CN102741314A - Method for producing a phosphorus-containing epoxy resin, epoxy resin composition, and cured product thereof - Google Patents
Method for producing a phosphorus-containing epoxy resin, epoxy resin composition, and cured product thereof Download PDFInfo
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- CN102741314A CN102741314A CN2011800087160A CN201180008716A CN102741314A CN 102741314 A CN102741314 A CN 102741314A CN 2011800087160 A CN2011800087160 A CN 2011800087160A CN 201180008716 A CN201180008716 A CN 201180008716A CN 102741314 A CN102741314 A CN 102741314A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
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Abstract
Provided is a method for producing a phosphorus-containing epoxy resin which produces a cured product that has excellent low viscosity properties and that is flame resistant.Also provided are an epoxy resin composition comprising the phosphorus-containing epoxy resin obtained by said production method, and a cured product of the epoxy resin composition.The production method comprises reacting an epoxy resin (A),which is formed from at least one of an epoxy resin (a1) represented by general formula (1),an epoxy resin (a2) represented by general formula (3) and an epoxy resin (a3) represented by general formula (4),with an organophosphorus compound (B),which comprises an organophosphorus compound (b1) represented by general formula (5) and/or an organophosphorus compound (b2) represented by general formula (6),to produce a phosphorus-containing epoxy resin having an epoxy equivalent of 200 to 600 g/eq and a phosphorus content of 1 to 6 wt%. The hydroxyl group concentration of the epoxy resin (A) is 200 mEq/100 g or less,the total chlorine content is 0.4 wt% or less,and the a-diol content is 10 meg/100 g or less. The weight ratio range of the organophosphorus compound (b1) / the organophosphorus compound (b2) of the organophosphorus compound (B) is 50/50 to 100/0.
Description
Technical field
The composition epoxy resin and the cured article thereof that the present invention relates to neo-epoxy resin and use this epoxy resin; The excellent cured article that said epoxy resin has flame retardant resistance when can prepare LV property excellence; The sealing, the coating material that can be used as with the semiconductor element electrical/electronic part etc. that is representative; Laminating material, the cured article of matrix material etc., the present invention is suitable for the insulating material in electric and electronic fields such as printing distributing board, encapsulating semiconductor etc.
Background technology
Epoxy resin is used to purposes widely in industry, but its desired performance is increasingly high in recent years.For example; There is semiconductor-encapsulating material in representative field with epoxy resin being the resin combination of principal constituent; But in recent years along with the raising of semiconductor element integrated level; When package size turned to big areaization, thinning, assembling mode also got into the transfer to surface-assembledization, hoped the more excellent material of exploitation welding thermotolerance.
In addition; Recently because technological trend highly integrated, High Density Packagingization; The assembling that replaces in the past relying on the transfer molding (ト ラ Application ス フ ァ ー shapings) that utilizes mould to be carried out mixes integrated IC, sheet support plate, band and carries and encapsulate, moulds the pin grid array, moulds that ball grid array etc. does not use mould and the mode that adopts liquid material to seal, assemble increases gradually.But liquid material is compared the shortcoming that exists safety low with the solid-state material that is used for transfer molding usually.Its reason is that there is the limit on the viscosity in liquid material, and there are restriction in employed resin, solidifying agent, filling agent etc.In addition, in the face of halogen-free flame-retardantization in recent years, when using the halogen fire retardant, even also improve in the requirement of not thinking fire-retardantization under these necessary purposes.
In addition, in the also progressively raising of requirement of field of compound material halogenization, but owing to need when guaranteeing flame retardant resistance, realize lowering viscousity, so do not obtain gratifying product as yet.
For overcoming these problems, hope epoxy resin and solidifying agent fire-retardantization in lowering viscousity, low moisture absorptionization, high heat-resistingization as principal constituent.As low viscosity epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin etc. is widely known by the people usually, but not only not enough aspect LV property, does not also have flame retardant resistance.As the excellent epoxy resin of LV property, disclose in the patent documentation 1 have the oxo methene chain epoxy resin, but thermotolerance, wet fastness still have the leeway of improvement, do not give consideration fully for flame retardant resistance.Disclose epoxy resin in the patent documentation 2, but do not give consideration fully for flame retardant resistance with dicyclohexyl ring.In patent documentation 3, disclose phosphorous epoxy resin, but belong to the phosphorous epoxy resin that makes by 2 functional group epoxy resins with aromatics skeleton and phosphorous phenol resins, existing problems aspect lowering viscousity with flame retardant resistance.In patent documentation 4; In phosphorous epoxy resin composition, flame retardant resistance is had mentioned; Record aliphatic epoxy resin and also can be used as the content of the raw material of phosphorous epoxy resin; But have nothing to do in the record of the effect of using aliphatic epoxy resin, also have nothing to do in addition, do not give consideration fully for viscosity in record as the characteristic of phosphorous epoxy resin.In patent documentation 5, disclose the compsn that contains phosphorous monocycle epoxy resins, but must share aliphatic series type thinner, can't use separately.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 4-359009 communique
Patent documentation 2: TOHKEMY 2006-188606 communique
Patent documentation 3: TOHKEMY 2001-288247 communique
Patent documentation 4: TOHKEMY 2002-249540 communique
Patent documentation 5: TOHKEMY 2001-106766 communique
Patent documentation 6: japanese kokai publication sho 61-268691 communique.
Summary of the invention
Invent problem to be solved
Be difficult to obtain to have the liquid-state epoxy resin of flame retardant resistance as stated.Therefore, the object of the present invention is to provide preparation method, the composition epoxy resin that contains the phosphorous epoxy resin that makes through this preparation method and this cured article of the phosphorous epoxy resin of the cured article that can prepare LV property excellence and have flame retardant resistance.
Solve the means of problem
The inventor furthers investigate for solving above-mentioned problem repeatedly; The result finds: be used to prepare the requirement that does not significantly damage the cured article rerum natura and have the necessary low viscosity epoxy resin of phosphorous epoxy resin of effective flame retardant resistance; Accomplish the preparation method of the phosphorous epoxy resin of the application's invention, solving the required means of above-mentioned problem is the following means that the claim scope is put down in writing.
(1) preparation method of phosphorous epoxy resin; It is characterized in that; Make by with the epoxy resin (a1) of general formula (1) expression, with at least a epoxy resin of forming (A) in the epoxy resin (a3) of the epoxy resin (a2) of general formula (3) expression or general formula (4) expression with by with the organo phosphorous compounds (b1) of general formula (5) expression and organo phosphorous compounds (B) reaction that constitutes with the organo phosphorous compounds (b2) of general formula (6) expression; Thereby the preparation epoxy equivalent (weight) is 200 ~ 600g/eq, phosphorus containing ratio is in the method for phosphorous epoxy resin of 1 ~ 6% weight; The hydroxyl concentration of epoxy resin (A) is below the 200meq/100g; Total chlorine amount is below 0.4% weight, and the α glycol content is below the 10meg/100g, and the weight ratio scope of organo phosphorous compounds (b1)/organo phosphorous compounds (b2) is 50/50 ~ 100/0 in the organo phosphorous compounds (B).
R in the formula
1Be the alkyl of carbonatoms 6 ~ 31, said alkyl has 1 aromatic ring at least, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, any in G expression (2) or the hydrogen.
R in the formula
2Be the aliphatic hydrocarbyl of carbonatoms 6 ~ 17, said aliphatic hydrocarbyl can be monocycle or heterocycle, has 1 cyclohexane ring at least, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, any in G expression (2) or the hydrogen.
R in the formula
3Be separately respectively the aliphatic hydrocarbyl that can contain the carbonatoms 1 ~ 4 of Sauerstoffatom, nitrogen-atoms, sulphur atom, R
4Expression-R
3-OG ,-R
3In-H or the hydrogen any, any in G expression (2) or the hydrogen, k representes 0 or 1 integer.
R in the formula
5, R
6Expression hydrogen or alkyl separately can be similar and different, can be straight chain shape, branched, ring-type.In addition, R
5With R
6But bonding forms ring texture.N representes 0 or 1 integer.Ar representes any in benzene, biphenyl, naphthalene, anthracene, phenanthrene and the hydrocarbon substituent thereof.
R in the formula
7, R
8Expression hydrogen or alkyl separately can be similar and different, can be straight chain shape, branched, ring-type.R in addition
7With R
8But bonding forms ring texture.M representes 0 or 1 integer.
(2) composition epoxy resin is characterized in that, contains phosphorous epoxy resin that the preparation method through phosphorous epoxy resin of record in (1) makes and solidifying agent as must composition.
(3) cured article, said cured article obtains through the composition epoxy resin curing of record in (2).
Epoxy resin of the present invention (A) is necessary for the epoxy resin (a1) of general formula (1) expression, with the epoxy resin (a2) of general formula (3) expression or the epoxy resin of representing with general formula (4) (a3).Even use epoxy resin in addition also can't obtain to have phosphorous epoxy resin as the LV and the flame retardant resistance of the object of the invention.
Usually, when making the reaction of epoxy resin and phenol resins class synthesize new epoxy resin, the inevitable remaining epoxy resin that has as raw material in the epoxy resin that makes.Therefore, in the phosphorous epoxy resin that makes, also need be considered as the influence of the epoxy resin (A) of raw material.
Unreacted remaining amount of hydroxyl groups has the trend that increases because of the reactivity difference makes to be derived from the glycidyl ether of alcohol hydroxyl group.Remaining hydroxyl in the raw material epoxy resin (A) stays out of with the reaction of phosphorus compound directly remaining; Make the end group purity drop of phosphorous epoxy resin; So the increase of the residual hydroxyl in the raw material epoxy resin (A) directly makes the water absorbability of phosphorous epoxy resin composition increase; For anhydride curing agent or microcapsule-type potential curing agent, become the reason that storage stability reduces.In addition, owing to the essential factor of cured article rerum naturas such as intensity that becomes cured article or thermotolerance reduction deterioration, so need make the remaining hydroxyl and high-purityization of raw material epoxy resin (A).Therefore, the remaining hydroxyl concentration of epoxy resin (A) is preferably below the 200meq/100g, more preferably below the 100meq/100g, further is preferably below the 50meq/100g.
In addition, for reducing remaining hydroxyl concentration, if reactive through raisings such as interpolation catalyzer, then parallel side reaction increases, and causes the total chlorine amount high densityization that is contained.Total chlorine amount in the raw material epoxy resin (A) significantly reduces owing to directly remaining in the electricity safety that makes cured article in the phosphorous epoxy resin, so for total chlorine amount, also need high purityization.The total chlorine amount of raw material epoxy resin (A) is preferably below 0.4% weight, more preferably below 0.2% weight, further is preferably below 0.1% weight.In coming from the glycidyl ether of alcohol hydroxyl group, because total chlorine amount is that the above situation of 1% weight is maximum, so need through highly purified reaction and distillation procedure or extracting operation reduction total chlorine amount.These methods do not have special stipulation, can use the whole bag of tricks of designing at present.
In addition; α glycol content in the raw material epoxy resin (A) is also the same with remaining hydroxyl concentration stay out of directly remaining with the reaction of phosphorus compound; Make the end group purity drop of phosphorous epoxy resin; So the increase of the α glycol content in the raw material epoxy resin (A) directly makes the water absorbability of phosphorous epoxy resin composition increase, and becomes the reason that storage stability reduces for anhydride curing agent or microcapsule-type potential curing agent.In addition, owing to cured article rerum naturas such as intensity that becomes cured article or thermotolerance reduction worsen, so the α glycol content of raw material epoxy resin (A) is reduced.Therefore, the α glycol content of epoxy resin (A) is preferably below the 10meq/100g, more preferably below the 5meq/100g, further is preferably below the 3meq/100g.
What need explanation is; Under the situation of the epoxy resin of representing with general formula (4) (a3); If remaining hydroxyl concentration or α glycol content are high; Then except that above-mentioned reason, do not increase owing to do not belong to 2 functional group epoxy resins that do not have cyclohexane ring of the above epoxy resin of 3 functional groups, not preferred so cause the reduction of flame retardant resistance.
At least have 1 aromatic ring with the epoxy resin (a1) with general formula (1) expression of organo phosphorous compounds reaction, and-O-CH
2-R
1-CH
2-O-structure is essential.Aromatic ring helps the raising of the flame retardant resistance of phosphorous epoxy resin ,-O-CH
2-R
1-CH
2-O-structure is effective to the lowering viscousity of phosphorous epoxy resin.When not have-O-CH
2-R
1-CH
2The aromatic species epoxy resin of-O-structure is during as raw material, because lowering viscousity is not enough, so need a large amount of aliphatic based epoxy resin isoreactivity thinners that use for the lowering viscousity of composition epoxy resin, can't guarantee flame retardant resistance.In addition, to guarantee flame retardant resistance, then the viscosity of composition epoxy resin significantly raises as if the usage quantity that reduces aliphatic based epoxy resin, thus unfavorable to lowering viscousity, can't obtain LV phosphorous epoxy resin composition as target.That is, this 2 functional group epoxy resin (a1) is the glycidyl ether thing of 2 functional group's primary alconols of the carbonatoms 8 ~ 33 that contains 1 aromatic ring in the skeleton at least.
Will be with R in the formula of 2 functional group epoxy resins (a1) of general formula (1) expression
1Specific examples be illustrated in formula (7) group.In addition, R
1Can be the isomer of formula (7) group, also can have substituting group.In addition, with regard to R
1, they can be single or more than 2 kinds.
J independently representes 0 or 1 integer separately in the formula.
J independently representes 0 or 1 integer separately in the formula.
In 2 functional group epoxy resins (a1), preferably with the glycidyl ether thing of the terephthalyl alcohol of general formula (8) expression or with the biphenyl of general formula (9) expression glycidyl ether thing to dimethanol with general formula (1) expression.
Must contain 1 cyclohexane ring at least with 2 functional group epoxy resins (a2) with general formula (3) expression of organo phosphorous compounds reaction.Cyclohexane ring helps the raising of the flame retardant resistance of phosphorous epoxy resin, and the aliphatic based epoxy resin that does not have cyclohexane ring can't be guaranteed flame retardant resistance.That is, this 2 functional group epoxy resin (a2) is the glycidyl ether thing of the 2 functional groups aliphatic series type primary alconol of the carbonatoms 6 ~ 17 that contains 1 cyclohexane ring in the skeleton at least.
Will be with R in the formula of 2 functional group epoxy resins (a2) of general formula (3) expression
2Specific examples be illustrated in 10 groups of the formulas.In addition, R
2Can be the isomer of 10 groups of formulas, also can have substituting group.In addition, with regard to R
2, they can be single or more than 2 kinds.
In 2 functional group epoxy resins (a2), preferably with the glycidyl ether thing of the cyclohexanedimethanol of general formula (11) expression or with the glycidyl ether thing of the Hydrogenated Bisphenol A 99 of general formula (12) expression with general formula (3) expression.
The polyfunctional epoxy resin (a3) with general formula (4) expression that reacts with organo phosphorous compounds is 3 functional group epoxy resins or 4 functional group epoxy resins with aliphatic chain of carbonatoms 1 ~ 4.In the aliphatic epoxy resin that does not contain cyclohexane ring, can't guarantee flame retardant resistance with the aliphatic based epoxy resin beyond the polyfunctional epoxy resin of general formula (4) expression.
In polyfunctional epoxy resin (a3), preferably with the glycidyl ether thing of the TriMethylolPropane(TMP) of general formula (13) expression with general formula 4 expression.
In addition, the organo phosphorous compounds (B) with epoxy resin (A) reaction is with the organo phosphorous compounds (b1) of general formula (5) expression and the organo phosphorous compounds of representing with general formula (6) (b2).
Organo phosphorous compounds (b1) with general formula (5) expression is the organo phosphorous compounds with 2 active hydrogens, the R in the formula
5, R
6Expression hydrogen or alkyl separately can be similar and different, can be straight chain shape, branched, ring-type, in addition R
5With R
6Also but bonding forms ring texture.As R
5, R
6Specific examples, can enumerate out methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, 1-methylbutyl, 1-methyl amyl, octyl group, nonyl, dodecyl, undecyl, dodecyl, benzyl, phenyl, tolyl, xylyl etc.In addition, as R
5With R
6Bonding forms the examples of groups of ring texture, for example can enumerate out inferior cyclobutyl, cyclopentylidene, cyclohexylidene, inferior suberyl, inferior ring octyl group, inferior ring decyl, inferior norcamphyl, biphenylene etc.Ar is an arylidene, as the instance of concrete example, can enumerate out phenylene, methylene phenyl, xylylene, naphthylidene, biphenylene etc.In addition, the number of n is 0 or 1.
These organo phosphorous compoundss (b1) are prone to obtain (patent documentation 6) through the reaction of the organo phosphorous compounds (b2) of general formula 6 and monocycle or polynucleation quinone compound.As the preferred organo phosphorous compounds that uses among the present invention; Can enumerate out with the P contained compound (following brief note is DOPO-HQ) of general formula (15) expression or the organo phosphorous compounds of representing with general formula (16) (following brief note is DOPO-NQ); Said P contained compound with general formula (15) expression serves as as 9 of the organo phosphorous compounds of representing with general formula (14); The 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (9; 10-ジ ヒ De ロ-9-オ キ サ-10-Off ォ ス Off ォ Off ェ Na Application ト レ Application-10-オ キ サ イ De) (following brief note is DOPO) and 1; The addition reaction thing of 4-benzoquinones, said organo phosphorous compounds with general formula (16) expression is DOPO and 1, the addition reaction thing of 4-naphthoquinones.
DOPO can be used as trade(brand)name " HCA " (Sanko Co., Ltd.'s system) and obtains, and DOPO-HQ can be used as trade(brand)name " HCA-HQ " (Sanko Co., Ltd.'s system) and obtains.
Organo phosphorous compounds (b2) with general formula (6) expression is the organo phosphorous compounds with 1 active hydrogen, the R in the formula
7, R
8Expression hydrogen or alkyl separately can be similar and different, can be straight chain shape, branched, ring-type, in addition R
7With R
8Also but bonding forms ring texture.As R
7, R
8Specific examples, can enumerate out methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, 1-methylbutyl, 1-methyl amyl, octyl group, nonyl, dodecyl, undecyl, dodecyl, benzyl, phenyl, tolyl, xylyl etc.In addition, as R
7With R
8Bonding forms the examples of groups of ring texture, for example can enumerate out inferior cyclobutyl, cyclopentylidene, cyclohexylidene, inferior suberyl, inferior ring octyl group, inferior ring decyl, inferior norcamphyl, biphenylene etc.In addition, the number of m is 0 or 1.The DOPO that wherein preferably representes with general formula (14).
For obtaining in the organo phosphorous compounds that phosphorous epoxy resin of the present invention uses; (b1)/(b2) weight ratio with general formula (5) organo phosphorous compounds of representing (b1) and the organo phosphorous compounds of representing with general formula 6 (b2) is 50/50 ~ 100/0; Be preferably 65/35 ~ 100/0; More preferably 80/20 ~ 100/0, further be preferably 90/10 ~ 100/0.If not enough (b1)/(b2) weight ratio=0/100 ~ 50/50; Though then raising or the viscosity to flame retardant resistance reduces effectively owing to be prone to adjustment phosphorus containing ratio; But mostly occur with the 1 functional group's organo phosphorous compounds (b2) of general formula (6) expression and the reaction of epoxy group(ing); The following epoxy resin of 1 functional group generates in a large number, and whole epoxy radix reduces, so reactivity significantly reduces.In addition, cause that the cementability of the cured article of acquisition reduces, thermotolerance reduces or wet fastness reduces, the electric insulation safety significantly reduces.If (b1)/(b2) scope of weight ratio=50/50 ~ 100/0 then can be guaranteed enough reactivities, so do not exist the rerum natura of cured article to reduce.If how in order to the organo phosphorous compounds (b1) of general formula (5) expression, then molecular weight increases, and can significantly improve cementability, if, then make to be prone to adjustment phosphorus containing ratio, so need be according to purpose characteristic adjustment usage quantity how in order to the organo phosphorous compounds (b2) of general formula (6) expression.In the scope of (b1)/(b2) weight ratio=50/50 ~ 100/0, when further requiring flame retardant resistance,, when further requiring cementability, need only the usage rate that increases organo phosphorous compounds (b1) as long as increase the usage rate of organo phosphorous compounds (b2).
Organo phosphorous compounds can mix uses with the organo phosphorous compounds (b1) of general formula (5) expression with organo phosphorous compounds (b2) with general formula 6 expressions with synthetic in advance, also can with the reaction of epoxy resin (A) before organo phosphorous compounds (b2) and the quinones represented with general formula 6 are reacted.At this moment, with respect to 1 mole the organo phosphorous compounds (b2) with general formula 6 expressions, quinones preferably reacts for 1 mole with less than.If the compound (b2) with general formula (6) expression with respect to 1 mole uses the quinones more than 1 mole, then remaining in the phosphorous epoxy resin that obtains have a raw material quinones, and the wet fastness of cured article worsens, so not preferred.
The epoxy resin that uses among the present invention (A) can known method carry out with the reaction of organic phosphorus compound (B).As temperature of reaction, can under agitation carry out in 100 ℃ ~ 200 ℃, preferred 120 ℃ ~ 180 ℃.Reaction times can be confirmed through the mensuration of carrying out epoxy equivalent (weight).With regard to mensuration, can measure according to the method for JIS K-7236.Reaction through epoxy resin (A) and organo phosphorous compounds makes epoxy equivalent (weight) increase, can through with theoretical epoxy equivalent (weight) relatively come to confirm reaction end.
In addition, when speed of response is slow, can use catalyzer to seek the improvement of throughput as required.Particularly, can use tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethyl ammonium chloride; Triphenyl phosphine, three (2; The 6-Dimethoxyphenyl) phosphine class such as phosphine, microcosmic salt classes such as Ethyltriphenylphosphonium brimide, various catalyzer such as imidazoles such as glyoxal ethyline, 2-ethyl-4-methylimidazole.These catalyzer can use separately or with share more than 2 kinds.
The epoxy equivalent (weight) of the phosphorous epoxy resin that obtains through preparation method of the present invention is preferably 200g/eq ~ 600g/eq.When epoxy equivalent (weight) deficiency 200g/eq, cementability is poor, if surpass 600g/eq, then viscosity increases, and the thermotolerance of the cured article of acquisition receives significantly infringement.Therefore, epoxy equivalent (weight) is preferably 200g/eq ~ 600g/eq, and more preferably 230g/eq ~ 550g/eq further is preferably 250g/eq ~ 500g/eq.
The phosphorus containing ratio of the phosphorous epoxy resin that obtains through preparation method of the present invention is preferably 1% weight ~ 6% weight.High from the preferred phosphorus containing ratio of the viewpoint of flame retardant resistance, but, cause that the viscosity of phosphorous epoxy resin increases or the epoxy equivalent (weight) increase along with the phosphorus containing ratio raises, the thermotolerance of the cured article of acquisition receives significantly infringement.Therefore, the phosphorus containing ratio is preferably 1% weight ~ 6% weight, and more preferably 1.5% weight ~ 4% weight further is preferably 2% weight ~ 3% weight.
The total chlorine amount of the phosphorous epoxy resin that obtains through preparation method of the present invention is relevant with the reduction of the electricity safety of the cured article of acquisition, if increase, then the electricity safety of cured article reduces, if reduce, and then electricity safety raising.Consider that from the electricity safety of permissible cured article total chlorine amount is preferably below 0.2% weight, more preferably, further be preferably below 0.05% weight with below 0.09% weight that general sealing material use epoxy resin equates.
The melt viscosity of phosphorous epoxy resin under 100 ℃ that obtains through preparation method of the present invention is preferably 1, below the 000mPas, more preferably below the 600mPas, further is preferably below the 300mPas.If the melt viscosity under 100 ℃ surpasses 1,000mPas, even then use the relatively low solidifying agent of viscosity, the viscosity of composition epoxy resin still raises, and makes the actually operating difficulty to be difficult to obtain normal forming composition.
In the scope of not damaging characteristic, but in the present composition also blending the epoxy resin beyond the phosphorous epoxy resin that obtains through preparation method of the present invention is arranged.
Though need not the phosphorus containing ratio with respect to whole epoxy resin compositions in the composition epoxy resin of the present invention is carried out special stipulation, high from the preferred phosphorus containing ratio of the viewpoint of flame retardant resistance, low from the preferred phosphorus containing ratio of the viewpoint of lowering viscousity.Therefore, for satisfying both, be preferably 0.5% weight ~ 5% weight, more preferably 1% weight ~ 4% weight further is preferably 2% weight ~ 3% weight.
As solidifying agent of the present invention; Can use with various polyphenol resenes or the anhydrides of resol as representative; With Dyhard RU 100 or diethylammonium diaminodiphenyl-methane is the amine of representative; Hydrazides class, the hardener for epoxy resin that acid polyester etc. are commonly used, these solidifying agent can only be used a kind or use more than 2 kinds.
In addition, composition epoxy resin of the present invention can use curing catalyst as required.As curing catalyst; Can enumerate out phosphine class, quaternary phosphonium salt, tertiary amines, quaternary ammonium salt, imidazolium compounds class, boron trifluoride complex class, 3-(3; 4-dichloro phenylbenzene)-1,1-dimethyl urea, 3-(4-chloro-phenyl-)-1,1-dimethyl urea, 3-phenyl-1; 1-dimethyl urea etc., but be not limited thereto.
These curing catalysts depend on the epoxy resin that is share, employed epoxy curing agent kind, forming method, solidification value, require characteristic; Epoxy resin with respect to 100 parts; Be preferably the scope of 0.01 ~ 20 weight part, further preferred 0.1 ~ 10 weight part.
Composition epoxy resin of the present invention is blending inorganic filler, organic filler as required.As the instance of filling agent, can enumerate out fused silica, crystalline silica, aluminum oxide, silicon nitride, white lake, talcum powder, mica, lime carbonate, Calucium Silicate powder, calcium hydroxide, magnesiumcarbonate, barium carbonate, permanent white, SP 1, carbon, thomel, spun glass, sapphire whisker, aluminum silicate fiber, silicon carbide fiber, trevira, cellulosic fibre, aramid fiber etc.These filling agents are preferably 1 ~ 95% weight in the composition epoxy resin.
Composition epoxy resin of the present invention can be further various additives such as blending silane coupling agent, inhibitor, releasing agent, skimmer, emulsifying agent, thixotropic agent, smooth agent, fire retardant, pigment as required.These additives are preferably the scope of 0.01 ~ 20% weight in the composition epoxy resin total amount.
Composition epoxy resin of the present invention can the basis method identical with known composition epoxy resin carry out moulding, curing, processes cured article.Forming method, curing can adopt the method identical with known composition epoxy resin, do not need composition epoxy resin inherent method of the present invention.
Forms such as epoxy resin cured product of the present invention can be made into and films, adhesive linkage, forming composition, laminate, film.
The effect of invention
Forming composition to using composition epoxy resin of the present invention to obtain is estimated, and the result compares with existing low viscosity resin compsn, can obtain to have flame retardant resistance and have the cured article than low water absorption.Can know preparation that this composition epoxy resin and cured article thereof can be used as the copper clad laminate that uses in the circuit substrate with the sealing material that uses in resin combination or the electronic component, formed material, notes type material, caking agent, mould material, electric insulation coating with material etc.
Embodiment
The synthetic example of following basis, embodiment and comparative example specify the present invention, but technical scope of the present invention is not limited in embodiment.What need explanation is, as long as no specified otherwise, the blending umber of each composition in embodiment and the comparative example is all represented weight part.
In addition, use following analytical procedure in the present invention.
Epoxy equivalent (weight): the method for putting down in writing among the JIS K-7236.Promptly; Sample is dissolved in the chloroform of 10mL; Add the aceticanhydride of 20mL, the 20% tetraethylammonium bromide acetum of 10mL respectively; Use the potential difference titration apparatus to carry out titration, according to concentration and the addition and the titer mensuration epoxy equivalent (weight) that epoxy resin contained of all ingredients with 0.1mol/L perchloric acid acetate standard liquid.
Perchloro-amount: the method for putting down in writing among the JIS K-7243-3.That is, sample is dissolved in the diethylene glycol monobutyl ether of 25mL, add 25mL 1mol/L Pottasium Hydroxide 1, the 2-propylene glycol solution makes it down to react refluxing in heating on the hot plate 10 minutes.To be cooled to room temperature, the aceticanhydride of adding 50mL uses the potential difference titration apparatus to carry out titration with the 0.01mol/L silver nitrate solution, according to concentration and the additive and the titer mensuration perchloro-amount that epoxy resin contained of all ingredients.
Viscosity: the method for putting down in writing among the JIS K-7233.That is, in the 500mL cylinder tank, take by weighing the resin of 400g, in 25 ± 0.2 ℃ Water Tank with Temp.-controlled, place and kept constant temperature in 5 hours, the rotor of rotational viscosimeter impregnated in the resin measure.
Softening temperature: the method for putting down in writing among the JIS K-7234.That is, sample is filled in the ring of regulation according to ring and ball method, maintenance level in glycerol bath places sample central authorities with the ball of regulation, with the 5 ℃/min mensuration that heats up.
Hydroxyl concentration:, add the above phenylcarbimide of equivalent and as the dibutyl toxilic acid tin of catalyzer, after hydroxyl and isocyanic ester are fully reacted with respect to the amount of hydroxyl groups that epoxy resin contained; Equivalent with respect to employed phenylcarbimide; Be added on the dibutylamine on this amount, consume remaining phenylcarbimide, carry out titration with perchloric acid at last; According to concentration and the addition and the titer of all ingredients, measure the hydroxyl concentration that epoxy resin contained.
The phosphorus containing ratio: in sample, add sulfuric acid, hydrochloric acid, perchloric acid, the heating carry out wet ashing, with all phosphorus atom by ortho-phosphoric acid.In sulfuric acid solution, make the reaction of metavanadate and molybdate; Measure the absorbancy of molybdic acid phosphorus vanadium complexes under 420nm that generates; Represent the phosphorus atom content obtained according to the typical curve of making in advance with % weight, measure the phosphorus containing ratio that epoxy resin contained.
α glycol content: the method for putting down in writing among the JIS K-7146.
That is, after in sample, adding dissolved in chloroform, add orthoperiodic acid (オ Le ト crosses the plain acid of ヨ ウ) solution, make it to react 2 hours.Then, add liquor kalii iodide, the iodine that produces is carried out titration with Sulfothiorine, according to concentration and the addition and the titer mensuration α glycol content that epoxy resin contained of all ingredients.
Dissolve viscosity: use cone and plate viscometer (East Asia Industrial Co., Ltd system, MOEDL CV-1S), rotor uses 5 pool awls (Φ: 24mm, θ: 0.5 °), under 100 ℃ mensuration temperature, measures.
Flame retardant resistance: according to UL (Underwriters Laboratories Inc.) specification; The UL94 vertical test method is measured, according to judge (lean on more back flame retardant resistance poor more) as 4 levels such as the V-0 of the criterion of this specification, V-1, V-2, NG (no flame retardant resistance).
Cementability: the method that is as the criterion with JIS C-6481 5.7.That is, between 1 prepreg and all the other 3 at right angles direction peel off mensuration with the speed of 50mm/min.
Rate of moisture absorption: the method that is as the criterion with JIS C-6481 5.13.Promptly; Use is cut into the test film of 50mm * 50mm; Be determined in 50 ℃ the baking oven after dry 24 hours dry weight, then be determined at the weight of keeping after 72 hours in the treatment trough that is adjusted to 85 ℃/85%RH, measure rate of moisture absorption according to increasing amount with respect to dry weight.
Thermotolerance: the method that is as the criterion with IPC-TM-650,2.4.24.1.That is, utilizing the mensuration of the separation time of TMA device, in the TMA device, remain on 260 ℃ steady temperature, is more than 10 minutes the time when the time that produces transposition to test film cracking, is judged to be zero, when less than in the time of 10 minutes, be judged to be *.What need explanation is that the TMA device uses SII NanoTechnology Inc. (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー Co., Ltd.) system TMA/SS120U.
Cl ions: cured article is pulverized, and is that the sample of the particle diameter of 1mm is in 150 ℃ of pressure cooking tests of carrying out 20 hours on 2mm, the sieve under the sieve with whole grain, and through the cl ions in the ion-chromatographic determination extraction water, the concentration that is converted in the cured article is tried to achieve then.
Embodiment 1.
Adding is as Epotohto (エ Port ト ー ト) TX-0929 (Toto Kasei KK's system, the terephthalyl alcohol 2-glycidyl ether resin of the 547.4g of 2 functional group's aromatic species epoxy resin (a1) of general formula 1 in the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed; Epoxy equivalent (weight): 144g/eq, perchloro-: 0.11% weight, viscosity: 50mPas; Hydroxyl concentration: 39meq/100g; α glycol content: 2.3meq/100g), as DOPO-HQ (Sanko Co., Ltd.'s system, trade(brand)name: HCA-HQ, the hydroxyl equivalent: 162g/eq of the 252.6g of organo phosphorous compounds; Phosphorus containing ratio: 9.5% weight); When stirring, be heated to 130 ℃ through sheathing formula well heater, (Co., Ltd.'s system, trade(brand)name: TPP) are learned in northern Xinghua when reaching 130 ℃, to add triphenyl phosphine as the 0.25g of catalyzer; Reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-1) of 795g.The proterties of the phosphorous epoxy resin that makes (E-1) is illustrated in the table 1.
Embodiment 2.
In the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed, add Epotohto (エ ポ ト ー ト) TX-0929 (above-mentioned) as the 602.5g of 2 functional group's aromatic species epoxy resin (a1) of general formula 1, as the DOPO-NQ (9 of the 197.5g of organo phosphorous compounds; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound 1; 4-naphthoquinones adducts; Hydroxyl equivalent: 187g/eq, phosphorus content: 8.1% weight), when stirring, be heated to 130 ℃ through sheathing formula well heater; (four countries change into Co., Ltd.'s system when reaching 130 ℃, to add 2-ethyl-4-methylimidazole as the 0.05g of catalyzer; Trade(brand)name: 2E4MZ), reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-2) of 795g.The proterties of the phosphorous epoxy resin that makes (E-2) is illustrated in the table 1.
Embodiment 3.
Adding is as Epotohto (エ ポ ト ー ト) TX-0934 (Toto Kasei KK's system of the 608.7g of 2 functional group's aromatic species epoxy resin (a1) of general formula 1 in the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed; Biphenyl is to dimethanol 2-glycidyl ether resin; Epoxy equivalent (weight): 184g/eq, total chlorine: 0.11% weight, viscosity: 200mPas; Hydroxyl concentration: 63meq/100g; α glycol content: 2.5meq/100g), as the DOPO-NQ (above-mentioned) of the 116.3g of organo phosphorous compounds and DOPO (Sanko Co., Ltd.'s system, trade(brand)name: HCA, the phosphorus containing ratio: 14.2% weight) of 75.0g; When stirring, be heated to 130 ℃ through sheathing formula well heater; When reaching 130 ℃, add the triphenyl phosphine (above-mentioned) as the 0.19g of catalyzer, reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-3) of 795g.The proterties of the phosphorous epoxy resin that makes (E-3) is illustrated in the table 1.
Embodiment 4.
Adding is as the DOPO (above-mentioned) of the 182.0g of organo phosphorous compounds and the toluene of 420g in the removable flask of 4 neck glass that whipping appts, TM, cooling tube, nitrogen gatherer are installed; Under nitrogen atmosphere, when stirring, heat, make it to dissolve fully.Then, gradation drops into as 1 of the 56.7g of quinones, 4-naphthoquinones (Kawasaki changes into Co., Ltd.'s system, 3% moisture article) when being careful the intensification that causes because of reaction heat.1 of this moment, the mol ratio of 4-naphthoquinones and DOPO is 1,4-naphthoquinones/DOPO=0.41.After reacting by heating, adding is as Epotohto (エ ポ ト ー ト) TX-0917 (Toto Kasei KK's system, the R of general formula 1 of the 563.0g of 2 functional group's aromatic species epoxy resin (a1) of general formula 1
1Be the compound of formula (7-12), epoxy equivalent (weight): 173g/eq, total chlorine: 0.10% weight; Viscosity: 46mPas, hydroxyl concentration: 72meq/100g, α glycol content: 2.8meq/100g); When importing nitrogen, stir,, toluene is got rid of to system heating below 130 ℃.Then, add the triphenyl phosphine (above-mentioned) as the 0.24g of catalyzer, reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-4) of 790g.The proterties of the phosphorous epoxy resin that makes (E-4) is illustrated in the table 1.
Embodiment 5.
Adding is as Epotohto (エ ポ ト ー ト) ZX-1658 (Toto Kasei KK's system of the 547.4g of the 2 functional groups aliphatic series based epoxy resins (a2) of general formula (3) in the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed; The cyclohexanedimethanodiglycidyl diglycidyl ether resin; Epoxy equivalent (weight): 140g/eq; Total chlorine: 0.075% weight, viscosity: 45mPas, hydroxyl concentration: 19meq/100g; α glycol content: 2.8meq/100g), as the DOPO-HQ (above-mentioned) of the 252.6g of organo phosphorous compounds; When stirring, be heated to 130 ℃ through sheathing formula well heater, insulation is 1 hour when reaching 130 ℃, adds the triphenyl phosphine (above-mentioned) as the 0.25g of catalyzer then; Reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-5) of 795g.The proterties of the phosphorous epoxy resin that makes (E-5) is illustrated in the table 1.
Embodiment 6.
Adding is as HBPADGE (Maruzen Petrochemical Co., Ltd.'s system of the 632.0g of the 2 functional groups aliphatic series based epoxy resins (a2) of general formula (3) in the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed; Hydrogenated Bisphenol A 99 type 2-glycidyl ether resin, epoxy equivalent (weight): 210g/eq, total chlorine: 0.14% weight; Viscosity: 780mPas; Hydroxyl concentration: 66meq/100g, α glycol content: 4.6meq/100g), as the DOPO-HQ (above-mentioned) of the 168.0g of organo phosphorous compounds, when stirring, be heated to 130 ℃ through sheathing formula well heater; Insulation is 1 hour when reaching 130 ℃; Add the triphenyl phosphine (above-mentioned) as the 0.17g of catalyzer then, reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-6) of 795g.The proterties of the phosphorous epoxy resin that makes (E-6) is illustrated in the table 1.
Embodiment 7.
Adding is as Epotohto (エ ポ ト ー ト) ZX-1542 (Toto Kasei KK's system of the 570.0g of the polyfunctional group aliphatic series based epoxy resin (a3) of general formula (4) in the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed; The TriMethylolPropane(TMP) polyglycidyl ether resins; Epoxy equivalent (weight): 118g/eq; Total chlorine: 0.072% weight; Viscosity: 80mPas, hydroxyl concentration: 195meq/100g, α glycol content: 1.4meq/100g), as the DOPO (above-mentioned) of the 50.0g of organo phosphorous compounds and the DOPO-HQ (above-mentioned) of 180.0g; When stirring, be heated to 130 ℃ through sheathing formula well heater; When reaching 130 ℃, add the triphenyl phosphine (above-mentioned) as the 0.23g of catalyzer, reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-7) of 795g.The proterties of the phosphorous epoxy resin that makes (E-7) is illustrated in the table 1.
[table 1]
Comparative example 1.
In the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed, add Epotohto (エ ポ ト ー ト) PG-207GS (Toto Kasei KK's system as the 632.0g of epoxy resin; The polypropylene glycol diglycidyl ether resin; Epoxy equivalent (weight): 319g/eq, total chlorine: 0.10% weight, viscosity: 45mPas; Hydroxyl concentration: 88meq/100g; α glycol content: 2.0meq/100g), as the DOPO-HQ (above-mentioned) of the 168.0g of organo phosphorous compounds, when stirring, be heated to 130 ℃, when reaching 130 ℃, add triphenyl phosphine (above-mentioned) as the 0.17g of catalyzer through sheathing formula well heater; Reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-8) of 795g.The proterties of the phosphorous epoxy resin that makes (E-8) is illustrated in the table 2.
Comparative example 2.
In the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed, add Epotohto (エ ポ ト ー ト) TX-0917 (above-mentioned) as the 757.9g of epoxy resin, as the DOPO-HQ (above-mentioned) of the 42.1g of organo phosphorous compounds; When stirring, be heated to 130 ℃ through sheathing formula well heater; When reaching 130 ℃, add triphenyl phosphine (above-mentioned) as the 0.05g of catalyzer; Reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-9) of 795g.The proterties of the phosphorous epoxy resin that makes (E-9) is illustrated in the table 2.
Comparative example 3.
In the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed, add Epotohto (エ ポ ト ー ト) TX-0917 (above-mentioned) as the 480.0g of epoxy resin, as the DOPO (above-mentioned) of the 220.0g of organo phosphorous compounds and the DOPO-HQ (above-mentioned) of 100.0g; When stirring, be heated to 130 ℃ through sheathing formula well heater; When reaching 130 ℃, add triphenyl phosphine (above-mentioned) as the 0.32g of catalyzer; Reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-10) of 795g.The proterties of the phosphorous epoxy resin that makes (E-10) is illustrated in the table 2.
Comparative example 4.
In the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed, add Epotohto (エ ポ ト ー ト) TX-0934 (above-mentioned) as the 505.0g of epoxy resin, as the DOPO-HQ (above-mentioned) of the 295.0g of organo phosphorous compounds; When stirring, be heated to 130 ℃ through sheathing formula well heater; When reaching 130 ℃, add triphenyl phosphine (above-mentioned) as the 0.30g of catalyzer; Reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-11) of 795g.The proterties of the phosphorous epoxy resin that makes (E-11) is illustrated in the table 2.
Comparative example 5.
Adding is as the DOPO (above-mentioned) of the 137.6g of organo phosphorous compounds and the toluene of 330g in the removable flask of 4 neck glass that whipping appts, TM, cooling tube, nitrogen gatherer are installed; Under nitrogen atmosphere, when stirring, heat, make it to dissolve fully.Then, gradation drops into as 1 of the 31.3g of quinones, 4-naphthoquinones (above-mentioned) when being careful the intensification that causes because of reaction heat.1 of this moment, the mol ratio of 4-naphthoquinones and DOPO is 1,4-naphthoquinones/DOPO=0.13.After reacting by heating, add Epotohto (エ Port ト ー ト) ZX-1659 (Toto Kasei KK's system, Hydrogenated Bisphenol A 99 type 2-glycidyl ether resin as the 632.0g of epoxy resin; Epoxy equivalent (weight): 215g/eq, total chlorine: 0.45% weight, viscosity: 1; 500mPas, hydroxyl concentration: 230meq/100g, α glycol content: 11meq/100g); When importing nitrogen, stir,, toluene is got rid of to system heating below 130 ℃.Then, add the triphenyl phosphine (above-mentioned) as the 0.17g of catalyzer, reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-13) of 790g.The proterties of the phosphorous epoxy resin that makes (E-12) is illustrated in the table 2.
Comparative example 6.
In the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed, add Epotohto (エ ポ ト ー ト) ZX-1542 (Toto Kasei KK's system, TriMethylolPropane(TMP) polyglycidyl ether resins as the 570.0g of epoxy resin; Epoxy equivalent (weight): 122g/eq; Total chlorine: 0.065% weight; Viscosity: 80mPas, hydroxyl concentration: 262meq/100g, α glycol content: 1.5meq/100g), as the DOPO (above-mentioned) of the 50.0g of organo phosphorous compounds and the DOPO-HQ (above-mentioned) of 180.0g; When stirring, be heated to 130 ℃ through sheathing formula well heater; When reaching 130 ℃, add the triphenyl phosphine (above-mentioned) as the 0.23g of catalyzer, reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-13) of 795g.The proterties of the phosphorous epoxy resin that makes (E-13) is illustrated in the table 2.
Comparative example 7.
In the removable flask of 4 neck glass that whipping appts, TM, nitrogen gatherer and cooling tube are installed, add Epotohto (エ ポ ト ー ト) YDF-170 (Toto Kasei KK's system as the 547.4g of epoxy resin; Bisphenol F 2-glycidyl ether resin; Epoxy equivalent (weight): 168g/eq; Total chlorine: 0.15% weight, viscosity: 3,000mPas), as the DOPO-HQ (above-mentioned) of the 252.6g of organo phosphorous compounds; When stirring, be heated to 130 ℃ through sheathing formula well heater; When reaching 130 ℃, add the triphenyl phosphine (above-mentioned) as the 0.25g of catalyzer, reaction is 4 hours when temperature of reaction being remained on 160 ℃ ~ 165 ℃, makes the phosphorous epoxy resin (E-14) of 795g.The proterties of the phosphorous epoxy resin that makes (E-14) is illustrated in the table 2.
[table 2]
Embodiment 8 ~ 10, comparative example 8 ~ 11
According to the prescription of the blending shown in the table 3 blending phosphorous epoxy resin, solidifying agent, curing catalyst etc.Phosphorous epoxy resin is dissolved with methylethylketone; Add the Dyhard RU 100 (DICY that is dissolved in methylcyclohexane, N in advance as solidifying agent; Ahew: 21.0g/eq) with as the 2-ethyl-4-methylimidazole (above-mentioned) of curing catalyst; Preparation resin combination varnish makes nonvolatile component reach 50% weight.Then, use the resinous varnish that makes, dipping is as woven fiber glass (Nitto Boseiki Co., Ltd.'s system of base material; WEA 116E 106S 136; Thick 100 μ m), the woven fiber glass of dipping is carried out 8 minutes drying with 150 ℃ heated air circulation type baking oven, make prepreg (プ リ プ レ グ).Then, 4 prepregs that make are overlapping, under the condition of 130 ℃ * 15 minutes and 170 ℃ * 2.0MPa * 70 minute, heat and pressurize, make the thick veneer sheet of 0.5mm.Each veneer sheet to making makes an experiment to various rerum naturas such as flame retardant resistance, cementability, rate of moisture absorption.Its result is illustrated in the table 4.
[table 3]
Notes) 2E4MZ is a 2-ethyl-4-methylimidazole
[table 4]
| ? | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 |
| Flame retardant resistance | V-0 | V-0 | V-1 | NG | NG | V-0 | V-0 |
| Cementability (kN/m) | 2.2 | 2 | 2 | 2 | 0.6 | 0.9 | 2.8 |
| Rate of moisture absorption (% weight) | 1.2 | 1 | 1.3 | 2.5 | 2.1 | 1.8 | 1.2 |
| Thermotolerance | ○ | ○ | ○ | ○ | ○ | × | × |
Comparative example 8 is owing to use aliphatic series type phosphorous epoxy resin, so cementability is good, but poor fire, anti-water absorbability is also poor.Comparative example 9 is the phosphorous epoxy resin of general formula 1, but because the phosphorus containing ratio is low to moderate 0.5% weight, so poor fire, because epoxy equivalent (weight) is low to moderate 196g/eq, so cementability is also poor.Comparative example 10 is the phosphorous epoxy resin of general formula 1, but since epoxy equivalent (weight) up to 705g/eq, so poor heat resistance because the weight ratio of phosphorus compound (b1)/phosphorus compound (b2) is 31/69 in the raw material, is lower than 50/50, so cementability is poor, anti-water absorbability is also poor.Comparative example 11 is the phosphorous epoxy resin of general formula 1, because epoxy equivalent (weight) is up to 880g/eq, melt viscosity is also up to 1,300mPas, so though cementability is good, but poor heat resistance.On the other side is that all embodiment not only can guarantee enough flame retardant resistances, and cementability is good, anti-water absorbability and thermotolerance.
Embodiment 11 ~ 14, comparative example 12 ~ 14
According to the prescription of the blending shown in the table 5 blending phosphorous epoxy resin, solidifying agent, curing catalyst etc.As solidifying agent, use diethylammonium diaminodiphenyl-methane (Nippon Kayaku K. K's system, trade(brand)name: Kayahard (カ ヤ ハ ー De) AA; Ahew: 63g/eq, viscosity: 2,500mPas); Be heated in 50 ℃, stirring homogenize, making composition epoxy resin.Composition epoxy resin to making carries out deaeration, injects mould, under 150 ℃ * 120 minutes temperature condition, makes it to solidify, and makes the thick cured article test film of 2mm.Cured article test film to making makes an experiment to various rerum naturas such as cl ions, flame retardant resistance, rate of moisture absorption.Its result is illustrated in the table 6.What need explanation is in comparative example 12, as epoxy resin, to use Epotohto (エ ポ ト ー ト) ZX-1059 (Toto Kasei KK's system; The mixture of Bisphenol F 2-glycidyl ether resin and bisphenol A diglycidyl ether resin, epoxy equivalent (weight): 165g/eq, total chlorine: 0.08% weight, viscosity: 2; 300mPas), as additive flame retardant, add 1; The 3-phenylene is two-two-2, and 6-tolyl SULPHOSUCCINIC ACID ESTER (1,3-Off ェ ニ レ Application PVC ス-ジ-2; 6-キ シ レ ニ Le ホ ス フ ェ ー ト 1,3-phelylenebis-di-2,6-xylenyl phosphate) (Daihachi Chemical Industry Co., Ltd.'s system; Trade(brand)name: PX-200, phosphorus content: 9.0% weight), make the phosphorus containing ratio in the composition epoxy resin reach 2.0% weight.
[table 5]
Notes) 2E4MZ is a 2-ethyl-4-methylimidazole
[table 6]
| ? | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Comparative example 12 | Comparative example 13 | Comparative example 14 |
| Cl ions (ppm) | 30 | 50 | 70 | 20 | 320 | 30 | 50 |
| Flame retardant resistance (UL94) | V-0 | V-0 | V-0 | V-0 | V-1 | V-1 | V-2 |
| Rate of moisture absorption (% weight) | 1.3 | 0.9 | 1 | 1.5 | 2.1 | 2.5 | 1.6 |
Comparative example 12 is the phosphorous epoxy resin of general formula 3, but since total chlorine of raw material epoxy resin up to 0.45% weight, so the cl ions of cured article is Duoed about 5 ~ 10 times than embodiment.This shows the safety variation.In addition, because hydroxyl concentration is up to 230meq/100g, the α glycol content is also up to 11meq/100g, so anti-water absorbability is also poor.In addition, because the weight ratio of phosphorus compound (b1)/phosphorus compound (b2) is 43/57 in the raw material, be lower than 50/50, so the solid state variation of cured article, flame retardant resistance is also slightly poor.Comparative example 13 is the phosphorous epoxy resin of general formula 4; But because the hydroxyl concentration of raw material epoxy resin is up to 262meq/100g; So anti-water absorbability is poor,, be lower than 50/50 because the weight ratio of phosphorus compound (b1)/phosphorus compound (b2) is 39/61 in the raw material; So the solid state variation of cured article, flame retardant resistance are also slightly poor.Comparative example 14 has the composition epoxy resin of fire retardant for blending in low chlorine liquid resin commonly used, although make the phosphorus containing ratio consistent with embodiment, flame retardant resistance is still poor, and anti-water absorbability is also poor.On the other side is that all embodiment not only can guarantee enough flame retardant resistances, and cl ions is few, anti-water absorbability.This shows good reliability.
Embodiment 15 ~ 17, comparative example 15 ~ 17
According to the prescription of the blending shown in the table 7 blending phosphorous epoxy resin, solidifying agent, curing catalyst etc.As solidifying agent, use triphenyl methane type phenol resins (Gunsaka Chem. Industry Co., Ltd.'s system, trade(brand)name: TMP-100, hydroxyl equivalent: 97.5g/eq, softening temperature: 107 ℃), be heated in 120 ℃, stir homogenize, make composition epoxy resin.Composition epoxy resin to making carries out deaeration, injects mould, under 150 ℃ * 120 minutes+180 ℃ * 60 minutes temperature condition, makes it to solidify, and makes the thick cured article test film of 2mm.Cured article test film to making makes an experiment to various rerum naturas such as formability, flame retardant resistance, rate of moisture absorption.Its result is illustrated in the table 8.What need explanation is; In embodiment 14, share Epotohto (エ ポ ト ー ト) ZX-1059 (above-mentioned) as the epoxy resin beyond the phosphorous epoxy resin; In comparative example 16, share Epotohto (エ ポ ト ー ト) ZX-1542 (Toto Kasei KK's system, TriMethylolPropane(TMP) polyglycidyl ether resins, epoxy equivalent (weight): 122g/eq as the epoxy resin beyond the phosphorous epoxy resin; Total chlorine: 0.065% weight, viscosity: 80mPas).
[table 7]
Notes) 2E4MZ is a 2-ethyl-4-methylimidazole
[table 8]
| ? | Embodiment 15 | Embodiment 16 | Embodiment 17 | Comparative example 15 | Comparative example 16 | Comparative example 17 |
| Flame retardant resistance (UL94) | V-0 | V-0 | V-1 | NG | — | NG |
| Rate of moisture absorption (% weight) | 0.8 | 0.9 | 1.1 | 1.6 | — | 1.8 |
Comparative example 15 is owing to use aliphatic series type phosphorous epoxy resin, so poor fire, anti-water absorbability is also poor.The phosphorous epoxy resin of comparative example 16 for making through disclosed method for making in the patent documentation 4, but be not the phosphorous epoxy resin of general formula 1, so the viscosity of composition epoxy resin is too high, can't prepare the required test film of test owing to be difficult to formed in mould cause.Comparative example 17 is for share thinner to reduce the composition epoxy resin of viscosity in the phosphorous epoxy resin that disclosed method for making makes in through patent documentation 4, though formability obtains improvement, flame retardant resistance worsens, and wet fastness also worsens.On the other side is that all embodiment not only can guarantee enough flame retardant resistances, and good moldability, anti-water absorbability.
Utilizability on the industry
Composition epoxy resin of the present invention is a low viscosity compositions, and the flame retardant resistance of its cured article, excellent moisture resistance, so can be used for cast material, laminating material, sealing material, matrix material etc.
Claims (6)
1. the preparation method of phosphorous epoxy resin; It is characterized in that; Make by with the epoxy resin (a1) of general formula (1) expression, with the epoxy resin (a2) of general formula (3) expression or with at least a epoxy resin of forming (A) in the epoxy resin (a3) of general formula (4) expression with by with the organo phosphorous compounds (b1) of general formula (5) expression and/or organo phosphorous compounds (B) reaction that constitutes with the organo phosphorous compounds (b2) of general formula (6) expression; Thereby the preparation epoxy equivalent (weight) is 200 ~ 600g/eq, phosphorus containing ratio is in the method for phosphorous epoxy resin of 1 ~ 6% weight; The hydroxyl concentration of epoxy resin (A) is below the 200meq/100g; Total chlorine amount is below 0.4% weight, and the α glycol content is below the 10meg/100g, and the weight ratio scope of organo phosphorous compounds (b1)/organo phosphorous compounds (b2) is 50/50 ~ 100/0 in the organo phosphorous compounds (B);
R in the formula
1Be the alkyl of carbonatoms 6 ~ 31, said alkyl has 1 aromatic ring at least, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, any in G expression (2) or the hydrogen;
R in the formula
2Be the aliphatic hydrocarbyl of carbonatoms 6 ~ 17, said aliphatic hydrocarbyl can be monocycle or heterocycle, has 1 cyclohexane ring at least, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, any in G expression (2) or the hydrogen;
R in the formula
3Be separately respectively the aliphatic hydrocarbyl that can contain the carbonatoms 1 ~ 4 of Sauerstoffatom, nitrogen-atoms, sulphur atom, R
4Expression-R
3-OG ,-R
3In-H or the hydrogen any, any in G expression (2) or the hydrogen, k representes 0 or 1 integer;
R in the formula
5, R
6Expression hydrogen or alkyl separately can be similar and different, can be straight chain shape, branched, ring-type, in addition R
5With R
6But bonding forms ring texture, and n representes 0 or 1 integer, and Ar representes any in benzene, biphenyl, naphthalene, anthracene, phenanthrene and the hydrocarbon substituent thereof;
R in the formula
7, R
8Expression hydrogen or alkyl separately can be similar and different, can be straight chain shape, branched, ring-type, in addition R
7With R
8But bonding forms ring texture, and m representes 0 or 1 integer.
2. the preparation method of the phosphorous epoxy resin of claim 1 is characterized in that, the epoxy resin of claim 1 (A) is with at least a kind in the epoxy resin of general formula (7), general formula (8), general formula (9), general formula (10) or general formula (11) expression
3. the preparation method of claim 1 or 2 phosphorous epoxy resin is characterized in that, the organo phosphorous compounds of claim 1 (b1) is with at least a kind in the organo phosphorous compounds of general formula (12) or general formula (13) expression
4. the preparation method of each phosphorous epoxy resin in the claim 1 ~ 3 is characterized in that, the organo phosphorous compounds of claim 1 (b2) is the organo phosphorous compounds with general formula (14) expression
5. composition epoxy resin is characterized in that, contains phosphorous epoxy resin and the solidifying agent that the preparation method through each phosphorous epoxy resin in the claim 1 ~ 4 makes and is essential composition.
6. cured article, said cured article solidify through the composition epoxy resin with claim 5 and obtain.
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| JP2010025187A JP5544184B2 (en) | 2010-02-08 | 2010-02-08 | Method for producing phosphorus-containing epoxy resin, epoxy resin composition and cured product thereof |
| JP2010-025187 | 2010-02-08 | ||
| PCT/JP2011/052680 WO2011096588A1 (en) | 2010-02-08 | 2011-02-02 | Method for producing a phosphorus-containing epoxy resin, epoxy resin composition, and cured product thereof |
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| KR (1) | KR101794366B1 (en) |
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|---|---|---|---|---|
| CN103333464A (en) * | 2013-06-28 | 2013-10-02 | 青岛富斯林化工科技有限公司 | Phosphorus-containing halogen-free flame-retardant epoxy resin composition and applications |
| CN106467653A (en) * | 2015-08-19 | 2017-03-01 | 新日铁住金化学株式会社 | Flame-retardant epoxy resin omposition, prepreg, insulating trip, adhesive sheet, plywood, encapsulant, cast material and solidfied material |
| CN110719926A (en) * | 2017-06-07 | 2020-01-21 | Dic株式会社 | Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof |
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| JP5917098B2 (en) * | 2011-11-11 | 2016-05-11 | 新日鉄住金化学株式会社 | Method for producing phosphorus-containing phenolic resin |
| 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 |
| SG11201408343TA (en) * | 2012-06-15 | 2015-01-29 | Nippon Steel & Sumikin Chem Co | Phosphorus-containing epoxy resin, composition containing phosphorus-containing epoxy resin as essential component, and cured product |
| JP6246126B2 (en) * | 2012-08-28 | 2017-12-13 | 新日鉄住金化学株式会社 | Method for producing cyanuric acid-modified phosphorus-containing epoxy resin, resin composition containing cyanuric acid-modified phosphorus-containing epoxy resin, and cured product thereof |
| TWI487781B (en) * | 2013-02-08 | 2015-06-11 | Hong Tai Electric Ind Co Ltd | Phosphorus and nitrogen hybrid halogen-free flame-resistance epoxy, prepreg, copper clad laminate and pcb thereof |
| CN103612437A (en) * | 2013-11-28 | 2014-03-05 | 铜陵浩荣电子科技有限公司 | Novel halogen-free composite type base plate and manufacture method thereof |
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| JP3642403B2 (en) * | 1999-02-23 | 2005-04-27 | 大日本インキ化学工業株式会社 | Flame retardant epoxy resin composition and method for producing flame retardant epoxy resin |
| JP3176356B2 (en) | 1999-09-03 | 2001-06-18 | 東芝ケミカル株式会社 | Flame retardant epoxy resin composition, prepreg and laminated product |
| JP2003027029A (en) | 2001-07-16 | 2003-01-29 | Kyocera Chemical Corp | Flame-retardant adhesive composition and flexible printed wiring board-related product |
| DE102005015605B4 (en) * | 2005-04-05 | 2008-04-17 | Schill + Seilacher "Struktol" Aktiengesellschaft | Organophosphorus-containing prepolymers and uses therefor |
| JP5153320B2 (en) * | 2007-12-28 | 2013-02-27 | 新日鉄住金化学株式会社 | Novel phosphorus-containing flame-retardant resin, epoxy resin composition containing the same, and cured product thereof |
| JP5587542B2 (en) * | 2008-02-01 | 2014-09-10 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin and phosphorus-containing epoxy resin composition, production method thereof, curable resin composition and cured product using the resin, and resin composition |
| TW201122014A (en) * | 2009-12-25 | 2011-07-01 | Nippon Steel Chemical Co | Epoxy resin, epoxy resin composition and cured article thereof |
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| JP2002226547A (en) * | 2001-01-30 | 2002-08-14 | Asahi Denka Kogyo Kk | Epoxy resin composition |
| WO2009060987A1 (en) * | 2007-11-09 | 2009-05-14 | Tohto Kasei Co., Ltd. | Phosphorus-containing epoxy resin and phosphorus-containing epoxy resin composition, process for producing the same, and curable resin composition and cured object each containing or obtained from the resin and the resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103333464A (en) * | 2013-06-28 | 2013-10-02 | 青岛富斯林化工科技有限公司 | Phosphorus-containing halogen-free flame-retardant epoxy resin composition and applications |
| CN106467653A (en) * | 2015-08-19 | 2017-03-01 | 新日铁住金化学株式会社 | Flame-retardant epoxy resin omposition, prepreg, insulating trip, adhesive sheet, plywood, encapsulant, cast material and solidfied material |
| CN110719926A (en) * | 2017-06-07 | 2020-01-21 | Dic株式会社 | Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof |
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| KR101794366B1 (en) | 2017-11-06 |
| JP2011162621A (en) | 2011-08-25 |
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| TW201132668A (en) | 2011-10-01 |
| CN102741314B (en) | 2014-12-31 |
| WO2011096588A1 (en) | 2011-08-11 |
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| JP5544184B2 (en) | 2014-07-09 |
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