluminium hydroxide, cunning
Stone, mica, calcium carbonate, calcium silicates, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fibers
Dimension, alumina fibre, silica alumina fiber, silicon carbide fibre, polyester fiber, cellulose fibre, aromatic polyamides are fine
Dimension etc..These fillers are preferably 1% to 70% in resin combination gross weight.
The phosphorous epoxy resin composition of the present invention can also coordinate silane coupler, antioxidant, the demoulding as needed
The various additives such as agent, defoamer, emulsifying agent, thixotropy conferring agents, smooth agent, incombustible agent, face material.These additives are preferably
0.01% to 20% scope in resin combination gross weight.
The phosphorous epoxy resin composition of the present invention can be entered by the method same with known composition epoxy resin
Row shaping, it is solidified to form solidfied material.Forming method, curing can use same with known composition epoxy resin
Method, without the intrinsic method of the resin combination of the present invention.
The phosphorous epoxy resin solidfied material of the present invention can use the modes such as sandwich, article shaped, sticky object, film, film.
The present invention is the phosphorous epoxy resin for having anti-flammability, due to the immersion good of the base materials such as glass cloth, therefore
Judge that its workability is excellent, also, the anti-flammability of phosphorous epoxy resin solidfied material and heat resistance, cementability are good, and it is as use
In the encapsulant of electrical and electronic parts, copper-clad laminated board, coatings, fire retardant coating, composite, the fire retardant bonding agent of insulation
It is useful Deng material.
Embodiment
Then, embodiments of the invention are shown, the scope of the present invention is not limited to these embodiments.As long as no special
Illustrate, then " part " represents parts by weight.In addition, analysis method, assay method are as follows.
Epoxide equivalent：Based on JIS K7236.
Phenolic hydroxyl group equivalent：Addition includes the THF of 4% methanol in the sample, adds 10% TBAH, uses
Ultraviolet-uisible spectrophotometer, measure wavelength are 400nm to the absorbance between 250nm.By being asked by same assay method
The calibration curve gone out, obtain weight of the phenolic hydroxyl group as the sample of every 1 equivalent of hydroxyl.
Nonvolatile component：JIS K7235-1986
Number-average molecular weight：Use gel permeation chromatography (HLC-8220GPC that TOSOH Co., Ltd produces) measure molecule
Amount distribution, is converted by the calibration curve obtained by polystyrene standard.
Phosphorus content：Sulfuric acid, hydrochloric acid, perchloric acid are added in the sample, and is heated, and are carried out wet type ashing, are made all phosphorus atoms
Form orthophosphoric acid.Make metavanadate and molybdic acid reactant salt in sulfuric acid solution, to caused phosphovanadomolybdic acid complex compound
Absorbance at 420nm is measured, and the phosphorus atoms content obtained by the calibration curve of pre-production is represented with weight %.
The phosphorus content of plywood represents in the form of relative to the content of the resin component of plywood.
Varnish viscosity：Using cone plate type viscometer (Tokimec societies system), rotor uses standard cone (1 ° 34 '), at 25 DEG C
It is measured under environment by 10rpm of revolution.
Infrared absorption spectroscopy：Using fourier-transform infrared spectrophotometer, (P Co., Ltd. erkin Elmer are produced
Spectum One), determined by tablet method (KBr).
Glass transition temperature：Device (SII NanoTechnology Co., Ltd. is determined with by means of differential scanning calorimetry
The EXSTAR6000DSC6200 of production) DSC extrapolated values when being measured under 10 DEG C/min of Elevated Temperature Conditions thermometer
Show.
Flammability：Based on UL94 (Underwriters Laboratories Inc. safety certification specification).5 are tried
Test piece to be tested, having after 1st time expressed in seconds and the 2nd time igniting (respectively to 5 every 2 10 igniting of progress altogether)
The total ascent time of flame firing duration.
Peel strength of copper foil and interlaminar strength：Based on JIS C6481.
T-288 is tested：Tested based on IPC TM-650 at 288 DEG C.
Embodiment 1
In the removable flask experimental provision of four mouthfuls of glass systems for possessing agitating device, thermometer, cooling tube, nitrogen ingress pipe
(Nippon Steel Chemical Co., Ltd produces middle input bisphenol f type epoxy resin, product entitled YDF-170, epoxide equivalent 170g/
Eq.) 687 parts, and put into 10- (2,5- dihydroxy phenyl) -10H-9- oxa- -10- phospho hetero phenanthrene -10- oxide (three light strain formula meetings
Society produces, the entitled HCA-HQ of product, and fusing point is 256 DEG C, and phosphorus content is 9.6 weight %, hydroxyl equivalent 162g/eq.) 314 parts.
Triphenylphosphine (be below designated as TPP) 0.06 part of the addition as catalyst thereto, after reaction in 4 hours is carried out at 165 DEG C, add
MEK (being designated as MEK below) is added to be diluted.Resulting phosphorous epoxy resin solution is pale yellow transparent, nonvolatile component
For 70%, varnish viscosity is 510mPas, and actual measurement epoxide equivalent is 301g/eq., hydroxyl equivalent 850g/eq., and phosphorus content is
3.0 weight %, number-average molecular weight 587.In addition, there is reactive official relative to the equivalent of epoxy radicals 1 of epoxy resin (a)
Can the functional group of compounds (b) of group be 0.48 equivalent, theoretical epoxy equivalent weight 474g/eq., survey epoxide equivalent relative to
The ratio of theoretical epoxy equivalent weight is 64%.Inventory and feed intake ratio, character of resin etc. are shown in table 1.
Embodiment 2
687 parts of YDF-170,251 parts of HCA-HQ, phenol novolak type resin (Showa are put into similarly to Example 1
Electrician Co., Ltd. produces, and the entitled Shonol BRG-557 of product, phenolic hydroxyl group equivalent be 105g/eq.) 63 parts, addition conduct
0.06 part of the TPP of catalyst, its reaction is made by method similarly to Example 1.After the completion of reaction, carried out with MEK dilute
Release.Resulting phosphorous epoxy resin solution is pale yellow transparent, and nonvolatile component 70%, varnish viscosity is 550mPas,
Actual measurement epoxide equivalent is 365g/eq., hydroxyl equivalent 1200g/eq., and phosphorus content is 2.4 weight %, number-average molecular weight 619.
In addition, the functional group of the compounds (b) with reactive functional groups relative to the equivalent of epoxy radicals 1 of epoxy resin (a)
For 0.53 equivalent, theoretical epoxy equivalent weight 527g/eq., actual measurement epoxide equivalent is 69% relative to the ratio of theoretical epoxy equivalent weight.
Inventory and feed intake ratio, character of resin etc. are shown in table 1.
Embodiment 3
In the removable flask experimental provision of four mouthfuls of glass systems for possessing agitating device, thermometer, cooling tube, nitrogen ingress pipe
(Sanko Co., Ltd. produces middle input 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the entitled HCA of product, phosphorus contains
Measure as 14.2 weight %) 209 parts and 1,4-naphthoquinone (Kawasaki Kasei Chemicals Ltd. produces, and amount of moisture is 3.4 weight %)
150 parts, 490 parts of toluene, its is set to react 90 at 110 DEG C after being stirred 30 minutes at 75 DEG C, during moisture in removal system
Minute, toluene is then removed, obtains 10- (epoxide of Isosorbide-5-Nitrae-two naphthalene) -10H-9- oxa- -10- phospho hetero phenanthrene -10- oxides (HCA-
NQ).641 parts of YDF-170,0.09 part of the TPP as catalyst are added thereto, are made by method similarly to Example 1
It reacts.After the completion of reaction, it is diluted with MEK.Resulting phosphorous epoxy resin solution is that persimmon is transparent, non-volatile
Composition is 70%, and varnish viscosity is 440mPas, and actual measurement epoxide equivalent is 409g/eq., hydroxyl equivalent 1750g/eq., phosphorus
Content is 3.0%, number-average molecular weight 603.In addition, relative to epoxy resin (a) the equivalent of epoxy radicals 1 have reactivity
The functional group of the compounds (b) of functional group is 0.50 equivalent, theoretical epoxy equivalent weight 538g/eq., it is relative to survey epoxide equivalent
In theoretical epoxy equivalent weight ratio be 76%.Inventory and feed intake ratio, character of resin etc. are shown in table 1.
Embodiment 4
141 parts of HCA, 101 parts of 1,4-naphthoquinone are put into similarly to Example 3, are made by method similarly to Example 3
It reacts, and obtains HCA-NQ.Adding phenol novolak type epoxy resin thereto, (Nippon Steel Chemical Co., Ltd produces, production
The name of an article is YDPN-638, epoxide equivalent 175g/eq.) 758 parts, 0.02 part of the TPP portions as catalyst, carried out at 165 DEG C
After reaction in 4.5 hours, it is diluted with MEK.Resulting phosphorous epoxy resin solution is that persimmon is transparent, and nonvolatile component is
70%, varnish viscosity is 1300mPas, and actual measurement epoxide equivalent is 292g/eq., hydroxyl equivalent 3600g/eq., and phosphorus content is
2.0%, number-average molecular weight 884.In addition, there are reactive functional groups relative to the equivalent of epoxy radicals 1 of epoxy resin (a)
The functional groups of compounds (b) be 0.30 equivalent, theoretical epoxy equivalent weight 318g/eq., actual measurement epoxide equivalent is relative to theory
The ratio of epoxide equivalent is 92%.Inventory and feed intake ratio, character of resin etc. are shown in table 1.
Embodiment 5
108 parts of HCA, 80 parts of 1,4-naphthoquinone are put into similarly to Example 3, and it is made by method similarly to Example 3
Reaction, obtains HCA-NQ.Adding triphenylmethane type epoxy resin thereto, (Nippon Kayaku K. K produces, and product is entitled
EPPN-501H, epoxide equivalent 167.2g/eq.) 833 parts, 0.02 part of the TPP as catalyst, it is small that 6 are carried out at 150 DEG C
After Shi Fanying, it is diluted with propylene glycol monomethyl ether (being designated as PGM below)/MEK mixed solvents.Resulting phosphorous epoxy resin
Solution is that persimmon is transparent, and nonvolatile component 70%, varnish viscosity is 540mPas, and actual measurement epoxide equivalent is 239g/eq.,
Hydroxyl equivalent is 4000g/eq., phosphorus content 1.5%, number-average molecular weight 628.In addition, relative to epoxy resin (a)
The functional group of the compounds (b) with reactive functional groups of the equivalent of epoxy radicals 1 is 0.20 equivalent, and theoretical epoxy equivalent weight is
255g/eq., actual measurement epoxide equivalent are 94% relative to the ratio of theoretical epoxy equivalent weight.Inventory is shown in table 1 and is fed intake
Ratio, character of resin etc..
Embodiment 6
108 parts of HCA, 80 parts of 1,4-naphthoquinone are put into similarly to Example 3, and it is made by method similarly to Example 3
Reaction, obtains HCA-NQ.Adding bisnaphthol aralkyl-type epoxy resin thereto, (Nippon Steel Chemical Co., Ltd produces, product
Entitled ESN-375, epoxide equivalent 167g/eq.) 833 parts, 0.02 part of the TPP as catalyst, it is small that 6 are carried out at 150 DEG C
After Shi Fanying, it is diluted with PGM/MEK mixed solvents.Resulting phosphorous epoxy resin solution is that persimmon is transparent, is not waved
It is 70% to send out composition, and varnish viscosity is 700mPas, and actual measurement epoxide equivalent is 239g/eq., hydroxyl equivalent 4000g/eq.,
Phosphorus content is 1.5%, number-average molecular weight 716.In addition, reacted relative to the having for the equivalent of epoxy radicals 1 of epoxy resin (a)
Property functional group the functional groups of compounds (b) be 0.20 equivalent, theoretical epoxy equivalent weight 254g/eq., survey epoxide equivalent phase
Ratio for theoretical epoxy equivalent weight is 94%.Inventory and feed intake ratio, character of resin etc. are shown in table 1.
Embodiment 7
In the phosphorous epoxy resin obtained in embodiment 1 with shown in table 3 solid constituent amount coordinate dicyandiamide (DICY,
Ahew is 21g/eq.) and curing accelerator, obtain resin combination.It is dissolved in MEK, obtains resin varnish.
Resulting epoxy resin varnish is infiltrated up to glass cloth (WEA 116E106S136, Nitto Boseki Co. Ltd's production, thickness
For 0.1mm) in, drying in 10 minutes is carried out in 150 DEG C of heated-air circulation oven, obtains prepreg.By resulting preimpregnation
Material base 4 is overlapping with copper foil (3EC-III, Mitsu Mining ＆ Smelting Co., Ltd's production, thickness are 35 μm), 130 DEG C × 15 points+
2MPa vacuum pressed is carried out under 170 DEG C × 70 points of temperature conditionss, obtains the plywood that thickness is 0.5mm.Shown in table 2
Compounding ratio and plywood evaluation result.
Embodiment 8
Similarly to Example 7 using the phosphorous epoxy resin and DICY obtained in example 2, epoxy resin is obtained
Solidfied material.Compounding ratio and plywood evaluation result are shown in table 2.
Embodiment 9
Similarly to Example 7 using the phosphorous epoxy resin and DICY obtained in embodiment 3, epoxy resin is obtained
Solidfied material.Compounding ratio and plywood evaluation result are shown in table 2.
Embodiment 10
Similarly to Example 7 using the phosphorous epoxy resin and cresol novolak type ring obtained in embodiment 3
Oxygen tree fat (Nippon Steel Chemical Co., Ltd produces, product entitled YDCN-704, epoxide equivalent 209g/eq.), DICY, are obtained
Epoxy resin cured product.Compounding ratio and plywood evaluation result are shown in table 2.
Embodiment 11
Similarly to Example 7 using the phosphorous epoxy resin and DICY obtained in example 4, epoxy resin is obtained
Solidfied material.Compounding ratio and plywood evaluation result are shown in table 2.
Embodiment 12
Similarly to Example 7 using the phosphorous epoxy resin and BRG-557 obtained in embodiment 3, presoaked
Material base.By resulting prepreg 4 and copper foil (3EC-III, Mitsu Mining ＆ Smelting Co., Ltd's production, thickness are 35 μm)
It is overlapping, 2MPa vacuum pressed is carried out under 130 DEG C × 15 points+190 DEG C × 80 points of temperature conditionss, it is 0.5mm to obtain thickness
Plywood.Compounding ratio and plywood evaluation result are shown in table 2.
Embodiment 13
The phosphorous epoxy resin and BRG-557 obtained in embodiment 5 is used similarly to Example 12, obtains epoxy
Resin cured matter.Compounding ratio and plywood evaluation result are shown in table 2.
Embodiment 14
The phosphorous epoxy resin and BRG-557 obtained in embodiment 6 is used similarly to Example 12, obtains epoxy
Resin cured matter.Compounding ratio and plywood evaluation result are shown in table 2.
Comparative example 1
687 parts of YDF-170,314 parts of HCA-HQ are put into similarly to Example 1, add the TPP as catalyst
0.31 part, after reaction in 2 hours is carried out at 165 DEG C, it is diluted with MEK.Resulting phosphorous epoxy resin solution is yellowish
Color is transparent, nonvolatile component 70%, and varnish viscosity is 1700mPas, and actual measurement epoxide equivalent is 493g/eq., hydroxyl equivalent
More than 10000g/eq., phosphorus content 3.0%, number-average molecular weight 1260.In addition, the epoxy relative to epoxy resin (a)
The functional group of the compounds (b) with reactive functional groups of the equivalent of base 1 is 0.48 equivalent, theoretical epoxy equivalent weight 474g/
Eq., it is 104% to survey epoxide equivalent relative to the ratio of theoretical epoxy equivalent weight.Inventory and rate of charge are shown in table 3
Rate, character of resin etc..
Comparative example 2
209 parts of HCA, 150 parts of 1,4-naphthoquinone are put into similarly to Example 3, are made by method similarly to Example 3
It reacts, and obtains HCA-NQ.Thereto add 641 parts of YDF-170,0.36 part of the TPP as catalyst, by with comparative example
1 same method makes its reaction.After the completion of reaction, it is diluted with MEK.Resulting phosphorous epoxy resin solution is dense brown
Color is transparent, nonvolatile component 70%, and varnish viscosity is 1500mPas, and actual measurement epoxide equivalent is 527g/eq., hydroxyl equivalent
More than 10000g/eq., phosphorus content 3.0%, number-average molecular weight 1038.In addition, the epoxy relative to epoxy resin (a)
The functional group of the compounds (b) with reactive functional groups of the equivalent of base 1 is 0.50 equivalent, theoretical epoxy equivalent weight 538g/
Eq., it is 98% to survey epoxide equivalent relative to the ratio of theoretical epoxy equivalent weight.Shown in table 3 inventory and feed intake ratio,
Character of resin etc..
Comparative example 3
141 parts of HCA, 101 parts of 1,4-naphthoquinone are put into similarly to Example 3, are made by method similarly to Example 3
It reacts, and obtains HCA-NQ.758 parts of YDPN-638,0.24 part of the TPP as catalyst are added thereto, are entered at 165 DEG C
Row reaction, gelation as a result occurs after reaction starts 1 hour.Therefore, plywood evaluation is not carried out.
Comparative example 4
154 parts of HCA, 77 parts of 1,4-naphthoquinone are put into similarly to Example 3, and it is made by method similarly to Example 3
Reaction, obtains HCA-NQ.246 parts of YDF-170,523 parts of YDPN-638, the TPP 0.23 as catalyst are added thereto
Part, after reaction in 2 hours is carried out at 165 DEG C, it is diluted with MEK.Resulting phosphorous epoxy resin solution is that persimmon is saturating
Bright, nonvolatile component 70%, varnish viscosity is 1500mPas, and actual measurement epoxide equivalent is 311g/eq., and hydroxyl equivalent is more than
10000g/eq., phosphorus content 2.2%, number-average molecular weight 822.In addition, work as relative to the epoxy radicals 1 of epoxy resin (a)
The functional group of the compounds (b) with reactive functional groups of amount is 0.22 equivalent, and theoretical epoxy equivalent weight 302g/eq. is real
It is 103% that epoxide equivalent, which is surveyed, relative to the ratio of theoretical epoxy equivalent weight.Inventory and feed intake ratio, resin are shown in table 3
Character etc..
Comparative example 5
108 parts of HCA, 80 parts of 1,4-naphthoquinone are put into similarly to Example 3, and it is made by method similarly to Example 3
Reaction, obtains HCA-NQ.833 parts of EPPN-501H, 0.19 part of the TPP as catalyst are added thereto, are entered at 150 DEG C
After row reaction in 3 hours, it is diluted with PGM/MEK mixed solvents.Resulting phosphorous epoxy resin solution is that persimmon is transparent,
Nonvolatile component is 70%, and varnish viscosity is 1000mPas, and actual measurement epoxide equivalent is 257g/eq., and hydroxyl equivalent is more than
10000g/eq., phosphorus content 1.5%, number-average molecular weight 796.In addition, work as relative to the epoxy radicals 1 of epoxy resin (a)
The functional group of the compounds (b) with reactive functional groups of amount is 0.20 equivalent, and theoretical epoxy equivalent weight 255g/eq. is real
It is 101% that epoxide equivalent, which is surveyed, relative to the ratio of theoretical epoxy equivalent weight.Inventory and feed intake ratio, resin are shown in table 3
Character etc..
Comparative example 6
108 parts of HCA, 80 parts of 1,4-naphthoquinone are put into similarly to Example 3, and it is made by method similarly to Example 3
Reaction, obtains HCA-NQ.833 parts of ESN-375,0.19 part of the TPP as catalyst are added thereto, and 6 are carried out at 150 DEG C
After hour reaction, it is diluted with PGM/MEK mixed solvents.Resulting phosphorous epoxy resin solution is that persimmon is transparent, no
Volatile ingredient is 70%, and varnish viscosity is 1400mPas, and actual measurement epoxide equivalent is 253g/eq., and hydroxyl equivalent is more than
10000g/eq., phosphorus content 1.5%, number-average molecular weight 892.In addition, work as relative to the epoxy radicals 1 of epoxy resin (a)
The functional group of the compounds (b) with reactive functional groups of amount is 0.20 equivalent, and theoretical epoxy equivalent weight 254g/eq. is real
It is 99% that epoxide equivalent, which is surveyed, relative to the ratio of theoretical epoxy equivalent weight.Show in table 3 inventory and the ratio that feeds intake, resin
Character etc..
Comparative example 7
Similarly to Example 7 using the phosphorous epoxy resin and DICY obtained in comparative example 1, obtain epoxy resin and consolidate
Compound.Compounding ratio and plywood evaluation result are shown in table 4.
Comparative example 8
Similarly to Example 7 using the phosphorous epoxy resin and DICY obtained in comparative example 2, obtain epoxy resin and consolidate
Compound.Compounding ratio and plywood evaluation result are shown in table 4.
Comparative example 9
Similarly to Example 7 using the phosphorous epoxy resin and DICY obtained in comparative example 4, obtain epoxy resin and consolidate
Compound.Compounding ratio and plywood evaluation result are shown in table 4.
Comparative example 10
Similarly to Example 11 using the phosphorous epoxy resin and BRG-557 obtained in comparative example 2, asphalt mixtures modified by epoxy resin is obtained
Fat solidfied material.Compounding ratio and plywood evaluation result are shown in table 4.
Comparative example 11
Similarly to Example 11 using the phosphorous epoxy resin and BRG-557 obtained in comparative example 5, asphalt mixtures modified by epoxy resin is obtained
Fat solidfied material.Compounding ratio and plywood evaluation result are shown in table 4.
Comparative example 12
Similarly to Example 11 using the phosphorous epoxy resin and BRG-557 obtained in comparative example 6, asphalt mixtures modified by epoxy resin is obtained
Fat solidfied material.Compounding ratio and plywood evaluation result are shown in table 4.
As shown in the embodiment 1 to embodiment 6 of table 1, phosphorous epoxy resin of the invention is by making terminal epoxy groups and end
End phenolic hydroxyl group coexists, and example 1 to comparative example 6 compares compared with the prior art, and number-average molecular weight is low, and epoxy resin varnish glues
Spend low.Therefore, to the immersion good of glass cloth, workability is excellent.In addition, as shown in embodiment 4, it can also synthesize and compare
Shown in example 3 be difficult to synthesize in the prior art phosphorous epoxy resin of the polyfunctional epoxy resin as epoxy resin is used only,
Its molecular weight and varnish viscosity are compared with conventional phosphorous epoxy resin and in no way inferior.
As shown in the embodiment 7 to embodiment 14 of table 2, coordinate epoxy resin cure in the phosphorous epoxy resin of the present invention
Compared with agent carries out the epoxy resin cured product that forms of solidification when using conventional phosphorous epoxy resin, not only glass transition temperature
Degree and resistance to thermal reliability are high, and anti-flammability is excellent.
Industrial applicability
Viscosity during the formation epoxy resin varnish of the phosphorous epoxy resin of the present invention is than conventional phosphorous epoxy resin also
It is low, therefore to the immersion good of the base materials such as glass cloth, workability is excellent.
In addition, the present invention phosphorous epoxy resin solidfied material compared with conventional phosphorous epoxy resin, glass transition temperature
Degree is high, and anti-flammability and cementability are also excellent.
Claims (13)
1. a kind of phosphorous epoxy resin composition, it is characterised in that it contains phosphorous epoxy resin as essential component
Phosphorous epoxy resin class (c) and epoxy curing agent,
Wherein, phosphorous epoxy resin is by making epoxy resin (a) and with the epoxy reaction with epoxy resin (a)
Obtained from compounds (b) reaction of reactive functional groups,
Phosphorous phenolic compound shown in compounds (b) with reactive functional groups using following formulas (1) is as must be into
Point,
The epoxide equivalent of phosphorous epoxy resin is 60% to 95% scope of the theoretical epoxy equivalent weight tried to achieve by following formula 1,
Phosphorous epoxy resin of the phosphorous epoxy resin class (c) containing 70~100 weight %,
Chemical formula 1
In formula, A represents the three-level aryl that carbon number is 6 to 20, and n represents 0 or 1；In addition, in formula, R1And R2Represent carbon atom
Number is 1 to 6 alkyl, can be the same or different, ring-type can also be formed together with phosphorus atoms,
Formula 1
Formula 2
Formula 3
2. phosphorous epoxy resin composition according to claim 1, wherein, the epoxy resin (a) is to be selected from Bisphenol F
Type epoxy resin, phenol novolak type epoxy resin, trihydroxy benzene methylmethane type epoxy resin and bisnaphthol aralkyl type ring
At least one of oxygen tree fat epoxy resin.
3. phosphorous epoxy resin composition according to claim 1, wherein, the phosphorous epoxy resin be by relative to
The reactive functional of the equivalent of epoxy radicals 1 of the epoxy resin (a) and the compounds (b) with reactive functional groups
Obtained from the scope reaction of group's 0.10 equivalent to 0.94 equivalent.
4. phosphorous epoxy resin composition according to claim 1, it is by relative to the phosphorous epoxy resin class
(c) the equivalent of epoxy radicals 1 coordinates what the scope of the equivalent of functional group 0.1 to 1.3 equivalents of the epoxy curing agent formed.
5. a kind of phosphorous epoxy resin solidfied material, it is by making phosphorous epoxy resin according to any one of claims 1 to 4
Composition solidification forms.
6. a kind of phosphorous epoxy resin, it is characterised in that it is by making epoxy resin (a) and having and epoxy resin
(a) obtained from compounds (b) reaction of the reactive functional groups of epoxy reaction,
Wherein, the phosphorous phenolic compound shown in the compounds (b) using following formulas (1) with reactive functional groups is as must
Palpus composition,
It is by the equivalent of epoxy radicals 1 relative to epoxy resin (a) and the compounds (b) with reactive functional groups
Obtained from the equivalent of reactive functional groups 0.10 to the scope reaction of 0.30 equivalent,
The epoxide equivalent of phosphorous epoxy resin is 60% to 95% scope of the theoretical epoxy equivalent weight tried to achieve by following formula 1,
Chemical formula 1
In formula, A represents the three-level aryl that carbon number is 6 to 20, and n represents 0 or 1；In addition, in formula, R1And R2Represent carbon atom
Number is 1 to 6 alkyl, can be the same or different, ring-type can also be formed together with phosphorus atoms,
Formula 1
Formula 2
Formula 3
7. a kind of phosphorous epoxy resin, it is characterised in that it is by making epoxy resin (a) and having and epoxy resin
(a) obtained from compounds (b) reaction of the reactive functional groups of epoxy reaction,
Wherein, the phosphorous phenolic compound shown in the compounds (b) using following formulas (1) with reactive functional groups is as must
Palpus composition,
The epoxide equivalent of phosphorous epoxy resin is 69% to 76% scope of the theoretical epoxy equivalent weight tried to achieve by following formula 1,
Chemical formula 1
In formula, A represents the three-level aryl that carbon number is 6 to 20, and n represents 0 or 1；In addition, in formula, R1And R2Represent carbon atom
Number is 1 to 6 alkyl, can be the same or different, ring-type can also be formed together with phosphorus atoms,
Formula 1
Formula 2
Formula 3
8. a kind of phosphorous epoxy resin composition, it is to contain phosphorous epoxy resin described in claim 6 or 7 as must be into
The phosphorous epoxy resin class (c) divided coordinates what is formed with epoxy curing agent, wherein, relative to phosphorous epoxy resin class (c)
The equivalent of epoxy radicals 1, the functional group of epoxy curing agent is the scope of 0.1 equivalent to 1.3 equivalents.
9. a kind of phosphorous epoxy resin solidfied material, it is by solidifying the phosphorous epoxy resin composition described in claim 8
Form.
10. a kind of manufacture method of phosphorous epoxy resin, it is characterised in that it is by epoxy resin (a) and had and epoxy
The manufacture method for the phosphorous epoxy resin that the compounds (b) of the reactive functional groups of the epoxy reaction of resinae (a) obtain,
Wherein, the phosphorous phenolic compound shown in the compounds (b) using following formulas (1) with reactive functional groups is as must
Palpus composition,
The reactive official of the equivalent of epoxy radicals 1 and the compounds (b) with reactive functional groups relative to epoxy resin (a)
The scope reaction of 0.10 equivalent to 0.30 equivalent can be rolled into a ball,
The epoxide equivalent for making resulting phosphorous epoxy resin is the 60% to 95% of the theoretical epoxy equivalent weight tried to achieve by following formula 1
Scope,
Chemical formula 1
In formula, A represents the three-level aryl that carbon number is 6 to 20, and n represents 0 or 1；In addition, in formula, R1And R2Represent carbon atom
Number is 1 to 6 alkyl, can be the same or different, ring-type can also be formed together with phosphorus atoms,
Formula 1
Formula 2
Formula 3
11. a kind of manufacture method of phosphorous epoxy resin, it is characterised in that it is by epoxy resin (a) and had and epoxy
The manufacture method for the phosphorous epoxy resin that the compounds (b) of the reactive functional groups of the epoxy reaction of resinae (a) obtain,
Wherein, the phosphorous phenolic compound shown in the compounds (b) using following formulas (1) with reactive functional groups is as must
Palpus composition,
The epoxide equivalent for making resulting phosphorous epoxy resin is the 69% to 76% of the theoretical epoxy equivalent weight tried to achieve by following formula 1
Scope,
Chemical formula 1
In formula, A represents the three-level aryl that carbon number is 6 to 20, and n represents 0 or 1；In addition, in formula, R1And R2Represent carbon atom
Number is 1 to 6 alkyl, can be the same or different, ring-type can also be formed together with phosphorus atoms,
Formula 1
Formula 2
Formula 3
12. a kind of phosphorous epoxy resin composition, it is characterised in that it contains phosphorous epoxy resin as essential component
Phosphorous epoxy resin class (c) and epoxy curing agent,
Wherein, the phosphorous epoxy resin is obtained by the manufacture method described in claim 10 or 11,
The phosphorous epoxy resin containing 70~100 weight % in the phosphorous epoxy resin class (c),
It is by coordinating the epoxy curing agent relative to the equivalent of epoxy radicals 1 of the phosphorous epoxy resin class (c)
What the scope of the equivalent of functional group 0.1 to 1.3 equivalents formed.
13. a kind of phosphorous epoxy resin solidfied material, it is by consolidating the phosphorous epoxy resin composition described in claim 12
Change what is formed.
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| JP2011036034A JP5633931B2 (en) | 2011-02-22 | 2011-02-22 | Phosphorus-containing epoxy resin, resin composition, and cured product |
| JP2011-036034 | 2011-02-22 | ||
| CN2012100427525A CN102649837A (en) | 2011-02-22 | 2012-02-22 | Phosphorus epoxy resin and composition and cured material having the same |
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| JP5917227B2 (en) * | 2012-03-28 | 2016-05-11 | 新日鉄住金化学株式会社 | Method for producing phosphorus-containing epoxy resin |
| JP2014108976A (en) * | 2012-11-30 | 2014-06-12 | Nippon Steel & Sumikin Chemical Co Ltd | Epoxy resin composition and cured article |
| TWI631173B (en) * | 2012-10-11 | 2018-08-01 | 新日鐵住金化學股份有限公司 | Epoxy resin composition and hardened material |
| JP6113454B2 (en) * | 2012-10-11 | 2017-04-12 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product |
| CN103289326B (en) * | 2013-06-28 | 2015-10-07 | 山东科技大学 | For the halogen-free flame retardant epoxy resin composition of potting compound |
| JP6193689B2 (en) * | 2013-09-09 | 2017-09-06 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin and composition, cured product |
| WO2015046626A1 (en) | 2013-09-30 | 2015-04-02 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin composition and cured article |
| CN103694638A (en) * | 2013-12-14 | 2014-04-02 | 大连理工大学 | Halogen-free epoxy resin applicable to liquid oxygen environment and preparation method thereof |
| CN110520433B (en) | 2017-03-29 | 2023-12-05 | 日铁化学材料株式会社 | Phosphorus-containing phenol compound, phosphorus-containing epoxy resin, curable resin composition or epoxy resin composition, and cured product thereof |
| WO2022040633A1 (en) | 2020-08-21 | 2022-02-24 | The University Of Southern Mississippi | Phenylphosphine oxide and oxygen stable epoxy polymers and methods of synthesis |
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|---|---|---|---|---|
| JP2000309624A (en) * | 1999-02-23 | 2000-11-07 | Dainippon Ink & Chem Inc | Flame-retardant epoxy resin composition and its production |
| JP2006342217A (en) * | 2005-06-07 | 2006-12-21 | Sanko Kk | Method for producing phosphorus-containing flame-retardant bisphenol-type epoxy resin, the resultant phosphorus-containing flame-retardant bisphenol-type epoxy resin, and phosphorus-containing flame-retardant bisphenol-type epoxy resin composition |
| CN1989166A (en) * | 2004-11-30 | 2007-06-27 | 松下电工株式会社 | Epoxy resin composition for prepreg, and multilayer printed wiring board |
| JP2010189466A (en) * | 2009-02-16 | 2010-09-02 | Nippon Steel Chem Co Ltd | Fire-resistant phosphorus-containing epoxy resin composition and hardened product obtained thereby |
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| JP3092009B2 (en) * | 1990-05-01 | 2000-09-25 | 東都化成株式会社 | Flame retardant and thermosetting flame-retardant resin composition containing the flame retardant |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000309624A (en) * | 1999-02-23 | 2000-11-07 | Dainippon Ink & Chem Inc | Flame-retardant epoxy resin composition and its production |
| CN1989166A (en) * | 2004-11-30 | 2007-06-27 | 松下电工株式会社 | Epoxy resin composition for prepreg, and multilayer printed wiring board |
| JP2006342217A (en) * | 2005-06-07 | 2006-12-21 | Sanko Kk | Method for producing phosphorus-containing flame-retardant bisphenol-type epoxy resin, the resultant phosphorus-containing flame-retardant bisphenol-type epoxy resin, and phosphorus-containing flame-retardant bisphenol-type epoxy resin composition |
| JP2010189466A (en) * | 2009-02-16 | 2010-09-02 | Nippon Steel Chem Co Ltd | Fire-resistant phosphorus-containing epoxy resin composition and hardened product obtained thereby |
Also Published As
| Publication number | Publication date |
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| TWI571477B (en) | 2017-02-21 |
| TW201241033A (en) | 2012-10-16 |
| JP2012172079A (en) | 2012-09-10 |
| CN107446120B (en) | 2020-01-21 |
| CN102649837A (en) | 2012-08-29 |
| JP5633931B2 (en) | 2014-12-03 |
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