CN101573428A - Phosphorus-containing flame retardant and curable flame -retarded resin compositions containing the same - Google Patents
Phosphorus-containing flame retardant and curable flame -retarded resin compositions containing the same Download PDFInfo
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Abstract
The invention aims at providing a phosphorus-containing flame retardant free from halogen compounds; and curable flame-retarded resin compositions containing the flame retardant, which are curable through radical polymerization and excellent in curability and which can give cured articles excellent in flame retardance, curing properties, and flexibility. The invention relates to a phosphorus-containing flame retardant obtained by reacting (meth)acryloyl of a polyfunctional (meth)acrylate having a specific structure with a phosphorus compound having a P-H bond; and curable flame-retarded resin compositions each comprising the flame retardant, an alkali-soluble resin, a (meth)acrylate compound, an epoxy resin, a photopolymerization initiator and, if necessary, a filler.
Description
Technology neck city
The present invention relates to the phosphonium flame retardant of halide not and contain this phosphonium flame retardant, can be solidified by radical polymerization, be suitable for electric substrate, electronic unit, the solidified nature flame retardant resin composition of (solder resist) material etc. that is particularly suitable for flexible welding resistance.
Background technology
The resin that in electric installation, electronic unit etc., uses, consider that from preventing security viewpoints such as fire hope has flame retardant resistance, before this, based on containing of bromide organic halogen compound as fire retardant, can use the solidified nature flame retardant resin composition that is engaged in the curable resin.Cooperated the solidified nature flame retardant resin composition that contains organic halogen compound, has excellent flame, but this solidified nature flame retardant resin composition might produce hazardous compounds such as corrosive hydrogen halide when burning, produce the problem that environment is impacted.Therefore, instead contain the fire retardant of organic halogen compound, proposed phosphate compounds such as trialkylphosphate and triaryl phosphate and reached the solidified nature flame retardant resin composition that in curable resin, cooperates red phosphorus.
But above-mentioned phosphate compounds is when cooperating in curable resin, hydrolysis takes place in resulting solidified nature flame retardant resin composition, easily produces the free phosphoric acid radical ion, adopt the cured article of this solidified nature flame retardant resin composition, electrical characteristic are worsened.As the fire retardant that prevents this hydrolysis, employing aromatic condensation type phosphoric acid ester (for example, patent documentation 1 and 2) has been proposed here.But aromatic condensation type phosphoric acid ester when use level increases, is oozed out (bleedout) from this aromatic condensation type phosphoric acid ester of cured article, so there is the problem that limits its consumption.
As its countermeasure, proposed to adopt phosphorus compound or the phosphorous epoxy resin (patent documentation 3, patent documentation 4, patent documentation 5) of adding response type in the solidified resin matrix.
But, the phosphorus compound of these response types or phosphorous epoxy resin, when independent use can be given full play to the amount of flame retardant resistance, it is hard and crisp that cured article becomes, and for example, uses in the solder resist material that can not use in flexible substrate.In addition, patent documentation 6 proposes, make (methyl) acrylic compound and reactive phosphorus compound react resulting phosphoric acrylic ester compound, but the balance of the flexibility of light sensitivity and cured article shortcoming, low to the adaptability of the solder resist material that uses in the flexible substrate.
Patent documentation 1: the spy opens flat 5-1079 communique
Patent documentation 2: the spy opens flat 8-277344 communique
Patent documentation 3: the spy opens flat 4-11662 communique
Patent documentation 4: the spy opens flat 11-279258 communique
Patent documentation 5: the spy opens the 2000-309623 communique
Patent documentation 6: the spy opens the 2002-121245 communique
Summary of the invention
The problem that invention will solve
The purpose of this invention is to provide the not phosphonium flame retardant and the solidified nature flame retardant resin composition of halide, said composition contains this phosphonium flame retardant, and can be solidified by radical polymerization, obtain the solidified nature excellence, simultaneously the cured article of flame retardant resistance, solidified nature, flexibility excellence.
Be used to solve the means of problem
The inventor etc. have carried out concentrated discussion in order to solve above-mentioned problem.The result as can be known; (methyl) acryl with multi-functional (methyl) acrylic compound of ad hoc structure reacts resulting phosphonium flame retardant with the phosphorus compound with P-H key; preferred (methyl) acryl and the phosphorus compound with the P-H key solidified nature flame retardant resin composition that reacts resulting phosphonium flame retardant and contain this phosphonium flame retardant with specific molar ratio; can solve above-mentioned problem, finish the present invention based on this opinion.
That is, the present invention relates to:
(1) phosphonium flame retardant, it is resulting with the phosphorus compound reaction with P-H key by (methyl) acryl of multi-functional (methyl) acrylic compound of following formula (1) expression:
Formula (1)
[changing 1]
(in the formula, R
1Expression hydrogen atom or methyl; In addition, the integer of n+m+l+o+p+q=0～12).
(2) according to the phosphonium flame retardant of record in above-mentioned (1), wherein, in formula (1), n+m+l+o+p+q is 3～12 integer.
(3) according to the phosphonium flame retardant of putting down in writing in above-mentioned (1) or (2); it obtains (methyl) acryl and the compound reaction with P-H key; wherein, with respect to 1 mole of (methyl) acryl, the phosphorus compound with P-H key is 0.35～0.7 mole.
(4) according to the phosphonium flame retardant of any one record in above-mentioned (1)～(3), wherein, the phosphorus compound with P-H key is the phosphine oxide compound with following formula (2) or formula (3) expression:
Formula (2)
[changing 2]
(in the formula, R
2And R
3Represent the fatty group of hydrogen atom, carbon number 1～10 or the aromatic series base of carbon number 6～10 respectively independently, r and s represent 1～4 integer respectively.As r and s when being a plurality of, each R
2And R
3Respectively both can be identical also can be inequality);
Formula (3)
[changing 3]
(in the formula, R
4And R
5Represent the fatty group of hydrogen atom, carbon number 1～10 or the aromatic series base of carbon number 6～10 respectively independently, t and u represent 1～5 integer.As t and u when being a plurality of, each R
4And R
5Respectively both can be identical also can be inequality).
(5) solidified nature flame retardant resin composition wherein contains the phosphonium flame retardant of any one record in alkali soluble resins, (methyl) acrylic compound, Resins, epoxy, Photoepolymerizationinitiater initiater and above-mentioned (1)～(4).
(6) according to the solidified nature flame retardant resin composition of record in above-mentioned (5), its be with have alkali soluble resins 20～70 quality %, (methyl) acrylic compound 5～30 quality %, Resins, epoxy 5～50 quality %, Photoepolymerizationinitiater initiater 1～10 quality %, and above-mentioned (1)～(4) in phosphonium flame retardant 5～40 quality % of any one record cooperate and form.
The invention effect
According to the present invention, the not phosphonium flame retardant of halide can be provided, and the solidified nature flame retardant resin composition, said composition contains this phosphonium flame retardant, and can be solidified by radical polymerization, obtain the solidified nature excellence, simultaneously the cured article of flame retardant resistance, solidified nature, flexibility excellence.
Embodiment
Below the present invention is described in detail.
The present invention relates to the solidified nature flame retardant resin composition; wherein contain: (methyl) acryl by (methyl) acrylic compound of following formula (1) expression reacts resulting phosphonium flame retardant with the phosphorus compound with P-H key; preferably contain: with respect to 1 mole of (methyl) acryl, by the phosphonium flame retardant that obtains with phosphorus compound 0.35～0.7 molar reactive with P-H key.
Compound by following formula (1) expression, it is the hydroxyl of Dipentaerythritol, compound (the n+m+l+o+p+q=0 that adopts (methyl) vinylformic acid to carry out dehydration condensation and obtain, for example, Dipentaerythritol six (methyl) acrylate), or on the hydroxyl of Dipentaerythritol behind the addition caprolactone, again the hydroxyl that generates is carried out dehydration condensation with (methyl) vinylformic acid and the compound that obtains.As the latter's concrete goods, can enumerate KAYARAD (registered trademark) DPCA-30 that Nippon Kayaku K. K makes (in the following formula (1), R
1Be hydrogen atom, n+m+o+p+q+r=3), DPCA-60 (in the following formula (1), R
1Be hydrogen atom, n+m+o+p+q+r=6), DPCA-120 (in the following formula (1), R
1Be hydrogen atom, n+m+o+p+q+r=12).When adopting Dipentaerythritol six (methyl) acrylate; when the phosphorus compound addition amount with P-H key after a little while, lose flexibility, so with respect to 1 mole of (methyl) acryl; phosphorus compound with P-H key is in 0.5～0.7 molar range, and it is preferred making reaction.
In addition, when n+m+o+p+q+r=3～12, the compound of above-mentioned formula (1) owing to have 6 (methyl) acryls in 1 molecule, has excellent solidified nature, simultaneously, because the effect of caprolactone residue also has flexibility.(methyl) acryl addition of the compound of through type (1) has the compound of P-H key, can import phosphorus atom.
Consider from the stability viewpoint of flame retardant resistance and compound,, can enumerate compound with above-mentioned formula (2) and formula (3) expression as the compound that preferably has the P-H key.
R in above-mentioned formula (2) and the formula (3)
2, R
3, R
4And R
5Object lesson, as the fatty group of carbon number 1～10, can enumerate methyl, ethyl, n-propyl, normal-butyl, hexyl, 2-ethylhexyl etc., as the aromatic series base of carbon number 6～10, can enumerate phenyl, tolyl, xylyl, naphthyl etc.Particularly preferred compound can be enumerated the R with following formula (4) expression
2, R
3, R
4And R
5Any one is the compound (9 of hydrogen atom, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound, Sanko Co., Ltd., trade(brand)name HCA), with the diphenyl phosphine oxide of formula (5) expression, with two (2-aminomethyl phenyl) phosphine oxides of formula (6) expression, with two (2 of formula (7) expression, the 5-3,5-dimethylphenyl) two (2 of phosphine oxide, usefulness formula (8) expression, 4, the 6-trimethylphenyl) phosphine oxide:
Formula (4)
[changing 4]
Formula (5)
[changing 5]
Formula (6)
[changing 6]
Formula (7)
[changing 7]
Formula (8)
[changing 8]
The addition amount of compound with relative formula of compound (1) of P-H key, the scope of 1 mole suitable 0.35～0.7 mole of (methyl) acryl relatively, preferred 0.35～0.5 mole.In the time of in the addition amount is in this scope, can obtain sufficient flame retardant resistance, and thermotolerance does not reduce yet.In addition, as mentioned above, when n+m+l+o+p+q=0, relatively 1 mole of (methyl) acryl from obtaining flexibility, is preferred 0.5～0.7 mole scope.
(methyl) propenyl compound of above-mentioned formula (1) expression and the reaction with P contained compound of P-H key for example, are undertaken by the reaction formula of following formula (9), can obtain phosphonium flame retardant.Method as reaction can adopt general method, mixes the heating of 2 limits at the reaction vessel inner edge and gets final product, and does not need catalyzer especially.Coronite is blown into the dry air limit carries out, 50～180 ℃ of temperature, preferred 100～130 ℃, and the reaction times is 0.5～50 hour.Cross when low when temperature, reaction is carried out slowly losing time, and when temperature was too high, (methyl) propenyl carried out polyreaction, generated the gelation thing.Also can not use solvent during reaction, but also can select inert solvent reaction according to the solvability of raw material and temperature of reaction.
Formula (9)
[changing 9]
(R
2, R
3, r and s represent implication same as described above, X represents alkyl).
So, the preferred phosphorus content of resulting phosphonium flame retardant is 1～9 quality %, more preferably 2～8.5 quality %.In the time of in phosphorus content is in 1～9 quality % scope, the presenting fully of flame retardant resistance, but do not reduce with the intermiscibility of other resinous principles, solidified nature does not reduce yet.
Phosphonium flame retardant of the present invention, owing to form P-C key to hydrolysis-stable, compare with phosphoric acid ester fire retardant as general fire retardant, the hydrolytic resistance height, the cured article that contains the solidified nature flame retardant resin composition of this phosphonium flame retardant, also have flexibility, can be preferred for the purposes that printed wiring board, electronic unit etc. require insulativity, be particularly suitable for the welding resistance purposes of used in flexible substrate.
Secondly, the solidified nature flame retardant resin composition is illustrated.
Solidified nature flame retardant resin composition of the present invention can contain various resinous principles, filler, fiber reinforced material, additive etc. according to purposes.For example, as the welding resistance purposes, except that phosphonium flame retardant of the present invention, general (1) alkali soluble resins that uses as principal constituent; (2) (methyl) acrylic compound; (3) Resins, epoxy; (4) Photoepolymerizationinitiater initiater; (5) filler as required etc.
(1) alkali soluble resins
Alkali soluble resins owing to contain carboxyl in the molecule, when dissolved in alkaline developer simultaneously, also use with the purpose of basic rerum naturas such as the thermotolerance of giving tunicle against corrosion, hardness, flexibility.
As alkali soluble resins, can enumerate the hydroxyl of the acrylic acid epoxy of addition in the following Resins, epoxy (methyl) (methyl) acrylate, with anhydride reactions such as succinyl oxide, tetrahydrochysene anhydride phthalic acid, methyl six hydrogen anhydride phthalic acids, six hydrogen anhydride phthalic acids and the Epocryl that obtains with carboxyl.As Resins, epoxy used herein, for example, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, tetramethyl-bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, Cyclopeutadiene type Resins, epoxy, xenyl aralkyl-type epoxy resin, naphthols aralkyl-type epoxy resin, naphthol novolac varnish type Resins, epoxy etc.
In addition, can enumerate the spy and open the urethane that has carboxyl like that (methyl) acrylate resin of putting down in writing in the 2002-229201 communique.
In addition; (methyl) vinylformic acid; acrylic acid dimer etc. have the carboxylic acid of alkene unsaturated group and other have the monomer of alkene unsaturated group; vinylbenzene for example; vinyl toluene; vinyl acetate between to for plastic; (methyl) methyl acrylate; (methyl) ethyl propenoate; (methyl) vinylformic acid n-propyl; (methyl) isopropyl acrylate; (methyl) n-butyl acrylate; (methyl) tert-butyl acrylate; the just own ester of (methyl) vinylformic acid; (methyl) cyclohexyl acrylate; (methyl) benzyl acrylate; benzene oxygen ethyl (methyl) acrylate; (methyl) vinylformic acid norborneol ester; (methyl) tetrahydrofurfuryl acrylate; (methyl) vinyl cyanide; 2-hydroxyethyl (methyl) acrylate; 2-hydroxypropyl (methyl) acrylate; the N-vinyl pyrrolidone; the N-caprolactam; N-(methyl) acryloyl morpholine etc. has the resin that the compound copolymerization of alkene unsaturated group obtains and the carboxyl part and glycidyl (methyl) acrylate of this resin; 3; 4-epoxycyclohexyl (methyl) methyl acrylate; 4-(2, the 3-epoxypropyl) butyl (methyl) acrylate; the compound that glycidyl allyl ether etc. have epoxy group(ing) reacts resulting resin.
Equally, glycidyl (methyl) acrylate, 3,4-epoxycyclohexyl (methyl) methyl acrylate, 4-(2, the 3-epoxypropyl) butyl (methyl) acrylate, the epoxy group(ing) of glycidyl allyl ether etc. and have the compound of alkene unsaturated group, with above-mentioned compound with alkene unsaturated group, the resin that obtains by copolymerization, and the epoxy group(ing) of this resin, with (methyl) vinylformic acid, after acrylic acid dimer etc. have the carboxyl addition of carboxylic acid of alkene unsaturated group, the hydroxyl of generation and succinyl oxide, the tetrahydrochysene anhydride phthalic acid, methyl six hydrogen anhydride phthalic acids, anhydride reactions such as six hydrogen anhydride phthalic acids and the resin that obtains.
The use level of this alkali soluble resins, preferred 20～70 quality %, more preferably 30～60 quality % in the solidified nature flame retardant resin composition.
(2) (methyl) acrylic compound
(methyl) acrylic compound uses with high light solidified in order to give solder resist material.As object lesson, can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, four ethylenes (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, two (methyl) acrylate such as bisglycidyl base (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, polyacrylic ester by the compound of formula (1) expression etc., the diacrylate of addition 4 moles of ethylene oxide of bisphenol S, the diacrylate of addition 4 moles of ethylene oxide of dihydroxyphenyl propane, fatty acid modified pentaerythritol diacrylate, the triacrylate of 3 moles of propylene oxide additions of TriMethylolPropane(TMP), the polyacrylic ester of the polyvalent alcohol of the modifications such as triacrylate of 6 moles of propylene oxide additions of TriMethylolPropane(TMP) etc.
Use level that should (methyl) acrylic compound, preferred 5～30 quality %, more preferably 10～25 quality % in the solidified nature flame retardant resin composition.
(3) Resins, epoxy
Resins, epoxy is in order to give tunicle against corrosion with thermotolerance, tenacity and use.As such Resins, epoxy, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, tetramethyl-bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, dicyclopentadiene-type epoxy resin, xenyl aralkyl-type epoxy resin, naphthols aralkyl-type epoxy resin, naphthol novolac varnish type Resins, epoxy, triphenyl methane type Resins, epoxy, N-Racemic glycidol fundamental mode Resins, epoxy etc.
In addition, in above-mentioned various Resins, epoxy, a part can adopt the various phosphorous epoxy resins that react, combine phosphorus atom with the reactive phosphorus compound.As this reactive phosphorus compound, for example, can enumerate 9, the 10-dihydro-9-oxy is assorted-resultant of reaction of 10-phosphorus phenanthrene-10-oxide compound or diphenyl phosphine oxide and benzoquinones or naphthoquinones (following formula a～d) etc.
Formula (a)
[changing 10]
Formula (b)
[changing 11]
Formula (c)
[changing 12]
Formula (d)
[changing 13]
The use level of this Resins, epoxy, preferred 5～50 quality %, more preferably 10～40 quality % in the solidified nature flame retardant resin composition.
(4) Photoepolymerizationinitiater initiater
Photoepolymerizationinitiater initiater is at light, particularly produces the compound of free radical in the ultra-violet region, be for give solder resist with light solidified in, form pattern and the compound that uses.The compound of below specifically listing can preferably use.For example; the benzoin ethyl isobutyl ether; the benzoin isopropyl ether; the benzoin ether; benzoin compounds such as benzyl dimethyl ketone acetal; the diethoxy phenyl methyl ketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; the 1-hydroxycyclohexylphenylketone; 2-methyl isophthalic acid-[4-(methyl is dredged generation) phenyl]-2-morpholino acetone-1; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-compounds such as phenyl methyl ketone such as butanone-1 grade; glyoxylic ester compounds such as aminomethyl phenyl glyoxylic ester; benzophenone; benzoyl M-nitro benzoic acid methyl esters; dihydroxy benaophenonel; the 4-phenyl benzophenone; benzophenone compounds such as the benzophenone of propenylization; 2; 4; acylphosphine oxide compounds such as 6-Three methyl Benzene accidental cause diphenyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide; two (2; 4,6-trimethylbenzoyl) two acylphosphine oxide compounds such as phenyl phosphine oxide etc.In addition, as sensitizer, for example, can use 2, thio-xanthene-one compounds such as 4-diethyl thio-xanthene-one, 2-isopropyl-thio-xanthone, 4,4 '-two (N, the N-dimethylamino) benzophenone, 4,4 '-two (N, N-diethylamino) benzophenone etc. also can and use.
The use level of this Photoepolymerizationinitiater initiater, preferred 1～10 quality %, more preferably 2～8 quality % in the solidified nature flame retardant resin composition.
(5) filler
The filler of Pei Heing as required is used to improve viscosity characteristics and cooperates, and for example, can enumerate lime carbonate, barium sulfate, aluminum oxide, talcum, silica, mica etc.
The use level of this filler, with respect to summation 100 mass parts of alkali soluble resins, (methyl) acrylic acid compound, Resins, epoxy, Photoepolymerizationinitiater initiater, phosphonium flame retardant of the present invention, preferred 10～100 mass parts, more preferably 20～80 mass parts.
(6) other additives
As other additives, can enumerate benzyldimethylamine, 2,4,6-three (N, the N-dimethylaminomethyl) phenol, 1,8-diazabicyclo (5.4.0) hendecene-1,2-ethyl-4-methylimidazole, the 2-phenylimidazole, the 2-undecylimidazole, the 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, epoxy curing agents such as 1-1-cyanoethyl-2-methylimidazole triphen six acid esters, the 3-glycidoxypropyltrime,hoxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, 3-(metacryloxy propyl group) Trimethoxy silane, silane coupling agents such as 3-aminopropyltriethoxywerene werene, and flow agent, defoamer, dispersion agent, oxidation inhibitor, stopper, dyestuff, pigment etc.In addition, addition type phosphorus type flame retardants such as triphenyl, trimethylphenyl phosphoric acid ester, the two phenyl phosphate ester of Resorcinol, the two tolyl phosphoric acid ester of Resorcinol, propoxy-phosphine piperazine, phenoxy group phosphine piperazine, a small amount of interpolation is also passable in the scope of not oozing out from cured article.In addition, mineral-type fire retardants such as aluminium hydroxide, magnesium hydroxide use also passable in the scope that rerum natura is reduced.
Phosphonium flame retardant of the present invention, owing to have flame retardant resistance, flexibility, high characteristics such as light solidified, so contain the solidified nature flame retardant resin composition of this fire retardant, the purposes that can be used for the requirement flexibility, for example, the dipping of the coating material of plastic film, the fibre reinforced plastics caking agent of resin, polyimide and Copper Foil etc.In addition, to solder resist, particularly the agent of used in flexible substrate welding resistance material also is suitable for.
Except that above-claimed cpd,, certainly cooperate organic composition arbitrarily in order to improve all characteristics.
Embodiment
Be described more specifically the present invention by embodiment, but the present invention is not subjected to the qualification of these embodiment again.Also have, except that being specifically noted, " part " in embodiment, the comparative example means " mass parts ".
[synthesis example of phosphonium flame retardant]
Embodiment 1
In reaction vessel, add KAYARADDPCA30 (trade(brand)name, R in formula (1) with whipping appts, thermometer, condenser
1Be hydrogen atom, n+m+l+o+p+q=3, Nippon Kayaku K. K's manufacturing) 921g (1 mole), HCA (trade(brand)name, 9, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound, Sanko Co., Ltd. makes) 388.8g (1.8 moles), propylene glycol methyl ether acetate 327g, p methoxy phenol (Metokinon) 1.3g, the air limit is blown in 110 ℃ of reactions 13 hours in the limit, and the phosphorus content that obtains non-volatile part concentration and be in 80 quality %, the non-volatile part is the compound 1 of 4.3 quality %.
Embodiment 2
In reaction vessel, add KAYARADDPCA30 (trade(brand)name with whipping appts, thermometer, condenser, Nippon Kayaku K. K's manufacturing) 921g (1 mole), HCA (trade(brand)name, Sanko Co., Ltd.'s manufacturing) 648g (3.0 moles), propylene glycol methyl ether acetate 392g, p methoxy phenol 1.5g, the air limit is blown in 110 ℃ of reactions 13 hours in the limit, and the phosphorus content that obtains non-volatile part concentration and be in 80 quality %, the non-volatile part is the compound 2 of 5.9 quality %.
Embodiment 3
In reaction vessel, add KAYARADDPCA60 (trade(brand)name, R in formula (1) with whipping appts, thermometer, condenser
1Be hydrogen atom, n+m+l+o+p+q=6, Nippon Kayaku K. K's manufacturing) 1263g (1 mole), HCA (trade(brand)name, Sanko Co., Ltd.'s manufacturing) 648g (3 moles), propylene glycol methyl ether acetate 478g, p methoxy phenol 1.9g, the air limit is blown in 110 ℃ of reactions 13 hours in the limit, and the phosphorus content that obtains non-volatile part concentration and be in 80 quality %, the non-volatile part is the compound 3 of 4.9 quality %.
Embodiment 4
In reaction vessel, add KAYARADDPCA60 (trade(brand)name with whipping appts, thermometer, condenser, Nippon Kayaku K. K's manufacturing) 1263g (1 mole), diphenyl phosphine oxide 607g (3 moles), propylene glycol methyl ether acetate 468g, p methoxy phenol 1.9g, the air limit is blown in 110 ℃ of reactions 13 hours in the limit, and the phosphorus content that obtains non-volatile part concentration and be in 80 quality %, the non-volatile part is the compound 4 of 5.1 quality %.
Embodiment 5
In reaction vessel, add KAYARAD DPCA60 (trade(brand)name with whipping appts, thermometer, condenser, Nippon Kayaku K. K makes) 1263g (1 mole), two (2, the 5-3,5-dimethylphenyl) phosphine oxide 775g (3 moles), propylene glycol methyl ether acetate 510g, p methoxy phenol 2.0g, the air limit is blown in 110 ℃ of reactions 13 hours in the limit, and the phosphorus content that obtains non-volatile part concentration and be in 80 quality %, the non-volatile part is the compound 5 of 4.6 quality %.
Embodiment 6
In reaction vessel, add KAYARAD DPHA (trade(brand)name with whipping appts, thermometer, condenser, dipentaerythritol acrylate, Nippon Kayaku K. K's manufacturing) 578g (1 mole), HCA 864g (4 moles), diethylene glycol ethyl ether acetic ester 618g, p methoxy phenol 1.44g, the air limit is blown in 110 ℃ of reactions 13 hours in the limit, obtains non-volatile content concentration and be the compound 6 that phosphorus content in 70 quality %, the non-volatile content reaches 8.6 quality %.
Embodiment 7
In reaction vessel, add KAYARAD DPHA578g (1 mole), diphenyl phosphine oxide 809g (4 moles), diethylene glycol ethyl ether acetic ester 595g, p methoxy phenol 1.44g with whipping appts, thermometer, condenser, the air limit is blown in 110 ℃ of reactions 13 hours in the limit, obtains non-volatile content concentration and be the compound 7 that phosphorus content in 70 quality %, the non-volatile content reaches 8.9 quality %.
Comparative example 1
In reaction vessel, add KAYARAD DPHA578g (1 mole), HCA (trade(brand)name with whipping appts, thermometer, condenser, Sanko Co., Ltd.'s manufacturing) 432g (2.0 moles), propylene glycol methyl ether acetate 252g, p methoxy phenol 1.0g, the air limit is blown in 110 ℃ of reactions 13 hours in the limit, and the phosphorus content that obtains non-volatile part concentration and be in 80 quality %, the non-volatile part is the compound 8 of 6.1 quality %.
Comparative example 2
In reaction vessel, add Viscoat 295 282g (1 mole), HCA (trade(brand)name with whipping appts, thermometer, condenser, Sanko Co., Ltd.'s manufacturing) 216g (1.0 moles), propylene glycol methyl ether acetate 125g, p methoxy phenol 0.5g, the air limit is blown in 110 ℃ of reactions 13 hours in the limit, and the phosphorus content that obtains non-volatile part concentration and be in 80 quality %, the non-volatile part is the compound 9 of 6.2 quality %.
[synthesizing of alkali soluble resins]
As alkali soluble resins, the urethane acrylate resin (UA-1) with carboxyl is synthetic by following main points.
In reaction vessel, add polytetramethylene glycol (Baotugu Chemical Industrial Co., Ltd's manufacturing with whipping appts, thermometer, condenser, PTG-850SN, molecular weight 850) 850g (1 mole), dimethylol propionic acid 938g (7 moles), isophorone diisocyanate 1998g (9 moles), propylene glycol methyl ether acetate 1006g.Stop when being heated to 60 ℃ while stirring, add dibutyltin dilaurate 1.4g.When the reaction vessel temperature begins to descend, be heated to 80 ℃ once again, the limit remains on 75～85 ℃ of limits and stirred 8 hours, synthetic urethane oligomers.In addition, after reaction vessel imports right-methoxyphenol (p-Methoxyphenol) and each 0.9g of two-tertiary butyl-hydroxytoluene, add 2-hydroxy ethyl methacrylate 238g (2.05 moles) respectively, begin again to react.Confirm the absorption spectrum (2280cm of isocyanate group in the infrared absorption spectrum
-1) disappear, reaction terminating obtains thick liquid urethane acrylate compound.The molecular-weight average of resulting urethane acrylate (UA-1) is 16000, and the solids component acid number is 90mgKOH/g, and non-volatile part is 80 quality %.
[preparation of solidified nature flame retardant resin composition]
Embodiment 8～14, comparative example 3,4
Adopt the cooperation ratio (mass parts) shown in following table 1-1, the table 1-2, synthetic phosphonium flame retardant, alkali soluble resins (UA-1), (methyl) acrylic compound, Resins, epoxy, Photoepolymerizationinitiater initiater, filler, hot polymerization catalyst are cooperated preparation solidified nature flame retardant resin composition.Here, the host of each embodiment and comparative example and solidifying agent respectively by three-roll grinder ((strain) little flat making manufacturing, model RIII-1RM-2) 3 times, carry out mixingly, are mixed with flame retardant resin composition.
As Resins, epoxy, use phosphorous epoxy resin ZX-1548-4 (trade(brand)name, phosphorous 4 quality %, Toto Kasei KK makes, be dissolved in the diethylene glycol ethyl ether acetic ester, being mixed with solid component concentration is 70 quality %), cresols phenolic resin varnish type epoxy resin EPICON, N680 (Dainippon Ink. ﹠ Chemicals Inc makes, and is dissolved in the diethylene glycol ethyl ether acetic ester, and being mixed with solid component concentration is 80 quality %).As Photoepolymerizationinitiater initiater; use Irgacure 907 (trade(brand)names; 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino acetone-1, Chiba specialty goods chemistry society makes), Lucirin TPO (trade(brand)name, 2; 4; 6-trimethylbenzoyl phenyl phosphine oxide, BASF society makes), EAB-F (trade(brand)name, 4; 4 '-two (diethylamino) benzophenone, Baotugu Chemical Industrial Co., Ltd makes).As epoxy resin cure promotor, use メ ラ ミ Application PC-1 (trade(brand)name, Nissan Chemical Ind Ltd makes).As the aluminium hydroxide of mineral-type fire retardant, use Ha イ ジ ラ イ ト H42ISTE (trade(brand)name, Showa Denko K. K makes).As the mineral-type filler, use Le Network Ha イ Off イ ラ-#5000PJ (trade(brand)name, Ishihara Sangyo Kaisha, Ltd. makes).
[making of test piece and evaluation]
(1) light sensitivity
The Copper Foil of thickness 35 μ m, (Ube Industries, Ltd makes, ユ ピ セ Le (registered trademark) N to be laminated to printed base plate on the single face of polyimide film of thickness 50 μ m, aqueous sulfuric acid with concentration 1 quality % washs, after the washing, carry out drying with airflow), heat to 60 ℃.The solidified nature flame retardant resin composition that on this substrate embodiment 8～14, comparative example 3,4 is obtained with 150 order polyester versions, adopts silk screen print method to be coated with, and makes to reach thickness 20～25 μ m.After this substrate carried out solvent seasoning in 80 ℃ * 30 minutes, employing has exposure machine [オ-Network (strain) manufacturing] HMW-680GW of metal halide lamp, and (Hitachi Chemical Co., Ltd. makes, OD value 0.05～3.05 by 21 sections stepped start-stop system tablets, Δ D=0.15), with 500mJ/cm
2Expose.Then, in 30 ℃ with the aqueous sodium carbonates of concentration 1 quality % spraying 60 seconds, remove unexposed part, after developing, read and reach completely crued hop count, with its light sensitivity as said composition.
(2) bendability
The solidified nature flame retardant resin composition that embodiment 8～14, comparative example 3,4 are obtained, with 150 order polyester versions, adopt silk screen print method, be coated on polyimide film (Dong Li Dupont Kabushiki Kaisha manufacturing of thickness 25 μ m, 70mm * 50mm, カ プ ト Application 100H) on the substrate single face, make to reach thickness 20～25 μ m, after solvent seasoning in 80 ℃ * 30 minutes, with above-mentioned exposure machine in 500mJ/cm
2Expose.After thermofixation in 150 ℃ * 60 minutes, the coated face outside curve is become 180 ° again, naked eyes judge that cured film has or not albefaction.Judging criterion is as follows:
Zero: cured film is albefaction not;
*: cured film generation albefaction, or chap.
(3) incendivity
In order to below manufactured incendivity test piece.Polyimide film (Dong Li Dupont Kabushiki Kaisha manufacturing at thickness 25 μ m, 200mm * 50mm, カ プ ト Application 100H) on the substrate single face, with 150 order polyester versions, the solidified nature flame retardant resin composition that adopts silk screen print method coating embodiment 8～14, comparative example 3,4 to obtain makes thickness reach 20～25 μ m.After 80 ℃ * 30 minutes condition is carried out solvent seasoning, carry out thermofixation in 150 ℃ * 60 minutes condition.On another side, adopt silk screen print method more equally, the solidified nature flame retardant resin composition that embodiment 6～10, comparative example 3,4 are obtained is coated with, after making thickness reach 20～25 μ m, adopt same condition to carry out solvent seasoning and thermofixation, make sample.
Combustioncharacteristics is estimated flame retardant resistance according to the method for the macromolecular material flame retardant test standard 94UL-VTM test in the insurance industry laboratory of the U.S. (being called for short UL).
Also have, " VTM " among table 1-1, the table 1-2 reaches " NOT " and adopts following standard.
VTM-0: must satisfy the following item that requires.
(1) all test pieces, each time contact flame are ended the back flaming combustion were not taken place above 10 seconds.
(2) respectively organize 5 test pieces totals and carry out contact flame 10 times, flaming combustion time total is no more than 50 seconds.
(3) burning of flaming combustion or red heat does not reach the graticule of 125mm.
(4) there is the following thing of flame that absorbent cotton is caught fire.
After (5) the 2nd times contact flame was ended, the flaming combustion of each sample and red heat burning total were no more than 30 seconds.
In (6) one groups of 5 test pieces only 1 when not meeting the demands item or have the flame time amount to 51 seconds～during 55 seconds scopes, get 5 test pieces again and test, all satisfy above-mentioned (1)～(5).
VTM-1: must satisfy the following item that requires.
(1) all test pieces, each time contact flame are ended the back flaming combustion were not taken place above 30 seconds.
(2) respectively organize 5 test pieces totals and carry out contact flame 10 times, flaming combustion time total is no more than 250 seconds.
(3) burning of flaming combustion or red heat does not reach the graticule of 125mm.
(4) there is the following thing of flame that absorbent cotton is caught fire.
After (5) the 2nd times contact flame was ended, the flaming combustion of each sample and red heat burning total were no more than 60 seconds.
In (6) one groups of 5 test pieces only 1 when not meeting the demands item or have the flame time amount to 251 seconds～during 255 seconds scope, get 5 test pieces again and test, all satisfy above-mentioned (1)～(5).
VTM-2: must satisfy the following item that requires.
(1) all test pieces, each time contact flame are ended the back flaming combustion were not taken place above 30 seconds.
(2) respectively organize 5 test pieces totals and carry out contact flame 10 times, flaming combustion time total is no more than 250 seconds.
(3) burning of flaming combustion or red heat does not reach the graticule of 125mm.
(4) there is the following thing of flame that absorbent cotton is caught fire.
After (5) the 2nd times contact flame was ended, the flaming combustion of each sample and red heat burning total were no more than 60 seconds.
In (6) one groups of 5 test pieces only 1 when not meeting the demands item or have the flame time amount to 251 seconds～255 seconds the time, get 5 test pieces again and test, all satisfy above-mentioned (1)～(5).
NOT: any one of above-mentioned grade is all defective.
The cooperation composition and the evaluation result of [table 1-1] each embodiment, comparative example
The cooperation composition and the evaluation result of [table 1-2] each embodiment, comparative example
As show shown in 1-1 and the table 1-2, the phosphonium flame retardant of the application of the invention shows to have sufficient flame retardant resistance, light sensitivity, flexibility.Therefore, phosphonium flame retardant of the present invention is particularly suitable for the purposes of requirement flexibility and flame retardant resistance.
Utilize possibility on the industry
According to the present invention, provide not phosphonium flame retardant and curing property anti-flammability tree of halide Oil/fat composition, said composition contain this phosphonium flame retardant, and are solidified by radical polymerization, Obtain curing property excellence, simultaneously the solidfied material of anti-flammability, curing property, flexibility excellence.
Claims (6)
1. phosphonium flame retardant, described phosphonium flame retardant are resulting with the phosphorus compound reaction with P-H key by (methyl) acryl of multi-functional (methyl) acrylic compound of following formula (1) expression:
Formula (1)
[changing 1]
In the formula, R
1Expression hydrogen atom or methyl; In addition, the integer of n+m+1+o+p+q=0～12.
2. according to the phosphonium flame retardant described in the claim 1, wherein, in formula (1), n+m+l+o+p+q is 3～12 integer.
3. according to the phosphonium flame retardant described in claim 1 or 2, it obtains (methyl) acryl and the compound reaction with P-H key, and wherein, with respect to 1 mole of (methyl) acryl, the compound with P-H key is 0.35～0.7 mole.
4. according to any one described phosphonium flame retardant in the claim 1～3, wherein, the phosphorus compound with P-H key is the phosphine oxide compound with following formula (2) or formula (3) expression:
Formula (2)
[changing 2]
In the formula, R
2And R
3Represent the fatty group of hydrogen atom, carbon number 1～10 or the aromatic series base of carbon number 6～10 respectively independently, r and s represent 1～4 integer respectively; When r and s are a plurality of, each R
2And R
3Respectively both can be identical also can be inequality;
Formula (3)
[changing 3]
In the formula, R
4And R
5Represent the fatty group of hydrogen atom, carbon number 1～10 or the aromatic series base of carbon number 6～10 respectively independently, t and u represent 1～5 integer; When t and u are a plurality of, each R
4And R
5Respectively both can be identical also can be inequality.
5. solidified nature flame retardant resin composition wherein contains the phosphonium flame retardant of any one record in alkali soluble resins, (methyl) acrylic compound, Resins, epoxy, Photoepolymerizationinitiater initiater and the claim 1～4.
6. according to the solidified nature flame retardant resin composition described in the claim 5, its be with alkali soluble resins 20～70 quality %, (methyl) acrylic compound 5～30 quality %, Resins, epoxy 5～50 quality %, Photoepolymerizationinitiater initiater 1～10 quality %, and claim 1～4 in phosphonium flame retardant 5～40 quality % of any one record cooperate and form.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP009072/2007 | 2007-01-18 | ||
| JP2007009072 | 2007-01-18 |
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| CN101573428A true CN101573428A (en) | 2009-11-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA200780048534XA Pending CN101573428A (en) | 2007-01-18 | 2007-12-13 | Phosphorus-containing flame retardant and curable flame -retarded resin compositions containing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2008087812A1 (en) |
| CN (1) | CN101573428A (en) |
| TW (1) | TW200846353A (en) |
| WO (1) | WO2008087812A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101320213B (en) * | 2007-06-04 | 2012-07-04 | 太阳控股株式会社 | Light sensitive resin composition and flexible printed circuit board produced with the same |
| CN106566155A (en) * | 2016-11-13 | 2017-04-19 | 惠州市大亚湾科翔科技电路板有限公司 | Insulation fire retardant for circuit board |
| CN109810134A (en) * | 2018-12-29 | 2019-05-28 | 张家港康得新光电材料有限公司 | High refractive index flame retardant type UV resin, preparation method and optical film |
| CN109957283A (en) * | 2019-02-27 | 2019-07-02 | 江苏艾森半导体材料股份有限公司 | High flame retardant solder mask |
| CN112662260A (en) * | 2020-12-29 | 2021-04-16 | 山西中涂交通科技股份有限公司 | Flame-retardant anti-skid road surface coating for tunnel |
| CN115260477A (en) * | 2022-08-26 | 2022-11-01 | 深圳市瑞世兴科技有限公司 | Intrinsic flame-retardant PET resin and preparation method and application thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101450928B1 (en) * | 2006-12-01 | 2014-10-14 | 교세라 케미카르 가부시키가이샤 | Photosensitive heat curing-type resin composition and flexible printed wiring board |
| KR101142735B1 (en) * | 2007-05-11 | 2012-05-07 | 미쓰이 가가쿠 가부시키가이샤 | Resin composition, dry film, and fabrications of the same |
| JP5485713B2 (en) * | 2010-01-07 | 2014-05-07 | 三菱製紙株式会社 | Photocrosslinkable resin composition |
| JP5764368B2 (en) * | 2011-04-05 | 2015-08-19 | 株式会社カネカ | Novel photosensitive resin composition and use thereof |
| JP5964608B2 (en) * | 2012-02-20 | 2016-08-03 | 株式会社タムラ製作所 | UV curable transparent resin composition |
| JP2015004009A (en) * | 2013-06-21 | 2015-01-08 | 味の素株式会社 | Resin compositions |
| CN104774343B (en) * | 2015-03-10 | 2017-08-01 | 三峡大学 | A kind of phenyl phosphate fire retardant containing DOPO, preparation method and applications |
| CN110577803B (en) | 2018-06-11 | 2021-11-26 | 3M创新有限公司 | Flame-retardant pressure-sensitive adhesive, flame-retardant pressure-sensitive adhesive sheet and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001213889A (en) * | 2000-01-28 | 2001-08-07 | Nippon Shokubai Co Ltd | Reactive phosphorus compound |
| AU2001273908A1 (en) * | 2000-04-03 | 2001-10-15 | U C B, S.A. | Phosphorus containing materials, their preparation and use |
| JP2001312054A (en) * | 2000-05-01 | 2001-11-09 | Dainippon Ink & Chem Inc | Energy beam-curable resin composition for resist |
-
2007
- 2007-12-13 WO PCT/JP2007/074020 patent/WO2008087812A1/en active Application Filing
- 2007-12-13 CN CNA200780048534XA patent/CN101573428A/en active Pending
- 2007-12-13 JP JP2008553983A patent/JPWO2008087812A1/en active Pending
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101320213B (en) * | 2007-06-04 | 2012-07-04 | 太阳控股株式会社 | Light sensitive resin composition and flexible printed circuit board produced with the same |
| CN106566155A (en) * | 2016-11-13 | 2017-04-19 | 惠州市大亚湾科翔科技电路板有限公司 | Insulation fire retardant for circuit board |
| CN109810134A (en) * | 2018-12-29 | 2019-05-28 | 张家港康得新光电材料有限公司 | High refractive index flame retardant type UV resin, preparation method and optical film |
| CN109957283A (en) * | 2019-02-27 | 2019-07-02 | 江苏艾森半导体材料股份有限公司 | High flame retardant solder mask |
| CN112662260A (en) * | 2020-12-29 | 2021-04-16 | 山西中涂交通科技股份有限公司 | Flame-retardant anti-skid road surface coating for tunnel |
| CN115260477A (en) * | 2022-08-26 | 2022-11-01 | 深圳市瑞世兴科技有限公司 | Intrinsic flame-retardant PET resin and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2008087812A1 (en) | 2010-05-06 |
| WO2008087812A1 (en) | 2008-07-24 |
| TW200846353A (en) | 2008-12-01 |
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