CN102741314B - 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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- CN102741314B CN102741314B CN201180008716.0A CN201180008716A CN102741314B CN 102741314 B CN102741314 B CN 102741314B CN 201180008716 A CN201180008716 A CN 201180008716A CN 102741314 B CN102741314 B CN 102741314B
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- JIIWHHKPVCGRJK-UHFFFAOYSA-N CC(C=C(C1=CCCC=C11)O)(C=C1O)P1(Oc(cccc2)c2C2=CCCC=C12)=O Chemical compound CC(C=C(C1=CCCC=C11)O)(C=C1O)P1(Oc(cccc2)c2C2=CCCC=C12)=O JIIWHHKPVCGRJK-UHFFFAOYSA-N 0.000 description 1
- 0 O=P1OC2C=CCCC2C2=CC*C=C12 Chemical compound O=P1OC2C=CCCC2C2=CC*C=C12 0.000 description 1
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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
- C08G59/14—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
- C08G59/18—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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- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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 present invention relates to neo-epoxy resin and use composition epoxy resin and the cured article thereof of this epoxy resin, described epoxy resin has the excellent cured article of flame retardant resistance while can preparing low viscosity excellence, can be used as the sealing of the electrical/electronic part etc. taking semiconductor element as representative, coating material, laminating material, the cured article of matrix material etc., the present invention is suitable for the insulating material etc. in the electric and electronic such as printing distributing board, encapsulating semiconductor field.
Background technology
Epoxy resin is industrially used to purposes widely, but performance required by it is more and more higher in recent years.Such as, semiconductor-encapsulating material is had in the representative field of the resin combination taking epoxy resin as principal constituent, but in recent years along with the raising of semiconductor element integrated level, while package size turns to big area, thinning, assembling mode also enters the transfer to surface-assembled, ites is desirable to develop the more excellent material of welding thermotolerance.
In addition, recently due to technological trend that is highly integrated, High Density Packaging, replace relying on the assembling utilizing the transfer molding of mould (ト ラ Application ス フ ァ ー is shaped) to carry out in the past, hybrid integrated IC, sheet support plate, carrier package, mould pin grid array, mould that ball grid array etc. does not use mould and the mode that adopts liquid material to carry out sealing, assembling increases gradually.But there is the low shortcoming of reliability in usual liquid material compared with the solid-state material for transfer molding.Its reason is, liquid material exists the limit in viscosity, there is restriction to used resin, solidifying agent, filling agent etc.In addition, in the face of halogen-free flame-retardant in recent years, when using halogen fire retardant, even if do not thinking that under these necessary purposes, flame-retarded requirement also improves.
In addition, also progressively improve in the requirement of field of compound material halogen, but owing to needing to realize lowering viscousity while guaranteeing flame retardant resistance, so not yet obtain gratifying product.
For overcoming these problems, wish as the epoxy resin of principal constituent and solidifying agent flame-retarded while lowering viscousity, low moisture absorption, high resistance to thermalization.As low viscosity epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin etc. are widely known by the people usually, but not only not enough in low viscosity, also do not have flame retardant resistance.As the epoxy resin of low viscosity excellence, disclose in patent documentation 1 have oxo methene chain epoxy resin, but thermotolerance, wet fastness still have the leeway of improvement, do not give consideration completely for flame retardant resistance.Disclose the epoxy resin with dicyclohexyl ring in patent documentation 2, but completely consideration is not given for flame retardant resistance.In patent documentation 3, disclose the phosphorous epoxy resin with flame retardant resistance, but belong to by the obtained phosphorous epoxy resin of 2 functional group epoxy resins and phosphorous phenol resins with aromatic backbone, have problems in lowering viscousity.In patent documentation 4, mentioned by having flame retardant resistance in phosphorous epoxy resin composition, record the content that aliphatic epoxy resin also can be used as the raw material of phosphorous epoxy resin, but have nothing to do in the record of the effect using aliphatic epoxy resin, in addition also have nothing to do in the record of the feature as phosphorous epoxy resin, completely consideration is not given for viscosity.In patent documentation 5, disclose the composition containing phosphorous monoepoxy resin, but aliphatic class thinner must be share, cannot be used alone.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 4-359009 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2006-188606 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2001-288247 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-249540 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2001-106766 publication
Patent documentation 6: Japanese Laid-Open Patent Publication 61-268691 publication.
Summary of the invention
Invent problem to be solved
Be difficult to as mentioned above obtain the liquid-state epoxy resin with flame retardant resistance.Therefore, the object of the present invention is to provide that can to prepare low viscosity excellent and have the preparation method of the phosphorous epoxy resin of the cured article of flame retardant resistance, the composition epoxy resin containing the phosphorous epoxy resin obtained by this preparation method and this cured article.
Solve the means of problem
The present inventor furthers investigate repeatedly for solving above-mentioned problem, found that: the requirement for the preparation of significantly not damaging cured article physical property with the necessary low viscosity epoxy resin of phosphorous epoxy resin of effective flame retardant resistance, complete the preparation method of the phosphorous epoxy resin of the present application, solve the following means of means described in right needed for above-mentioned problem.
(1) preparation method of phosphorous epoxy resin, it is characterized in that, make by the epoxy resin (a1) represented with general formula (1), in the epoxy resin (a3) that the epoxy resin (a2) represented with general formula (3) or general formula (4) represent at least one composition epoxy resin (A) with react by the organo phosphorous compounds (b1) represented with general formula (5) with the organo phosphorous compounds (B) that the organo phosphorous compounds (b2) that general formula (6) represents is formed, thus to prepare epoxy equivalent (weight) be 200 ~ 600g/eq, phosphorus containing ratio is in the method for the phosphorous epoxy resin of 1 ~ 6% weight, the hydroxyl concentration of epoxy resin (A) is below 200meq/100g, total chlorine amount is below 0.4% weight, α glycol content is below 10meg/100g, and the weight ratio of organo phosphorous compounds (b1)/organo phosphorous compounds (b2) is 50/50 ~ 100/0 in organo phosphorous compounds (B).
R in formula
1for the alkyl of carbonatoms 6 ~ 31, described alkyl at least has 1 aromatic ring, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, any one in G expression (2) or hydrogen.
R in formula
2for the aliphatic hydrocarbyl of carbonatoms 6 ~ 17, described aliphatic hydrocarbyl can be monocycle or heterocycle, at least has 1 cyclohexane ring, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, any one in G expression (2) or hydrogen.
R in formula
3be individually the aliphatic hydrocarbyl that can contain the carbonatoms 1 ~ 4 of Sauerstoffatom, nitrogen-atoms, sulphur atom, R
4expression-R
3-OG ,-R
3any one in-H or hydrogen, any one in G expression (2) or hydrogen, k represents the integer of 0 or 1.
R in formula
5, R
6represent hydrogen or alkyl, separately can be similar and different, can be straight-chain, branched, ring-type.In addition, R
5with R
6bonding formation ring texture.N represents the integer of 0 or 1.Ar represents any one in benzene, biphenyl, naphthalene, anthracene, phenanthrene and hydrocarbon substituent thereof.
R in formula
7, R
8represent hydrogen or alkyl, separately can be similar and different, can be straight-chain, branched, ring-type.R in addition
7with R
8bonding formation ring texture.M represents the integer of 0 or 1.
(2) composition epoxy resin, is characterized in that, the phosphorous epoxy resin that the preparation method containing the phosphorous epoxy resin by recording in (1) obtains and solidifying agent are as required composition.
(3) cured article, described cured article is by obtaining the epoxy resin composition recorded in (2).
The epoxy resin (a3) that epoxy resin of the present invention (A) is necessary for the epoxy resin (a1) represented with general formula (1), the epoxy resin (a2) represented with general formula (3) or represents with general formula (4).Even if use epoxy resin in addition also cannot obtain the phosphorous epoxy resin of low viscosity and the flame retardant resistance had as the object of the invention.
Usually, when making epoxy resin and the new epoxy resin of phenol resins class Reactive Synthesis, the inevitable remaining epoxy resin had as raw material in obtained epoxy resin.Therefore, in obtained phosphorous epoxy resin, also need the impact of the epoxy resin (A) being considered as raw material.
The glycidyl ether being derived from alcohol hydroxyl group makes unreacted remaining amount of hydroxyl groups have the trend increased because of reactivity difference.Remaining hydroxyl in raw material epoxy resin (A) stays out of with the reaction of phosphorus compound and directly remaining, make the end group purity drop of phosphorous epoxy resin, so the increase of residual hydroxyl in 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 becoming the essential factor that the cured article physical property such as the intensity of cured article or thermotolerance reduction worsen, so need the remaining hydroxyl and high-purity making raw material epoxy resin (A).Therefore, the remaining hydroxyl concentration of epoxy resin (A) is preferably below 200meq/100g, is more preferably below 100meq/100g, more preferably below 50meq/100g.
In addition, for reducing remaining hydroxyl concentration, if improve reactive by adding catalyzer etc., then parallel side reaction increases, and causes contained total chlorine amount high concentration.Total chlorine amount in raw material epoxy resin (A) makes the electrical reliability of cured article significantly reduce, so also need high purity for total chlorine amount owing to directly remaining in phosphorous epoxy resin.The total chlorine amount of raw material epoxy resin (A) is preferably below 0.4% weight, is more preferably below 0.2% weight, more preferably below 0.1% weight.In the glycidyl ether coming from alcohol hydroxyl group, because total chlorine amount is that the situation of more than 1% weight is maximum, so need to reduce total chlorine amount by highly purified reaction and distillation procedure or extracting operation.These methods there is no special stipulation, can use the various methods designed at present.
In addition, α glycol content in raw material epoxy resin (A) is also the same with remaining hydroxyl concentration to be stayed out of with the reaction of phosphorus compound and directly remaining, make the end group purity drop of phosphorous epoxy resin, so the increase of α glycol content in raw material epoxy resin (A) directly makes the water absorbability of phosphorous epoxy resin composition increase, the reason that storage stability reduces is become for anhydride curing agent or microcapsule-type potential curing agent.In addition, worsen, so need the α glycol content making raw material epoxy resin (A) to reduce owing to becoming the cured article physical property such as the intensity of cured article or thermotolerance reduction.Therefore, the α glycol content of epoxy resin (A) is preferably below 10meq/100g, is more preferably below 5meq/100g, more preferably below 3meq/100g.
It should be noted that, when epoxy resin (a3) represented with general formula (4), if remaining hydroxyl concentration or α glycol content high, then except above-mentioned reason, because 2 functional group epoxy resins without cyclohexane ring not belonging to the epoxy resin of more than 3 functional groups increase, so cause the reduction of flame retardant resistance and not preferred.
The epoxy resin (a1) represented with general formula (1) reacted with organo phosphorous compounds at least has 1 aromatic ring, and-O-CH
2-R
1-CH
2-O-structure is required.Aromatic ring contributes to the raising of the flame retardant resistance of phosphorous epoxy resin ,-O-CH
2-R
1-CH
2the lowering viscousity of-O-structure to phosphorous epoxy resin is effective.When not there is-O-CH
2-R
1-CH
2when the aromatic species epoxy resin of-O-structure is as raw material, because lowering viscousity is not enough, so need in order to the lowering viscousity of composition epoxy resin to use aliphatic based epoxy resin isoreactivity thinner in a large number, flame retardant resistance cannot be guaranteed.In addition, if the usage quantity reducing aliphatic based epoxy resin is to guarantee flame retardant resistance, then the viscosity of composition epoxy resin significantly raises, so unfavorable to lowering viscousity, cannot obtain the low viscosity phosphorous epoxy resin composition as target.That is, this 2 functional group epoxy resin (a1) is the glycidyl ether compound of 2 functional group's primary alconols of the carbonatoms 8 ~ 33 at least containing 1 aromatic ring in skeleton.
R in the formula of 2 functional group epoxy resins (a1) that will represent with general formula (1)
1specific examples be illustrated in formula (7) group.In addition, R
1can be the isomer that formula (7) is organized, also can have substituting group.In addition, with regard to R
1, they can be single or two or more.
In formula, j independently represents the integer of 0 or 1 separately.
In formula, j independently represents the integer of 0 or 1 separately.
In 2 functional group epoxy resins (a1) represented with general formula (1), the glycidyl ether compound of the terephthalyl alcohol preferably represented with general formula (8) or the biphenyl that represents with general formula (9) are to the glycidyl ether compound of dimethanol.
2 functional group epoxy resins (a2) represented with general formula (3) reacted with organo phosphorous compounds at least must contain 1 cyclohexane ring.Cyclohexane ring contributes to the raising of the flame retardant resistance of phosphorous epoxy resin, and the aliphatic based epoxy resin without cyclohexane ring cannot guarantee flame retardant resistance.That is, this 2 functional group epoxy resin (a2) is the glycidyl ether compound of 2 functional groups' aliphatic series class primary alconols of the carbonatoms 6 ~ 17 at least containing 1 cyclohexane ring in skeleton.
R in the formula of 2 functional group epoxy resins (a2) that will represent with general formula (3)
2specific examples be illustrated in formula 10 groups.In addition, R
2can be the isomer of formula 10 groups, also can have substituting group.In addition, with regard to R
2, they can be single or two or more.
In 2 functional group epoxy resins (a2) represented with general formula (3), the glycidyl ether compound of the cyclohexanedimethanol preferably represented with general formula (11) or the glycidyl ether compound of Hydrogenated Bisphenol A represented with general formula (12).
The polyfunctional epoxy resin (a3) represented with general formula (4) reacted with organo phosphorous compounds is for having 3 functional group epoxy resins or 4 functional group epoxy resins of the aliphatic chain of carbonatoms 1 ~ 4.Do not containing in the aliphatic epoxy resin of cyclohexane ring, the aliphatic based epoxy resin beyond the polyfunctional epoxy resin represented with general formula (4) cannot guarantee flame retardant resistance.
In the polyfunctional epoxy resin represented with general formula 4 (a3), the glycidyl ether compound of the TriMethylolPropane(TMP) preferably represented with general formula (13).
In addition, the organo phosphorous compounds (B) reacted with epoxy resin (A) is the organo phosphorous compounds (b1) represented with general formula (5) and the organo phosphorous compounds (b2) represented with general formula (6).
The organo phosphorous compounds (b1) represented with general formula (5) for having the organo phosphorous compounds of 2 active hydrogens, the R in formula
5, R
6represent hydrogen or alkyl, separately can be similar and different, can be straight-chain, branched, ring-type, in addition R
5with R
6also bonding formation ring texture.As R
5, R
6specific examples, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, 1-methyl butyl, 1-methyl amyl, octyl group, nonyl, dodecyl, undecyl, dodecyl, benzyl, phenyl, tolyl, xylyl etc. can be listed.In addition, as R
5with R
6bonding forms the example of the group of ring texture, include, for example out sub-cyclobutyl, cyclopentylidene, cyclohexylidene, sub-suberyl, sub-ring octyl group, sub-ring decyl, sub-norcamphyl, biphenylene etc.Ar is arylidene, as the example of concrete example, can list phenylene, xylene, xylylene, naphthylidene, biphenylene etc.In addition, the number of n is 0 or 1.
These organo phosphorous compoundss (b1) are easily obtained (patent documentation 6) with the reaction of monocycle or polynucleation quinone compound by the organo phosphorous compounds (b2) of general formula 6.As the preferred organo phosphorous compounds used in the present invention, the P contained compound (hereinafter referred to as DOPO-HQ) represented with general formula (15) or the organo phosphorous compounds (hereinafter referred to as DOPO-NQ) represented with general formula (16) can be listed, the described P contained compound represented using general formula (15) is as the organo phosphorous compounds represented with general formula (14) 9, 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) (hereinafter referred to as DOPO) and 1, the addition reaction thing of 4-benzoquinones, the described organo phosphorous compounds represented with general formula (16) 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.
The organo phosphorous compounds (b2) represented with general formula (6) for having the organo phosphorous compounds of 1 active hydrogen, the R in formula
7, R
8represent hydrogen or alkyl, separately can be similar and different, can be straight-chain, branched, ring-type, in addition R
7with R
8also bonding formation ring texture.As R
7, R
8specific examples, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, 1-methyl butyl, 1-methyl amyl, octyl group, nonyl, dodecyl, undecyl, dodecyl, benzyl, phenyl, tolyl, xylyl etc. can be listed.In addition, as R
7with R
8bonding forms the example of the group of ring texture, include, for example out sub-cyclobutyl, cyclopentylidene, cyclohexylidene, sub-suberyl, sub-ring octyl group, sub-ring decyl, sub-norcamphyl, biphenylene etc.In addition, the number of m is 0 or 1.The wherein preferred DOPO represented with general formula (14).
For obtaining in organo phosphorous compounds that phosphorous epoxy resin of the present invention uses, (b1)/(b2) weight ratio of the organo phosphorous compounds (b1) represented with general formula (5) and the organo phosphorous compounds (b2) represented with general formula 6 is for 50/50 ~ 100/0, be preferably 65/35 ~ 100/0, be more preferably 80/20 ~ 100/0, more preferably 90/10 ~ 100/0.If not enough (b1)/(b2) weight ratio=0/100 ~ 50/50, although then reduce effectively owing to easily adjusting phosphorus containing ratio to the raising of flame retardant resistance or viscosity, but the reaction of mostly occur 1 functional group's organo phosphorous compounds (b2) of representing with general formula (6) and epoxy group(ing), the 1 following epoxy resin of functional group generates in a large number, overall 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, electric insulation reliability significantly reduces.If (b1)/(b2) scope of weight ratio=50/50 ~ 100/0, then can guarantee enough reactivities, so the physical property that there is not cured article reduces.If the multiplex organo phosphorous compounds (b1) represented with general formula (5), then molecular weight increases, significantly can improve cementability, if the multiplex organo phosphorous compounds (b2) represented with general formula (6), then make easily to adjust phosphorus containing ratio, so need according to object characteristic adjustment usage quantity.In the scope of (b1)/(b2) weight ratio=50/50 ~ 100/0, as long as increase the usage rate of organo phosphorous compounds (b2) when requiring flame retardant resistance further, as long as increase the usage rate of organo phosphorous compounds (b1) when requiring cementability further.
Organo phosphorous compounds can by used in combination with the organo phosphorous compounds (b2) represented with general formula 6 for the pre-synthesis organo phosphorous compounds (b1) represented with general formula (5), also can with the reaction of epoxy resin (A) before the organo phosphorous compounds (b2) that represents with general formula 6 and quinones are reacted.Now, the organo phosphorous compounds (b2) represented with general formula 6 relative to 1 mole, quinones is preferably to react less than 1 mole.If the compound (b2) represented with general formula (6) relative to 1 mole uses the quinones of more than 1 mole, then remaining in the phosphorous epoxy resin obtained have raw material quinones, and the wet fastness of cured article worsens, therefore not preferred.
The epoxy resin Class (A) used in the present invention can carry out in a known manner with the reaction of organo phosphorous compounds (B).As temperature of reaction, can in 100 DEG C ~ 200 DEG C, preferably 120 DEG C ~ 180 DEG C under agitation carry out.Reaction times is determined by the mensuration of carrying out epoxy equivalent (weight).With regard to mensuration, can measure according to the method for JIS K-7236.Epoxy equivalent (weight) is increased, by determining reaction end with comparing of theoretical epoxy equivalent weight by epoxy resin (A) and the reaction of organo phosphorous compounds.
In addition, when speed of response is slow, catalyzer can be used as required to seek the improvement of throughput.Specifically, the tertiary amines such as benzyldimethylamine can be used, the quaternary ammonium salts such as tetramethyl ammonium chloride, triphenyl phosphine, three (2,6-Dimethoxyphenyl) the phosphine class such as phosphine, the microcosmic salt classes such as Ethyltriphenylphosphonium brimide, the various catalyzer such as the imidazoles such as glyoxal ethyline, 2-ethyl-4-methylimidazole.These catalyzer can be used alone or two or more share.
The epoxy equivalent (weight) of the phosphorous epoxy resin obtained by preparation method of the present invention is preferably 200g/eq ~ 600g/eq.When epoxy equivalent (weight) is less than 200g/eq, cementability is poor, if more than 600g/eq, then viscosity increases, and the thermotolerance of the cured article of acquisition is significantly damaged.Therefore, epoxy equivalent (weight) is preferably 200g/eq ~ 600g/eq, is more preferably 230g/eq ~ 550g/eq, more preferably 250g/eq ~ 500g/eq.
The phosphorus containing ratio of the phosphorous epoxy resin obtained by preparation method of the present invention is preferably 1% weight ~ 6% weight.High from the viewpoint of flame retardant resistance preferred phosphorus containing ratio, but along with the rising of phosphorus containing ratio, cause the viscosity of phosphorous epoxy resin to increase or epoxy equivalent (weight) increase, the thermotolerance of the cured article of acquisition is significantly damaged.Therefore, phosphorus containing ratio is preferably 1% weight ~ 6% weight, is more preferably 1.5% weight ~ 4% weight, more preferably 2% weight ~ 3% weight.
The total chlorine amount of the phosphorous epoxy resin obtained by preparation method of the present invention is relevant with the reduction of the electrical reliability of the cured article of acquisition, if increase, then the electrical reliability of cured article reduces, if reduce, then electrical reliability improves.Consider from the electrical reliability of permissible cured article, total chlorine amount is preferably below 0.2% weight, is more preferably below 0.09% weight equal with general sealing material use epoxy resin, more preferably below 0.05% weight.
The melt viscosity of the phosphorous epoxy resin obtained by preparation method of the present invention at 100 DEG C is preferably 1, below 000mPas, is more preferably below 600mPas, more preferably below 300mPas.If the melt viscosity at 100 DEG C is more than 1,000mPas, even if the solidifying agent then using viscosity relatively low, the viscosity of composition epoxy resin still raises, and makes actually operating difficulty, is difficult to obtain normal forming composition.
Not damaging in the scope of characteristic, in the present composition, also blending epoxy resin beyond the phosphorous epoxy resin that obtained by preparation method of the present invention can be had.
Although without the need to carrying out special stipulation to the phosphorus containing ratio relative to epoxy resin ingredient whole in composition epoxy resin of the present invention, high from the viewpoint of flame retardant resistance preferred phosphorus containing ratio, low from the viewpoint of lowering viscousity preferred phosphorus containing ratio.Therefore, for meeting both, being preferably 0.5% weight ~ 5% weight, being more preferably 1% weight ~ 4% weight, more preferably 2% weight ~ 3% weight.
As solidifying agent of the present invention, can use with resol is various polyphenol resene or the anhydrides of representative, with the amine that Dyhard RU 100 or diethyl diaminodiphenyl-methane are representative, hydrazides class, the hardener for epoxy resin that acidic polyester class etc. are conventional, these solidifying agent only can use a kind or use two or more.
In addition, composition epoxy resin of the present invention can use curing catalyst as required.As curing catalyst, phosphine class, quaternary phosphonium salt, tertiary amines, quaternary ammonium salt, imidazolium compounds class, boron trifluoride complex class, 3-(3 can be listed, 4-dichlorophenyl)-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 share epoxy resin, use epoxy curing agent kind, forming method, solidification value, require characteristic, relative to the epoxy resin of 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 can blending inorganic filler, organic filler as required.As the example of filling agent, fused silica, crystalline silica, aluminum oxide, silicon nitride, aluminium hydroxide, talcum powder, mica, calcium carbonate, Calucium Silicate powder, calcium hydroxide, magnesiumcarbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fibre, sapphire whisker, aluminum silicate fiber, silicon carbide fiber, trevira, cellulosic fibre, aramid fiber etc. can be listed.These filling agents are preferably 1 ~ 95% weight in composition epoxy resin.
Composition epoxy resin of the present invention can the various additive such as blending silane coupling agent, antioxidant, releasing agent, defoamer, emulsifying agent, thixotropic agent, smooth agent, fire retardant, pigment as required further.These additives are preferably the scope of 0.01 ~ 20% weight in composition epoxy resin total amount.
Composition epoxy resin of the present invention can according to the method identical with known composition epoxy resin carry out shaping, solidify, make cured article.Forming method, curing can adopt the method identical with known composition epoxy resin, do not need the method that composition epoxy resin of the present invention is intrinsic.
Epoxy resin cured product of the present invention can be made into the forms such as film, adhesive linkage, forming composition, laminate, film.
The effect of invention
Evaluate the forming composition using composition epoxy resin of the present invention to obtain, result, compared with existing low viscosity resin composition, can obtain and have flame retardant resistance and the cured article had compared with low water absorption.This composition epoxy resin known and cured article thereof can be used as the sealing material, formed material, note shaped material, caking agent, mould material, electric insulation coating material etc. that use in the preparation resin combination of the copper clad laminate used in circuit substrate or electronic component.
Embodiment
According to synthesis example, embodiment and comparative example, the present invention to be specifically described below, but technical scope of the present invention is not limited in embodiment.It should be noted that, as long as without specified otherwise, the blending number of each composition in embodiment and comparative example all represents weight part.
In addition, following analytical procedure is used in the present invention.
Epoxy equivalent (weight): the method recorded in JIS K-7236.Namely, sample is dissolved in the chloroform of 10mL, add the 20% tetraethylammonium bromide acetum of the aceticanhydride of 20mL, 10mL respectively, use potential difference titration apparatus to carry out titration with 0.1mol/L perchloric acid acetate standard liquid, measure the epoxy equivalent (weight) contained by epoxy resin according to the concentration of all ingredients and addition and titer.
Perchloro-amount: the method recorded in JIS K-7243-3.That is, sample is dissolved in the diethylene glycol monobutyl ether of 25mL, adds the 1,2-PD solution of the 1mol/L potassium hydroxide of 25mL, on hot plate, heating makes it reaction for 10 minutes under reflux.To be cooled to room temperature, add the aceticanhydride of 50mL, use potential difference titration apparatus to carry out titration with 0.01mol/L silver nitrate solution, measure the perchloro-amount contained by epoxy resin according to the concentration of all ingredients and additive and titer.
Viscosity: the method recorded in JIS K-7233.That is, in 500mL cylinder tank, take the resin of 400g, place in the Water Tank with Temp.-controlled of 25 ± 0.2 DEG C and keep constant temperature in 5 hours, the rotor of rotational viscosimeter be impregnated in resin and measure.
Softening temperature: the method recorded in JIS K-7234.That is, according to ring and ball method by sample load in regulation ring in, in glycerol bath, keep level, the ball of regulation be placed in sample central authorities, with 5 DEG C/min carry out intensifications mensuration.
Hydroxyl concentration: relative to the amount of hydroxyl groups contained by epoxy resin, add the phenylcarbimide of more than equivalent and the dibutyl toxilic acid tin as catalyzer, after making hydroxyl and isocyanic ester fully react, relative to the equivalent of used phenylcarbimide, be added on the dibutylamine on this amount, consume remaining phenylcarbimide, finally carry out titration with perchloric acid, according to the concentration of all ingredients and addition and titer, measure the hydroxyl concentration contained by epoxy resin.
Phosphorus containing ratio: add sulfuric acid, hydrochloric acid, perchloric acid in sample, heating carries out wet ashing, by all phosphorus atom by ortho-phosphoric acid.Metavanadate and molybdate reaction is made in sulfuric acid solution, measure the absorbancy of molybdic acid phosphorus vanadium complexes under 420nm generated, represent the phosphorus atom content obtained according to the typical curve made in advance with % weight, measure the phosphorus containing ratio contained by epoxy resin.
α glycol content: the method recorded in JIS K-7146.
That is, after add chloroform dissolving in sample, add ortho-periodic acid (acid of オ ル ト Over ヨ ウ element) solution, make it reaction 2 hours.Then, add liquor kalii iodide, the iodine Sulfothiorine of generation is carried out titration, measure the α glycol content contained by epoxy resin according to the concentration of all ingredients and addition and titer.
Dissolve viscosity: use cone and plate viscometer (East Asia Industrial Co., Ltd system, MOEDL CV-1S), rotor uses 5 pools cone (Φ: 24mm, θ: 0.5 °), measures at the mensuration temperature of 100 DEG C.
Flame retardant resistance: according to UL (Underwriters Laboratories Inc.) specification, UL94 vertical test method measures, and carries out judging (flame retardant resistance is poorer more rearward) according to 4 levels such as V-0, V-1, V-2, the NG (without flame retardant resistance) of the criterion as this specification.
Cementability: the method be as the criterion with JIS C-6481 5.7.That is, between 1 prepreg and all the other 3, stripping mensuration is carried out with the speed of 50mm/min in rectangular direction.
Rate of moisture absorption: the method be as the criterion with JIS C-6481 5.13.Namely, use is cut into the test film of 50mm × 50mm, to dry weight after being determined in the baking oven of 50 DEG C dry 24 hours, be then determined at be adjusted to 85 DEG C/85%RH treatment trough in the weight of keeping after 72 hours, measure rate of moisture absorption according to the increasing amount relative to dry weight.
Thermotolerance: the method be as the criterion with IPC-TM-650,2.4.24.1.That is, utilize the mensuration of the separation time of TMA device, in TMA device, remain on the steady temperature of 260 DEG C, when the time producing transposition to test film cracking is more than 10 minutes, be judged to be zero, when less than 10 minutes, be judged to be ×.It should be noted that, TMA device uses SII NanoTechnology Inc. (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー Co., Ltd.) TMA/SS120U processed.
Chlorion: pulverized by cured article, be that the sample of the particle diameter of 1mm on the lower 2mm of sieve, sieve is tested in the pressure cooking that 150 DEG C are carried out 20 hours by whole grain, then by the chlorion in ion-chromatographic determination extraction water, the concentration be converted in cured article is tried to achieve.
Embodiment 1.
To being provided with whipping appts, thermometer, Epotohto (エ ポ ト ー ト) TX-0929 (Toto Kasei KK's system of the 547.4g of 2 functional groups' aromatic species epoxy resin (a1) as general formula 1 is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, terephthalyl alcohol 2-glycidyl ether resin, 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 of the 252.6g of organo phosphorous compounds, trade(brand)name: HCA-HQ, hydroxyl equivalent: 162g/eq, phosphorus containing ratio: 9.5% weight), while stirring, 130 DEG C are heated to by sheathing formula well heater, triphenyl phosphine (the Bei Xing KCC system of the 0.25g as catalyzer is added when reaching 130 DEG C, trade(brand)name: TPP), temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-1) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-1) is illustrated in table 1.
Embodiment 2.
To being provided with whipping appts, thermometer, Epotohto (the エ ポ ト ー ト) TX-0929 (above-mentioned) of the 602.5g of 2 functional groups' aromatic species epoxy resin (a1) as general formula 1 is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, as the DOPO-NQ (9 of the 197.5g of organo phosphorous compounds, 10-dihydro-9-oxy is mixed 1 of-10-phospho hetero phenanthrene-10-oxide compound, 4-naphthoquinones adducts, hydroxyl equivalent: 187g/eq, phosphorus content: 8.1% weight), while stirring, 130 DEG C are heated to by sheathing formula well heater, add the 2-ethyl-4-methylimidazole of the 0.05g as catalyzer (four countries change into Co., Ltd.'s system when reaching 130 DEG C, trade(brand)name: 2E4MZ), temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-2) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-2) is illustrated in table 1.
Embodiment 3.
To being provided with whipping appts, thermometer, Epotohto (エ ポ ト ー ト) TX-0934 (Toto Kasei KK's system of the 608.7g of 2 functional groups' aromatic species epoxy resin (a1) as general formula 1 is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, 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 of 75.0g, trade(brand)name: HCA, phosphorus containing ratio: 14.2% weight), while stirring, 130 DEG C are heated to by sheathing formula well heater, the triphenyl phosphine (above-mentioned) of the 0.19g as catalyzer is added when reaching 130 DEG C, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-3) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-3) is illustrated in table 1.
Embodiment 4.
The DOPO (above-mentioned) of the 182.0g as organo phosphorous compounds and the toluene of 420g is added in the removable flask of 4 neck glass system being provided with whipping appts, thermometer, cooling tube, nitrogen gatherer, heat while stirring under nitrogen atmosphere, make it to dissolve completely.Then, while noticing the intensification caused because of reaction heat, gradation drops into the 1,4-naphthoquinone (Kawasaki changes into Co., Ltd.'s system, 3% moisture product) as the 56.7g of quinones.1,4-naphthoquinone now and the mol ratio of DOPO are 1,4-naphthoquinone/DOPO=0.41.After reacting by heating, add 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 groups' aromatic species epoxy resin (a1) as general formula 1
1for 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), stir while importing nitrogen, heat below 130 DEG C, toluene is got rid of to outside system.Then, add the triphenyl phosphine (above-mentioned) of the 0.24g as catalyzer, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-4) of obtained 790g.The proterties of obtained phosphorous epoxy resin (E-4) is illustrated in table 1.
Embodiment 5.
To being provided with whipping appts, thermometer, Epotohto (エ ポ ト ー ト) ZX-1658 (Toto Kasei KK's system of the 547.4g of 2 functional groups' aliphatic series based epoxy resin (a2) as general formula (3) is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, 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, while stirring, 130 DEG C are heated to by sheathing formula well heater, 1 hour is incubated when reaching 130 DEG C, then the triphenyl phosphine (above-mentioned) of the 0.25g as catalyzer is added, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-5) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-5) is illustrated in table 1.
Embodiment 6.
To being provided with whipping appts, thermometer, HBPADGE (Maruzen Petrochemical Co., Ltd.'s system of the 632.0g of 2 functional groups' aliphatic series based epoxy resin (a2) as general formula (3) is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, hydrogenated bisphenol A 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, while stirring, 130 DEG C are heated to by sheathing formula well heater, 1 hour is incubated when reaching 130 DEG C, then the triphenyl phosphine (above-mentioned) of the 0.17g as catalyzer is added, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-6) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-6) is illustrated in table 1.
Embodiment 7.
To being provided with whipping appts, thermometer, Epotohto (エ ポ ト ー ト) ZX-1542 (Toto Kasei KK's system of the 570.0g of polyfunctional group aliphatic series based epoxy resin (a3) as general formula (4) is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, 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, while stirring, 130 DEG C are heated to by sheathing formula well heater, the triphenyl phosphine (above-mentioned) of the 0.23g as catalyzer is added when reaching 130 DEG C, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-7) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-7) is illustrated in table 1.
[table 1]
Comparative example 1.
To being provided with whipping appts, thermometer, Epotohto (エ ポ ト ー ト) PG-207GS (Toto Kasei KK's system of the 632.0g as epoxy resin is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, 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, while stirring, 130 DEG C are heated to by sheathing formula well heater, the triphenyl phosphine (above-mentioned) of the 0.17g as catalyzer is added when reaching 130 DEG C, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-8) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-8) is illustrated in table 2.
Comparative example 2.
To being provided with whipping appts, thermometer, Epotohto (the エ ポ ト ー ト) TX-0917 (above-mentioned) of the 757.9g as epoxy resin is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, as the DOPO-HQ (above-mentioned) of the 42.1g of organo phosphorous compounds, while stirring, 130 DEG C are heated to by sheathing formula well heater, the triphenyl phosphine (above-mentioned) of the 0.05g as catalyzer is added when reaching 130 DEG C, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-9) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-9) is illustrated in table 2.
Comparative example 3.
To being provided with whipping appts, thermometer, Epotohto (the エ ポ ト ー ト) TX-0917 (above-mentioned) of the 480.0g as epoxy resin is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, as the DOPO (above-mentioned) of the 220.0g of organo phosphorous compounds and the DOPO-HQ (above-mentioned) of 100.0g, while stirring, 130 DEG C are heated to by sheathing formula well heater, the triphenyl phosphine (above-mentioned) of the 0.32g as catalyzer is added when reaching 130 DEG C, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-10) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-10) is illustrated in table 2.
Comparative example 4.
To being provided with whipping appts, thermometer, Epotohto (the エ ポ ト ー ト) TX-0934 (above-mentioned) of the 505.0g as epoxy resin is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, as the DOPO-HQ (above-mentioned) of the 295.0g of organo phosphorous compounds, while stirring, 130 DEG C are heated to by sheathing formula well heater, the triphenyl phosphine (above-mentioned) of the 0.30g as catalyzer is added when reaching 130 DEG C, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-11) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-11) is illustrated in table 2.
Comparative example 5.
The DOPO (above-mentioned) of the 137.6g as organo phosphorous compounds and the toluene of 330g is added in the removable flask of 4 neck glass system being provided with whipping appts, thermometer, cooling tube, nitrogen gatherer, heat while stirring under nitrogen atmosphere, make it to dissolve completely.Then, while noticing the intensification caused because of reaction heat, gradation drops into the 1,4-naphthoquinone (above-mentioned) as the 31.3g of quinones.1,4-naphthoquinone now and the mol ratio of DOPO are 1,4-naphthoquinone/DOPO=0.13.After reacting by heating, add Epotohto (エ Port ト ー ト) ZX-1659 (Toto Kasei KK's system, hydrogenated bisphenol A type 2-glycidyl ether resin, the epoxy equivalent (weight): 215g/eq of the 632.0g as epoxy resin, total chlorine: 0.45% weight, viscosity: 1,500mPas, hydroxyl concentration: 230meq/100g, α glycol content: 11meq/100g), stir while importing nitrogen, heat below 130 DEG C, toluene is got rid of to outside system.Then, add the triphenyl phosphine (above-mentioned) of the 0.17g as catalyzer, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-13) of obtained 790g.The proterties of obtained phosphorous epoxy resin (E-12) is illustrated in table 2.
Comparative example 6.
To being provided with whipping appts, thermometer, Epotohto (エ ポ ト ー ト) ZX-1542 (Toto Kasei KK's system of the 570.0g as epoxy resin is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, TriMethylolPropane(TMP) polyglycidyl ether resins, 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, while stirring, 130 DEG C are heated to by sheathing formula well heater, the triphenyl phosphine (above-mentioned) of the 0.23g as catalyzer is added when reaching 130 DEG C, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-13) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-13) is illustrated in table 2.
Comparative example 7.
To being provided with whipping appts, thermometer, Epotohto (エ ポ ト ー ト) YDF-170 (Toto Kasei KK's system of the 547.4g as epoxy resin is added in the removable flask of 4 neck glass system of nitrogen gatherer and cooling tube, 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, while stirring, 130 DEG C are heated to by sheathing formula well heater, the triphenyl phosphine (above-mentioned) of the 0.25g as catalyzer is added when reaching 130 DEG C, temperature of reaction is being remained on the simultaneous reactions 4 hours of 160 DEG C ~ 165 DEG C, the phosphorous epoxy resin (E-14) of obtained 795g.The proterties of obtained phosphorous epoxy resin (E-14) is illustrated in table 2.
[table 2]
Embodiment 8 ~ 10, comparative example 8 ~ 11
According to blending prescription blending phosphorous epoxy resin, solidifying agent, curing catalyst etc. shown in table 3.Phosphorous epoxy resin methylethylketone is dissolved, add the Dyhard RU 100 (DICY as solidifying agent being dissolved in methylcyclohexane, dimethyl formamide in advance, Ahew: 21.0g/eq) and as the 2-ethyl-4-methylimidazole (above-mentioned) of curing catalyst, prepare resin composition Chinese varnish, make nonvolatile component reach 50% weight.Then, use obtained resinous varnish, flood woven fiber glass (Nitto Boseiki Co., Ltd.'s system as base material, WEA 116E 106S 136, thick 100 μm), the woven fiber glass of dipping is carried out the drying of 8 minutes with the heated air circulation type baking oven of 150 DEG C, obtained prepreg (プ リ プ レ グ).Then, 4 obtained prepregs are overlapping, carry out heating and pressurizeing under the condition of 130 DEG C × 15 minutes and 170 DEG C × 2.0MPa × 70 minute, obtain the veneer sheet that 0.5mm is thick.For each obtained veneer sheet, the various physical property such as flame retardant resistance, cementability, rate of moisture absorption are tested.Its result is illustrated in table 4.
[table 3]
Note) 2E4MZ is 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 using aliphatic class phosphorous epoxy resin, so cementability is good, but poor fire, resistance to water absorbability is also poor.Comparative example 9 is the phosphorous epoxy resin of general formula 1, but 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 due to phosphorus containing ratio.Comparative example 10 is the phosphorous epoxy resin of general formula 1, but because epoxy equivalent (weight) is up to 705g/eq, so poor heat resistance, because the weight ratio of phosphorus compound in raw material (b1)/phosphorus compound (b2) is 31/69, lower than 50/50, so cementability is poor, resistance to 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 also up to 1,300mPas, although so cementability is good, but poor heat resistance.On the other side, all embodiments not only can guarantee enough flame retardant resistances, and cementability is good, and resistance to water absorbability and thermotolerance might as well.
Embodiment 11 ~ 14, comparative example 12 ~ 14
According to blending prescription blending phosphorous epoxy resin, solidifying agent, curing catalyst etc. shown in table 5.As solidifying agent, use diethyl 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 to while 50 DEG C, stir homogenize, obtained composition epoxy resin.Deaeration is carried out to obtained composition epoxy resin, injects mould, under the temperature condition of 150 DEG C × 120 minutes, make it solidification, the cured article test film that obtained 2mm is thick.For obtained cured article test film, the various physical property such as chlorion, flame retardant resistance, rate of moisture absorption are tested.Its result is illustrated in table 6.It should be noted that, in comparative example 12, as epoxy resin, 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, 3-phenylene two-two-2, 6-tolyl phosphate (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), the phosphorus containing ratio in composition epoxy resin is made to reach 2.0% weight.
[table 5]
Note) 2E4MZ is 2-ethyl-4-methylimidazole
[table 6]
| ? | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Comparative example 12 | Comparative example 13 | Comparative example 14 |
| Chlorion (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 because total chlorine of raw material epoxy resin is up to 0.45% weight, so more than embodiment about 5 ~ 10 times of the chlorion of cured article.This shows less reliable.In addition, due to hydroxyl concentration up to 230meq/100g, α glycol content also up to 11meq/100g, so resistance to water absorbability is also poor.In addition, because the weight ratio of phosphorus compound in raw material (b1)/phosphorus compound (b2) is 43/57, lower than 50/50, so the solid state of cured article is deteriorated, 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 resistance to water absorbability is poor, because the weight ratio of phosphorus compound in raw material (b1)/phosphorus compound (b2) is 39/61, lower than 50/50, so the solid state of cured article is deteriorated, flame retardant resistance is also slightly poor.Comparative example 14 is the composition epoxy resin that blending has fire retardant in conventional low chlorine liquid resin, although make phosphorus containing ratio consistent with embodiment, flame retardant resistance is still poor, and resistance to water absorbability is also poor.On the other side, all embodiments not only can guarantee enough flame retardant resistances, and chlorion is few, and resistance to water absorbability might as well.This shows good reliability.
Embodiment 15 ~ 17, comparative example 15 ~ 17
According to blending prescription blending phosphorous epoxy resin, solidifying agent, curing catalyst etc. shown in table 7.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 DEG C), be heated to while 120 DEG C, stir homogenize, obtained composition epoxy resin.Deaeration is carried out to obtained composition epoxy resin, injects mould, under the temperature condition of 150 DEG C × 120 minutes+180 DEG C × 60 minutes, make it solidification, the cured article test film that obtained 2mm is thick.For obtained cured article test film, the various physical property such as formability, flame retardant resistance, rate of moisture absorption are tested.Its result is illustrated in table 8.It should be noted that, Epotohto (エ ポ ト ー ト) ZX-1059 (above-mentioned) is share as the epoxy resin beyond phosphorous epoxy resin in embodiment 14, Epotohto (エ ポ ト ー ト) ZX-1542 (Toto Kasei KK's system is share as the epoxy resin beyond phosphorous epoxy resin in comparative example 16, TriMethylolPropane(TMP) polyglycidyl ether resins, epoxy equivalent (weight): 122g/eq, total chlorine: 0.065% weight, viscosity: 80mPas).
[table 7]
Note) 2E4MZ is 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 using aliphatic class phosphorous epoxy resin, so poor fire, resistance to water absorbability is also poor.The phosphorous epoxy resin of comparative example 16 for being obtained by method for making disclosed in patent documentation 4, but be not the phosphorous epoxy resin of general formula 1, so the viscosity of composition epoxy resin is too high, the test film cannot prepared needed for test owing to being difficult to formed in mould cause.Comparative example 17 for share thinner to fall low viscous composition epoxy resin in the phosphorous epoxy resin obtained by method for making disclosed in patent documentation 4, although formability is improved, flame retardant resistance worsens, and wet fastness also worsens.On the other side, all embodiments not only can guarantee enough flame retardant resistances, and good moldability, and resistance to water absorbability might as well.
Utilizability in industry
Composition epoxy resin of the present invention is 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 the epoxy resin (a1) represented with general formula (1), the epoxy resin (A) of at least one composition in the epoxy resin (a2) represented with general formula (3) or the epoxy resin (a3) represented with general formula (4) with react by the organo phosphorous compounds (b1) represented with general formula (5) and/or with the organo phosphorous compounds (B) that the organo phosphorous compounds (b2) that general formula (6) represents is formed, thus to prepare epoxy equivalent (weight) be 200 ~ 600g/eq, phosphorus containing ratio is in the method for the phosphorous epoxy resin of 1 ~ 6% weight, the hydroxyl concentration of epoxy resin (A) is below 200meq/100g, total chlorine amount is below 0.4% weight, α glycol content is below 10meg/100g, and the weight ratio of organo phosphorous compounds (b1)/organo phosphorous compounds (b2) is 50/50 ~ 100/0 in organo phosphorous compounds (B),
R in formula
1for the alkyl of carbonatoms 6 ~ 31, described alkyl at least has 1 aromatic ring, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, any one in G expression (2) or hydrogen;
R in formula
2for the aliphatic hydrocarbyl of carbonatoms 6 ~ 17, described aliphatic hydrocarbyl can be monocycle or heterocycle, at least has 1 cyclohexane ring, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, any one in G expression (2) or hydrogen;
R in formula
3be individually the aliphatic hydrocarbyl that can contain the carbonatoms 1 ~ 4 of Sauerstoffatom, nitrogen-atoms, sulphur atom, R
4expression-R
3-OG ,-R
3any one in-H or hydrogen, any one in G expression (2) or hydrogen, k represents the integer of 0 or 1;
R in formula
5, R
6represent hydrogen or alkyl, separately can be similar and different, can be straight-chain, branched, ring-type, in addition R
5with R
6bonding formation ring texture, n represents the integer of 0 or 1, and Ar represents any one in benzene, biphenyl, naphthalene, anthracene, phenanthrene and hydrocarbon substituent thereof;
R in formula
7, R
8represent hydrogen or alkyl, separately can be similar and different, can be straight-chain, branched, ring-type, in addition R
7with R
8bonding formation ring texture, m represents the integer of 0 or 1.
2. the preparation method of the phosphorous epoxy resin of claim 1, it is characterized in that, the epoxy resin (A) of claim 1 is at least a kind in the epoxy resin represented with general formula (7), general formula (8), general formula (9), general formula (10) or general formula (11)
。
3. the preparation method of the phosphorous epoxy resin of claim 1 or 2, is characterized in that, the organo phosphorous compounds (b1) of claim 1 is at least a kind in the organo phosphorous compounds represented with general formula (12) or general formula (13)
。
4. the preparation method of the phosphorous epoxy resin of claim 1 or 2, is characterized in that, the organo phosphorous compounds (b2) of claim 1 is the organo phosphorous compounds represented with general formula (14)
。
5. composition epoxy resin, is characterized in that, is required composition containing the phosphorous epoxy resin obtained by the preparation method of the phosphorous epoxy resin any one of claim 1 ~ 4 and solidifying agent.
6. cured article, described cured article is by obtaining the epoxy resin composition of claim 5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN102741314B true CN102741314B (en) | 2014-12-31 |
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| JP (1) | JP5544184B2 (en) |
| KR (1) | KR101794366B1 (en) |
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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 |
| CN103333464B (en) * | 2013-06-28 | 2015-12-23 | 青岛富斯林化工科技有限公司 | A kind of phosphor-containing halogen-free fire retarded epoxy resin composition and application |
| 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 |
| JP6770793B2 (en) * | 2015-08-19 | 2020-10-21 | 日鉄ケミカル＆マテリアル株式会社 | Flame-retardant epoxy resin composition and its cured product |
| CN110719926B (en) * | 2017-06-07 | 2022-05-13 | Dic株式会社 | Epoxy resin, method for producing same, epoxy resin composition, and cured product 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 |
| JP4753475B2 (en) * | 2001-01-30 | 2011-08-24 | 株式会社Ａｄｅｋａ | Epoxy resin composition |
| 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 |
| JP5632163B2 (en) * | 2007-11-09 | 2014-11-26 | 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 |
| 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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| KR20120140648A (en) | 2012-12-31 |
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| JP5544184B2 (en) | 2014-07-09 |
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