CN103068877B - Potentiality hardener composition and a liquid hardening composition epoxy resin - Google Patents
Potentiality hardener composition and a liquid hardening composition epoxy resin Download PDFInfo
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- CN103068877B CN103068877B CN201180039127.9A CN201180039127A CN103068877B CN 103068877 B CN103068877 B CN 103068877B CN 201180039127 A CN201180039127 A CN 201180039127A CN 103068877 B CN103068877 B CN 103068877B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
- C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- 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
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- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
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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
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- 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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Abstract
The present invention is a kind of potentiality hardener composition, for the addition reaction that the amine compound having an active hydrogen base by (a) containing (A) reacts with (b) multi-epoxy compound and obtain, and the potentiality hardener composition used for epoxy resin that (B) phenol resins is formed; The feature of this potentiality hardener composition is: this phenol resins contains two nucleomes of 10% ~ 40 quality %, several molecular-weight average (Mn) of this phenol resins are 900 ~ 2000 simultaneously, weight average molecular weight (Mw) is 2500 ~ 5000, and molecular weight distribution (Mw/Mn) is 2.0 ~ 4.0.
Description
Technical field
The present invention relates to and polyepoxides and/or cyanate are used and applicable potentiality hardener composition together, particularly, relate to containing making amine compound and multi-epoxy compound react the addition reaction obtained, and it is stable under the normal temperature that forms of the phenol resins of molecular weight optimization, the potentiality hardener composition of stiffening agent function is can be used as during heating, and containing the liquid hardening composition epoxy resin that this potentiality hardener composition is formed.
Background technology
The tackiness of epoxy resin to various base material is excellent, again, to be hardened formed hardening thing by stiffening agent owing to making epoxy resin, thermotolerance, resistance to chemical reagents, electrical specification, mechanical characteristics etc. are more excellent, therefore can be applicable to industrial field widely, especially, can be used as the commercial use in coating, tackiness agent field.
Previous composition epoxy resin, to be divided into main flow by the twenty percent of interpolation stiffening agent, hardening accelerator before use.This kind of twenty percent is divided into composition epoxy resin, there is the feature of " it can be made to harden under normal temperature or low temperature ", but its reverse side, due to the event must measured before being about to use, mix, the spendable time is very short, there is the shortcoming of " to the applicable difficulty etc. of automation, its working conditions is restricted ".For eliminating this kind of shortcoming, thus expect a liquid hardening composition epoxy resin.
For obtaining this kind liquid hardening composition epoxy resin, must have and at room temperature not react, during heating, starting the stiffening agent of the character of sclerous reaction, be i.e. so-called potentiality stiffening agent.This kind of potentiality stiffening agent, has such as Dyhard RU 100 (dicyandiamide), binary acid dihydrazide, borontrifluoride boron amide wrong salt, guanamines (guanamine) class, trimeric cyanamide and imidazoles etc. to be suggested.
But, such as Dyhard RU 100, trimeric cyanamide or guanidine amine are mixed with epoxy resin, though storage stability is excellent, but there is the shortcoming of " must harden for a long time under the high temperature more than 150 DEG C, be curing condition unaccommodated when reality uses ".Again, though also carry out its grade and hardening accelerator widely and use, shorten setting time, but now produce the shortcoming of " obviously undermining storage stability ".
On the other hand, when using binary acid dihydrazide, imidazoles, can harden under relatively low temperature, but shortcoming storage stability.When using borontrifluoride boron amide mistake salt, though there is the speciality of " storage stability is excellent, and setting time is also short " simultaneously, but have except water tolerance is deteriorated, by various shortcomings such as metallic corrosion.
Moreover, though also have what propose to make polyamino compound and epoxy compounds react to obtain to be that the epoxy adduct of the isophorone diamine of adducts upgrading amine uses (patent documentation 1) as potentiality stiffening agent, but it is when being used alone, storage stability is poor.So, also have the resultant of reaction proposing imidazolium compounds and epoxy compounds and resol to use (patent documentation 2) as potentiality stiffening agent, but now have the shortcoming of " can only poor adherence person be obtained ".
Moreover, in the purposes such as sealing, shaping of semi-conductor, be only used alone or as a mixture the situation that existing epoxy resin is still insufficient, many use high heat resistance cyanate-epoxy composite resin compositions.Use amine type hardeners to be also suggested (patent documentation 3) as the stiffening agent for this kind of compound resin, but now also have the shortcoming of " can not get abundant storage stability ".
Especially, in purposes about the electronic component such as miniature motor, driving mechanism, though seek high adhesion, but for meeting a liquid curable resin composition of these use epoxy resin required, epoxy-cyanate compound resin, suitable potentiality stiffening agent occurs not yet.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Laid-Open Patent Publication 58-147417 publication
[patent documentation 2] United States Patent (USP) No. 4066625 publication
[patent documentation 3] Japanese Laid-Open Patent Publication 60-250026 publication
Summary of the invention
Technical problem
Therefore, the 1st object of the present invention is excellent for being provided as storage stability, simultaneously hardening and the used potentiality hardener composition be applicable to of the also excellent liquid curable resin composition of tackiness.
2nd object of the present invention for providing storage stability excellent, simultaneously hardening and the also excellent liquid curable resin composition of tackiness.
Technical scheme
The present inventor etc., the result of wholwe-hearted self-criticism is repeated for realizing above-mentioned all objects, find to use the mixture adding the phenol resins that mixture upgrading polyamino compound and molecular weight are optimized to use as potentiality stiffening agent, contain a liquid curable resin composition of polyepoxides and/or cyanate simultaneously, there is good storage stability, hardening and tackiness, so realize the present invention.
That is, the liquid curable resin composition that the present invention is a kind of potentiality hardener composition and is formed containing this potentiality hardener composition, this potentiality hardener composition has the amine compound of active hydrogen base and (b) multi-epoxy compound by (a) and reacts for containing (A) the potentiality hardener composition used for epoxy resin that the addition reaction that obtains and (B) phenol resins form; The feature of this potentiality hardener composition is: this phenol resins contains two nucleomes of 10 ~ 40 quality %, several molecular-weight average (Mn) of this phenol resins are 900 ~ 2000 simultaneously, weight average molecular weight (Mw) is 2500 ~ 5000, and molecular weight distribution (Mw/Mn) is 2.0 ~ 4.0.
Invention effect
By by potentiality hardener composition of the present invention and polyepoxides and the cyanate recombinant that optionally uses, the liquid curable resin composition that storage stability, hardening and tackiness are excellent can be obtained.
[carry out an invention form used]
Potentiality hardener composition of the present invention is for having by (a) the used for epoxy resin potentiality hardener composition of phenol resins as essential component that the amine compound of active hydrogen base and (b) multi-epoxy compound react addition reaction and (B) composition obtained using (A) composition.
The above-mentioned amine compound with active hydrogen base used as (a) composition, can be the alkylene base Diamines of such as ethylene group diamines, 1,2-bis-amido propane, 1,3-bis-amido propane, 1,3-diaminobutane, Isosorbide-5-Nitrae-diaminobutane etc., many alkyl polyamines class of diethyl support group triamine, three ethylene group triamines, four ethylene group five amine etc., the ester ring type polyamine class of 1,3-diaminomethylcyclohexane, 1,2-diamines butylcyclohexane, Isosorbide-5-Nitrae-two amido-3,6-diethyl cyclohexane, isophorone diamine etc., the aromatic polyamine class of m-xylene diamine, two aminodiphenylmethane, two amido sulfobenzides etc., the guanidine amine of benzoguanamine, acetylguanamine etc., the imidazoles of glyoxal ethyline, 2-ethyl-4-methylimidazole, 2 isopropyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-aminocarbonyl propyl imidazoles etc., two hydrazides classes of grass acid dihydrazide, acid dihydrazide, succinic acid hydrazide ii, glutaric, adipic dihydrazide, suberic acid two hydrazides, nonane diacid two hydrazides, sebacic dihydrazide, phthalein acid dihydrazide etc., N, N-dimethyl amido ethylamine, N, N-diethyl amido ethylamine, N, N-diisopropyl amido ethylamine, N, N-diallyl amido ethylamine, N-phenmethyl-N-methyl amido ethylamine, N, N-diphenyl-methyl amido ethylamine, N-cyclohexyl-N-methyl amido ethylamine, N, N-dicyclohexyl amido ethylamine, N, N-Dimethylaminopropyl amine, N, N-diethyl aminocarbonyl propyl amine, N, N-diisopropyl amido propyl group amine, N, N-diallyl amido propyl group amine, N-phenmethyl-N-methyl aminocarbonyl propyl amine, N, N-diphenyl-methyl amido propyl group amine, N, N-cyclohexyl methyl aminocarbonyl propyl amine, N, N-dicyclohexyl amido propyl group amine, N-(2-amido ethyl) Pyrrolizidine, N-(3-aminocarbonyl propyl) Pyrrolizidine, N-(2-amido ethyl) piperidines, N-(3-aminocarbonyl propyl) piperidines, N-(2-amido ethyl) morpholine, N-(3-aminocarbonyl propyl) morpholine, N-(2-amido ethyl)-N '-methylpiperazine, N-(2-amido ethyl) piperazine, N-(3-aminocarbonyl propyl) piperazine, N-(3-aminocarbonyl propyl)-N '-methyl piperidine, 4-(N, N-dimethyl amido) phenmethyl amine, 4-(N, N-diethyl amido) phenmethyl amine, 4-(N, N-diisopropyl amido) phenmethyl amine, N, N-dimethyl isophorone diamine, N, N-dimethyl-p-phenylenediamine butylcyclohexane, N, N, N '-trimethylammonium ethylene group diamines, N '-ethyl-N, N-ethylene dimethyl base diamines, N, N, N '-trimethylammonium ethylene group diamines, N '-ethyl-N, N-dimethylpropane diamines, N '-ethyl-N, N-diphenyl-methyl amido propyl group amine, N, N-(two aminocarbonyl propyls)-N-methylamine, N, N-bis-amido ethylamine, N, N-bis-aminocarbonyl propyl propyl group amine, N, N-bis-amido propylbutylamine, N, N-bis-amido propylpentyl amine, N, N-bis-aminocarbonyl propyl hexyl amine, N, N-bis-aminocarbonyl propyl-2-DEHA, N, N-bis-amido propylcyclohexyl amine, N, N-bis-amido propylbenzene methylamine, N, N-bis-amido allyl amine, two [3-(N, N-Dimethylaminopropyl)] amine, two [3-(N, N-diethyl aminocarbonyl propyl)] amine, two [3-(N, N-diisopropyl amido propyl group)] amine, two [3-(N, N-dibutyl aminocarbonyl propyl)] amine etc.
In the present invention, from the viewpoint making low-temperature stiffening become good, in above-mentioned amine compound, preferred use at least has the amine compound of more than 1 tertiary amine base, and from the viewpoint of hardening thing thermotolerance, particularly preferably use the alkyl amine group alkylamine that following general formula (I) represents, or the imidazolium compounds that following general formula (II) represents.
General formula (I)
But, in general formula (I), R
1and R
2be the alkyl of carbon number 1 ~ 8 independently of one another, or R
1and R
2in conjunction with, represent the alkylene base that can contain Sauerstoffatom or nitrogen-atoms, n represents the integer of 1 ~ 6.
General formula (II)
But, in general formula (II), R
3~ R
5represent hydrogen atom, substituent alkyl or aryl can be had.
R in above-mentioned general formula (I)
1and R
2the alkyl of the carbonatoms 1 ~ 8 represented, can be the group of such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, tertiary octyl group etc.
R in above-mentioned general formula (II)
3, R
4and R
5the alkyl of the carbonatoms 1 ~ 18 represented, can be the group of such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, tertiary octyl group, nonyl, different nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, vinyl, allyl group, hydroxymethyl, hydroxyethyl, aminomethyl, aminocarbonyl propyl etc.
Again, R
3, R
4and R
5the aryl represented, as the base of phenyl, naphthyl etc.These aryl also can through abovementioned alkyl 1 to 4 replacement.
For in the amine compound that the general formula (I) of above-mentioned (a) composition represents, can be such as N, the such as N of N-dialkylamine pheynylalkylamine, N-Dimethylaminopropyl amine, N, N-diethyl aminocarbonyl propyl amine, N, N-dipropyl aminocarbonyl propyl amine, N, N-dibutyl aminocarbonyl propyl amine, N, N-dimethyl amido ethylamine, N, N-dimethyl amido ethylamine, N, N-dimethyl amido butylamine, aminocarbonyl propyl morpholine, amido ethyl piperidine, 1-(2-amido ethyl)-4-methylpiperazine etc.
The imidazolium compounds represented for the general formula (II) of above-mentioned (a) composition can be such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2 isopropyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-aminocarbonyl propyl imidazoles etc.
Be used in the multi-epoxy compound for (b) composition of (A) composition in the present invention, can be the poly epihydric alcohol ether compound of the monokaryon polyphenol compounds such as such as quinhydrones, Resorcinol, pyrocatechol, Phloroglucinol (phloroglucinol), dihydroxy naphthlene, '-biphenyl diphenol, methylene radical bis-phenol (Bisphenol F), methylene radical two (ortho-cresol), ethylidene bis-phenol, isopropylidene bisphenol (dihydroxyphenyl propane), isopropylidene two (ortho-cresol), tetrabromo-bisphenol, 1, 3-bis-(4-hydroxyisopropyl benzene), 1, 4-bis-(4-hydroxyisopropyl benzene), 1, 1, 3-joins (4-hydroxy phenyl) butane, 1, 1, 2, 2,-wantonly (4-hydroxy phenyl) ethane, thiodiphenol, sulfonyldiphenol (sulfonyl bisphenol), oxygen base bis-phenol (oxy bisphenol), phenol novolacs, o-cresol novolak, ethyl phenol phenolic varnish, butylphenol phenolic varnish, octyl phenol phenolic varnish, Resorcinol phenolic varnish, terpene phenolic, the poly epihydric alcohol ether compound of the multinuclear polyphenol compounds such as phenolate Dicyclopentadiene (DCPD), the polyglycidyl ether of the polyalcohols such as ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, polyoxyethylene glycol, thiobis ethylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, bisphenol A-propylene oxide affixture, toxilic acid, fumaric acid, methylene-succinic acid, succsinic acid, pentanedioic acid, suberic acid, hexanodioic acid, nonane diacid, sebacic acid, dimeracid, trimer acid, phthalandione, m-phthalic acid, terephthalic acid, trimellitic acid (trimellitic acid), trimesic acid (trimesic acid), pyromellitic acid (pyromellitic acid), tetrahydrochysene phthalandione, six hydrogen phthalandiones, the aliphatics such as interior methylene radical tetrahydrochysene phthalandione, the Racemic glycidol ethers of aromatic series or alicyclic polyprotonic acid and the homopolymer of glycidyl methacrylate or multipolymer, N, N-diglycidylaniline, two (4-(N-methyl-N-glycidyl amido) phenyl) methane etc. have the epoxy compounds of glycidyl amido, vinyl cyclohexane epoxide, Dicyclopentadiene (DCPD) diepoxide, 6-butylcyclohexane carboxylic acid 3, the epoxide of the cyclic alkene compound of 4-epoxy group(ing)-6-methylcyclohexyl methyl esters, hexanodioic acid two (3,4-epoxy group(ing)-6-methylcyclohexyl methyl esters) etc., the heterogeneous ring compound of the epoxidation conjugated diolefin polymer, isocyanuric acid three-glycidyl ester etc. of epoxidized polybutadiene, epoxidized styrene-butadiene multipolymer etc.
The reaction of the polyamino compound of above-mentioned (a) composition and the multi-epoxy compound of (b) composition in the present invention, for being 1 equivalent with the active hydrogen of the polyamino compound relative to (a) composition, b the epoxy equivalent (weight) of () composition is 0.5 ~ 2 equivalent, and preferably carry out with the ratio of 0.8 ~ 1.5 equivalent.When epoxy equivalent (weight) due to (b) composition used is less than 0.5 equivalent, the storage stability of a liquid curable resin composition of the present invention probably becomes not enough, when use is more than 2 equivalent, the hardening of a liquid curable resin composition of the present invention probably reduces, therefore not preferred.
For the phenol resins of (B) composition used in the present invention, it is the phenol resins synthesized from phenols and aldehydes.Above-mentioned phenols can be such as phenol, cresols, ethyl phenol, n-propyl phenol, isopropyl-phenol, butylphenol, tert-butyl phenol, octyl phenol, nonyl phenol, decyl phenol, cyclohexyl phenol, chlorophenol, bromine phenol, Resorcinol, catechol, quinhydrones, 2,2-bis-(4-hydroxy phenyl) propane, 4,4 '-thiodiphenol, dihydroxydiphenyl methane, naphthols, terpene phenolic, phenolate dichloro pentadiene etc., above-mentioned aldehydes can be formaldehyde.
For the phenol resins of (B) composition used in the present invention, 2 nucleome 10 ~ 40 quality % must be contained, its number average molecular weight (Mn) is 900 ~ 2000, preferably 950 ~ 1500, weight average molecular weight (Mw) is 2500 ~ 5000, preferably 3000 ~ 4000, molecular weight distribution (Mw/Mn) is necessary for 2.0 ~ 4.0.Above-mentioned several molecular-weight average (Mn) preferably 950 ~ 1500, weight average molecular weight (Mw) preferably 3000 ~ 4000, molecular weight distribution (Mw/Mn) preferably 2.5 ~ 3.5.During the potentiality hardener composition that use obtains with the phenol resins exceeding above-mentioned scope, the stability combining the liquid hardening composition epoxy resin obtained with polyepoxides reduces, and tackiness reduces, therefore not preferred.
For the usage quantity of the phenol resins of above-mentioned (B) composition, relative to addition reaction 100 mass parts for (A) composition, preferably below 150 mass parts, particularly preferably 10 ~ 100 mass parts.Use is not only wasted more than 150 mass parts, probably also can cause detrimentally affect to hardening.
For above-mentioned (B) though the phenol resins of composition can add separately, but its blocker as the active dydrogen compounds of above-mentioned (a) composition also can be made to react and use.
Potentiality hardener composition of the present invention also can contain the carboxylic acid of such as hexanodioic acid, pentanedioic acid, pimelic acid, suberic acid, sebacic acid, toxilic acid, methylene-succinic acid, phthalandione, m-phthalic acid, terephthalic acid, trimellitic acid (trimelliticacid), pyromellitic acid (pyromellitic acid) etc.
For easily operating potentiality hardener composition of the present invention, can dissolve in all kinds of SOLVENTS and use.This equal solvent can be the ethers of such as tetrahydrofuran (THF), 1,2-glycol dimethyl ether, 1,2-diethoxyethane etc.; The alcohols of the n-butanols of XOR, the n-propyl alcohol of XOR, amylalcohol, hexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol etc.; The aromatic hydrocarbons of benzene,toluene,xylene etc.; Aniline, triethylamine, pyridine, dioxan, acetonitrile etc.
The usage quantity of above-mentioned organic solvent, relative to total amount 100 mass parts of solid substance, is 0 ~ 200 mass parts, preferably 30 ~ 150 mass parts.If the usage quantity of organic solvent is more than 200 mass parts, except volatilization is harmful, also can the danger such as ignition be produced, therefore not preferred.
Potentiality hardener composition of the present invention, also can use polyepoxides and/or cyanate, combines and use with the host for principal constituent.
Above-mentioned polyepoxides can be the poly epihydric alcohol ether compound of the monokaryon polyphenol compounds such as such as quinhydrones, Resorcinol, pyrocatechol, Phloroglucinol (phloroglucinol), dihydroxy naphthlene, '-biphenyl diphenol, methylene radical bis-phenol (Bisphenol F), methylene radical two (ortho-cresol), ethylidene bis-phenol, isopropylidene bisphenol (dihydroxyphenyl propane), isopropylidene two (ortho-cresol), tetrabromo-bisphenol, 1, 3-bis-(4-hydroxyisopropyl benzene), 1, 4-bis-(4-hydroxyisopropyl benzene), 1, 1, 3-joins (4-hydroxy phenyl) butane, 1, 1, 2, 2,-wantonly (4-hydroxy phenyl) ethane, thiodiphenol, sulfonyldiphenol, oxygen base bis-phenol, phenol novolacs, o-cresol novolak, ethyl phenol phenolic varnish, butylphenol phenolic varnish, octyl phenol phenolic varnish, Resorcinol phenolic varnish, the poly epihydric alcohol ether compound of the multinuclear polyphenol compounds such as terpene phenolic, the polyglycidyl ether of the polyalcohols such as ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, polyoxyethylene glycol, thiobis ethylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, bisphenol A-propylene oxide affixture, toxilic acid, fumaric acid, methylene-succinic acid, succsinic acid, pentanedioic acid, suberic acid, hexanodioic acid, nonane diacid, sebacic acid, dimeracid, trimer acid, phthalandione, m-phthalic acid, terephthalic acid, trimellitic acid (trimellitic acid), trimesic acid (trimesic acid), pyromellitic acid (pyromellitic acid), tetrahydrochysene phthalandione, six hydrogen phthalandiones, the aliphatics such as interior methylene radical tetrahydrochysene phthalandione, the Racemic glycidol ethers of aromatic series or alicyclic polyprotonic acid and the homopolymer of glycidyl methacrylate or multipolymer, N, N-diglycidylaniline, two (4-(N-methyl-N-glycidyl amido) phenyl) methane etc. have the epoxy compounds of glycidyl amido, vinyl cyclohexane epoxide, Dicyclopentadiene (DCPD) diepoxide, 6-butylcyclohexane carboxylic acid 3, the epoxide of the cyclic alkene compound of 4-epoxy group(ing)-6-methylcyclohexyl methyl esters, hexanodioic acid two (3,4-epoxy group(ing)-6-methylcyclohexyl methyl esters) etc., the heterogeneous ring compound of the epoxidation conjugated diolefin polymer, isocyanuric acid three-glycidyl ester etc. of epoxidized polybutadiene, epoxidized styrene-butadiene multipolymer etc.Again, even if these epoxy resin terminal isocyanate acidic groups carry out internal crosslinking by prepolymer, also by multicomponent reactive hydrogen compound (polyphenol, polyamine, poly phosphate etc.), polymer quantizes.
Again, the polyepoxides used in the present invention, epoxy equivalent (weight) preferably 100 ~ 2000, particularly preferably 150 ~ 1500.When using epoxy equivalent (weight) to be less than 100, probably hardening reduces, and when use is greater than 2000, probably can not get sufficient Physical properties of coating film, therefore not preferred.
Above-mentioned polyepoxides, because easily operate, so can dissolve and use in all kinds of SOLVENTS.Now used solvent, except above-mentioned solvent, can be the ketone of such as methyl ethyl ketone, Methyl amyl ketone, metacetone, acetone, methyl isopropyl Ketone, propylene glycol monomethyl ether, pimelinketone etc.; The ester class of vinyl acetic monomer, n-butyl acetate etc.; The terpenes hydrocarbon ils of terpenes oil, D-limonene (limonene), firpene (pinene) etc.; The high boiling point paraffin class solvent etc. of mineral turpentine (mineral spirit), Swazol#310 (Cosmo Guia Hill oil (stock) company), Solvesso#100 (Exxon chemistry (stock) company) etc.
The usage quantity of above-mentioned organic solvent, relative to polyepoxides 100 mass parts, is 0 ~ 200 mass parts, and with 30 ~ 150 mass parts particularly preferably.If the usage quantity of above-mentioned organic solvent is more than 200 mass parts, except volatilization is harmful, also can the danger such as ignition be produced, therefore not preferred.
Again, polyepoxides used in the present invention is in main host, also can use reactive or non-reacted thinner.Reactive diluent can be the glycidyl etherified compound of list of such as phenol, cresols, ethyl phenol, propyl phenoxy, three grades of butylphenols, three grades of amylic phenols, hexyl phenol, octyl phenol, nonyl phenol, 4-dodecylphenol, octadecyl phenol or terpene phenolic etc.On the other hand, non-reactive diluent can be such as dioctyl phthalate, Dibutyl phthalate, phenylcarbinol etc.
Polyepoxides in a liquid curable resin composition of the present invention, with the usage quantity of potentiality hardener composition of the present invention, though preferably the former epoxy equivalent (weight) and the equal use of Ahew of the latter, but its amount also can optionally change in meaning in office.
Potentiality hardener composition of the present invention, can be used in the combination of the host based on polyepoxides, such as, for coating or the tackiness agent of concrete, sand-cement slurry, various metal, leather, glass, rubber, plastics, wood, cloth, paper etc.; Packaging adheres to the tackiness agent that adhesive tape, adhesion label, frozen product label, removable label, POS label, adhesion wallpaper, adhesion bed material etc. use; The converted paper of enamelled paper (art paper), light weight coated paper, mirror copper millboard (cast coat paper), coating paperboard, noncarbon recording paper, impregnation paper etc.; The fibre finish collecting agent, off-line preventing agent, machining agent etc. of natural fiber, synthon, glass fibre, carbon fiber, steel fiber etc.; The material of construction of pointing, cement admixture, water-proof material etc.; The extensive use of electric, the electronic material of laminated plates, semi-conductor sealing material etc. etc.
Again, potentiality hardener composition of the present invention, combinationally uses particularly preferably with the host that above-mentioned polyepoxides is common and cyanate are principal constituent.
In the present invention, spendable cyanate is not particularly limited, and can be the compound that such as following general formula (1) represents:
N≡C－O－R
2－R
1－R
3－O－C≡N (1)
Or, the compound that following general formula (2) represents:
But, R in above-mentioned general formula (1)
1indicate without the divalent alkyl replaced or fluorine replaces, or-O-,-S-or singly-bound, R
2and R
3indicate independently of one another and stretch phenyl without what replace or replace through 1 ~ 4 alkyl, the n in general formula (2) represents the integer of more than 1, R
4represent the alkyl of hydrogen atom or carbon number 1 ~ 4.
Again, the part of the cyanic acid base in the compound of above-mentioned general formula (1) or (2) forms the prepolymer of triazine ring, and also can be used as with cyanate is the host of principal constituent.Above-mentioned prepolymer can be such as with all or part of trimerizing of compound person that above-mentioned general formula (1) represents.
Being used as in the present invention with cyanate is the host of principal constituent, the compound that preferred following general formula (3) represents, and their prepolymer:
In the present invention particularly preferably 4,4 '-ethylene stretches phenylcyanate, 2,2-bis-(4-cyanic acid base phenyl) propane and two (4-cyanic acid base-3,5-3,5-dimethylphenyl) methane as host.
Moreover, the R in above-mentioned general formula (3)
5, the base for following:
Or, base:
N in above-mentioned base is the integer of 4 ~ 12, R
6, R
7, R
8and R
9the methyl being hydrogen atom independently of one another or replacing without replacement or fluorine, R
10and R
11the methyl being hydrogen atom independently of one another or replacing without replacement or fluorine.
In the present invention, can be used alone above-mentioned cyanate, also two or more combination can be used.
In a liquid curable resin composition of the present invention, optionally also can contain filling agent or the pigment such as resin particle of glass fibre, carbon fiber, Mierocrystalline cellulose, fine sand, cement, kaolin, clay, aluminium hydroxide, bentonite, talcum, silica, micropowder silica, titanium dioxide, carbon black, graphite, ferric oxide, asphaltic substances, metallics, coating metal; Tackifier; Shake change agent; Incombustible agent; Defoamer; Rust-preventive agent; The additive that colloidal silica, colloidal alumina etc. are conventional, moreover, also can also with the adhesive resene such as xylene resin, petroleum resin.
A liquid curable resin composition of the present invention also can use with a solvent-free liquid type as aforesaid way.For this kind solvent-free time, due to the generation of such as VOC can be suppressed, not only can provide and suppress carrying capacity of environment and the high material of security, and produce the advantage of " narrow positions is soaked into and sclerosis etc., also can use even if can not use in the purposes of solvent ".
A liquid curable resin composition of the present invention, can be used in such as the extensive use of the coating or tackiness agent etc. of concrete, sand-cement slurry, various metal, leather, glass, rubber, plastics, wood, cloth, paper etc.Especially, owing to having high heat resistance and excellent tackiness, the electronic material purposes or the automotive material purposes that are used in semi-conductor sealing, electronic component adhesion etc. can be applicable to.
By following Production Example and embodiment, illustrate in greater detail the present invention, but the present invention is not restricted because of its grade.
[Production Example 1 ~ 6]
The manufacture of phenol resins (PR1 ~ PR6)
In the four mouthfuls of detachable flasks possessing thermometer, whipping appts, instillation device and cooling tube, add phenol, 50% formlinata aquae concentratac and oxalic acid and heat, making it react 4 hours in reflux temperature.After back flow reaction, concentrated through 3 hours after making it be warming up to 160 DEG C at ambient pressure, still be held in again 160 DEG C and be decompressed to 20 ~ 30 holder (torr), carry out being evaporated to overhead product no longer out, obtain the tawny phenol resins (PR1 ~ PR6) with the molecular weight distribution shown in following [table 1].
After each test portion 0.01g obtained is dissolved in THF 10g, use gel permeation chromatography (gelpermeation chromatography) (the Shodex GPC-101 of Showa electrician (stock) Inc.), use the Shodex KF-802 of Showa electrician's (stock) Inc. as mensuration corpse or other object for laboratory examination and chemical testing tubing string simultaneously, use the Shodex KF-800RH tubing string in contrast of Showa electrician's (stock) Inc., use THF as developing solvent, from the measured value deriving from RI detector, calculate the polystyrene conversion number molecular-weight average of each test portion, and weight average molecular weight and molecular weight distribution.
[table 1]
PH: phenol
[embodiment 1]
In the flask possessing thermometer, refrigerating unit, whipping appts, instillation device and dewatering unit, add propylene glycol monomethyl ether 300g and N, N-diethyl aminocarbonyl propyl amine 100g, reaction system is warming up to 70 ~ 75 DEG C, instillation Adeka Resin EP-4100E (trade(brand)name of ADEKA (stock) company: Bisphenol A type epoxy resin, epoxy equivalent (weight) 190) 213g.Instillation in 110 ~ 130 DEG C of maturations 1 hour, and in 110 ~ 130 DEG C, spends 1 hour after ending under normal pressure, in 175 ~ 185 DEG C, spend 1 hour, carry out desolventizing under 20 ~ 30 holders.Then, add in 175 ~ 185 DEG C of phenol resins PR1 by 210g in batches, make phenol resins dissolve simultaneously.Moreover, in 180 ~ 190 DEG C, spend 1 hour under 20 ~ 30 holders, carry out decompression degassed, obtain hardener composition (HC-1).Ground in mortar by the hardener composition obtained, when using the melting point apparatus (MP-S3, below equally) of Yanaco Inc. to measure, fusing point is 85 DEG C.
[embodiment 2]
Outside use 1,2-bis-amido propane 74g replacement N, N-diethyl aminocarbonyl propyl amine 100g, mode is reacted similarly to Example 1, processes, and obtains hardener composition (HCH-1).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 91 DEG C.
[embodiment 3]
Except use phenol resins PR2 replaces except phenol resins PR1, mode is reacted similarly to Example 1, processes, and obtains hardener composition (HC-2).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 85 DEG C.
[embodiment 4]
Beyond use 1,2-bis-amido propane 74g replacement N, N-diethyl aminocarbonyl propyl amine 100g, mode is reacted similarly to Example 3, processes, and obtains hardener composition (HCH-2).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 90 DEG C.
[embodiment 5]
Except use phenol resins PR3 replaces except phenol resins PR1, mode is reacted similarly to Example 1, processes, and obtains hardener composition (HC-3).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 82 DEG C.
[embodiment 6]
Beyond use 1,2-bis-amido propane 74g replacement N, N-diethyl aminocarbonyl propyl amine 100g, react with Production Example 5 the same manner, process, obtain hardener composition (HCH-3).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 88 DEG C.
[comparative example 1]
Except use phenol resins PR4 replaces except phenol resins PR1, mode is reacted similarly to Example 1, processes, and obtains hardener composition (HC-4).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 86 DEG C.
[comparative example 2]
Beyond use 1,2-bis-amido propane 74g replacement N, N-diethyl aminocarbonyl propyl amine 100g, react with comparative example 1 the same manner, process, obtain hardener composition (HCH-4).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 89 DEG C.
[comparative example 3]
Except use phenol resins PR5 replaces except phenol resins PR1, mode is reacted similarly to Example 1, processes, and obtains hardener composition (HC-5).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 95 DEG C.
[comparative example 4]
Beyond use 1,2-bis-amido propane 74g replacement N, N-diethyl aminocarbonyl propyl amine 100g, react with comparative example 3 the same manner, process, obtain hardener composition (HCH-5).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 91 DEG C.
[comparative example 5]
Except use phenol resins PR6 replaces except phenol resins PR1, mode is reacted similarly to Example 1, processes, and obtains hardener composition (HC-6).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 82 DEG C.
[comparative example 6]
Beyond use 1,2-bis-amido propane 74g replacement N, N-diethyl aminocarbonyl propyl amine 100g, react with comparative example 3 the same manner, process, obtain hardener composition (HCH-6).Ground in mortar by the hardener composition obtained, when using the melting point apparatus of Yanaco Inc. to measure, fusing point is 87 DEG C.
[embodiment 7 ~ 9 and comparative example 7 ~ 9]
In above-described embodiment and comparative example, the hardener composition manufactured is added according to the composition shown in [table 2], manufactures a liquid hardening composition epoxy resin, carry out following performance evaluation.Its result is as shown in [table 3].
(hardening)
The hardening of the liquid hardening composition epoxy resin obtained according to table 2, for after just manufacturing, uses gelatinization test machine (hot plate type gelatinization test machine GT-DS-SF:Yukari skill grinds the trade(brand)name of (stock) Inc.) to measure.Now, not form the time point of wire drawing as gel time.
(reaction starts temperature)
Use SII Nanotec Solution differential scanning calorimetry DSC6220, with heat-up rate 10 DEG C/minute, scanning temperature range 25 ~ 300 DEG C measures, and using reading from DSC form, heating temp starts temperature as reaction.
(viscosity)
The liquid hardening composition epoxy resin obtained according to table 2 is positioned over 25 DEG C, uses BrookfieldE type revolution viscometer, viscosity when measuring 25 DEG C with 5rpm.
(tackiness)
About the liquid hardening composition epoxy resin obtained according to table 2, by the method according to JIS K 6850, ask for the shearing clinging power of the steel plate/steel plate after hardening through 60 minutes at 80 DEG C.
[table 2]
EP:Adeka Resin EP-4100L; ADEKA (stock) Inc.; Bisphenol A type epoxy resin, epoxy equivalent (weight) 170
CY:Primaset LECY; Lonza Inc.; Bisphenol E-type cyanate resin
[table 3]
From the result of embodiment, can confirm manufacturing containing when being reacted potentiality hardener composition used for epoxy resin that the addition reaction that obtains and phenol resins form by the amine compound and multi-epoxy compound with active hydrogen base significantly, the phenol resins used contains 2 nucleome 10 quality % ~ 40 quality %, number average molecular weight (Mn) is 900 ~ 2000, weight average molecular weight (Mw) is 2500 ~ 5000, when molecular weight distribution (Mw/Mn) is 2.0 ~ 4.0, the hardening of the liquid hardening composition epoxy resin containing potentiality hardener composition obtained, stability and tackiness are very excellent.
On the other hand, 2 nucleome content are used to be less than 10 quality % persons as (comparative example 1) during phenol resins, even if 2 nucleomes are below 10 ~ 40 quality %, weight average molecular weight is greater than 5000, when molecular weight distribution is greater than 4.0 (comparative example 2), a liquid hardening composition epoxy resin that can only obtain poor adherence can be confirmed; Use 2 nucleome content to be greater than 40 quality %, number molecular-weight average is less than 900 as (comparative example 3) during phenol resins, can confirm a liquid hardening composition epoxy resin that can only obtain poor stability.
Industrial usability
Due to by by potentiality hardener composition of the present invention and polyepoxides and the cyanate recombinant that optionally uses, the liquid curable resin composition that storage stability, hardening and tackiness are excellent can be obtained, used automation, can efficiency be used in such as coating or the tackiness agent of concrete, various metal, leather, glass, rubber, plastics etc. well; Packaging adheres to the tackiness agent of adhesive tape, adhesion label, frozen product label, adhesion wallpaper, adhesion bed material etc.; The converted paper of impregnation paper etc.; The fibre finish collecting agent, off-line preventing agent, machining agent etc. of natural fiber, synthon, glass fibre etc.; The material of construction of pointing, cement admixture, water-proof material etc.; The extensive use of electric, the electronic material of laminated plates, semi-conductor sealing material etc. etc., can have great expectations of the development of industry thus.
Claims (7)
1. a potentiality hardener composition, for the amine compound and (b) multi-epoxy compound that have an active hydrogen base by (a) containing (A) react the potentiality hardener composition used for epoxy resin that the addition reaction of gained and (B) phenol resins form; The feature of this potentiality hardener composition is: this phenol resins contains two nucleomes of 10 ~ 40 quality %, several molecular-weight average (Mn) of this phenol resins are 900 ~ 2000 simultaneously, weight average molecular weight (Mw) is 2500 ~ 5000, and molecular weight distribution (Mw/Mn) is 2.0 ~ 4.0.
2. potentiality hardener composition according to claim 1, is characterized in that, the amine compound that this (a) has active hydrogen base comprises the amine compound with more than at least 13 grades of amidos.
3. potentiality hardener composition according to claim 2, it is characterized in that, this has the dialkylamine pheynylalkylamine of amine compound represented by following general formula (I) of more than at least 13 grades of amidos or the imidazolium compounds represented by following general formula (II):
General formula (I):
In formula, the R in above-mentioned general formula (I)
1and R
2separately represent the alkyl of carbonatoms 1 ~ 8, or R
1with R
2bond, represent the alkylene base that can contain Sauerstoffatom or nitrogen-atoms, n represents the integer of 1 ~ 6;
General formula (II):
R in above-mentioned general formula (II)
3~ R
5represent hydrogen atom, substituent alkyl or aryl can be had.
4. potentiality hardener composition according to claim 2, is characterized in that, this amine compound with more than at least 13 grades of amidos is be selected from least one in diethyl amido propylamine, diethyl amido ethamine, N-amido ethyl piperazidine.
5. potentiality hardener composition according to any one of claim 1 to 4, is characterized in that, the phenol resins of this (B) composition is the phenol resins from phenol and formaldehyde gained.
6. a liquid curable resin composition, containing polyepoxides and at least one potentiality hardener composition according to any one of claim 1 to 5.
7. a liquid curable resin composition, containing polyepoxides, cyanate and at least one potentiality hardener composition according to any one of claim 1 to 5.
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| PCT/JP2011/004551 WO2012020572A1 (en) | 2010-08-12 | 2011-08-11 | Latent curing agent composition and one-part curable epoxy resin composition |
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| KR101515488B1 (en) * | 2014-07-01 | 2015-04-30 | 주식회사 신아티앤씨 | Hardener for epoxy resin |
| KR101741652B1 (en) | 2015-05-08 | 2017-06-01 | 주식회사 케이씨씨 | Latent crosslinker for powder coatings and powder coating composition comprising the same |
| JP2020100727A (en) * | 2018-12-21 | 2020-07-02 | 株式会社Adeka | Latent curing agent composition and curable resin composition containing the same |
| CN113544120B (en) | 2019-02-28 | 2023-05-02 | 株式会社Adeka | Novel compound, composition containing same, self-repairing material, surface coating agent, paint, adhesive, battery material, and cured product |
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| US4066625A (en) * | 1967-05-02 | 1978-01-03 | Amicon Corporation | Unitary curable resin compositions |
| CN101633724A (en) * | 2003-07-03 | 2010-01-27 | 日本电气株式会社 | Epoxy resin composition |
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| JP5058486B2 (en) * | 2003-07-03 | 2012-10-24 | 日本電気株式会社 | Epoxy resin composition |
| JP2007079588A (en) * | 2006-10-11 | 2007-03-29 | Nippon Kayaku Co Ltd | Liquid crystal sealant and liquid crystal cell |
| JP5415947B2 (en) * | 2007-06-22 | 2014-02-12 | 株式会社Ａｄｅｋａ | One-component cyanate-epoxy composite resin composition |
| JP5517326B2 (en) * | 2008-06-27 | 2014-06-11 | 株式会社Ａｄｅｋａ | One-component cyanate-epoxy composite resin composition |
| JP5355113B2 (en) * | 2009-01-29 | 2013-11-27 | 株式会社Ａｄｅｋａ | One-component cyanate ester-epoxy composite resin composition |
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| US4066625A (en) * | 1967-05-02 | 1978-01-03 | Amicon Corporation | Unitary curable resin compositions |
| CN101633724A (en) * | 2003-07-03 | 2010-01-27 | 日本电气株式会社 | Epoxy resin composition |
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