CN105324363A - Thiol-group-containing compound and single-liquid epoxy resin composition - Google Patents
Thiol-group-containing compound and single-liquid epoxy resin composition Download PDFInfo
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- CN105324363A CN105324363A CN201480035301.6A CN201480035301A CN105324363A CN 105324363 A CN105324363 A CN 105324363A CN 201480035301 A CN201480035301 A CN 201480035301A CN 105324363 A CN105324363 A CN 105324363A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/32—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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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
- C08G59/66—Mercaptans
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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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
Abstract
Provided is a novel thiol-group-containing compound. Further provided are: an epoxy resin curing agent containing the thiol compound; and a single-liquid epoxy resin composition containing same. Specifically, provided is a thiol-group-containing compound represented by formula (1) (in formula (1): R represents a hydrogen atom, a hydrocarbon group optionally having a substituent group, or -CH2-OC(O)-[CH2]l-SH (where l is an integer from 1 to 8); X and Z each independently represent a divalent aliphatic hydrocarbon group optionally having a substituent group; Y represents a divalent group selected from -OC(O)-, -C(O)O-, -NHC(O)-, -C(O)NH-, -SC(O)-, and -C(O)S-; m represents an integer from 1 to 8; n represents an integer from 1 to 8; and l represents an integer from 1 to 8).
Description
Technical field
The present invention relates to the specific compound containing thiol group, and then the hardener for epoxy resin related to containing this mercaptan compound and containing its one-component epoxy resin composition etc.
Background technology
Use the compound containing thiol group excellent as the composition curability at low temperatures of the solidifying agent of epoxy resin, therefore various research has been carried out to it.Such as, disclose a kind of polyether polymer containing thiol group halogen end thereof polyether polymer and hydrogen Sodium Sulphide and/or many Sodium Sulphide being reacted in amides gained in Japanese Unexamined Patent Publication 8-269203 publication (patent documentation 1) as the resin combination of resin solidifying agent, described halogen end thereof polyether polymer obtains by making epihalohydrin and main chain have polyether moiety, end has more than 3 hydroxyls polyvalent alcohol addition.Solidifying agent is according to the material that is cured, and the requirement of the curing characteristics such as set time, solidification value is different, and therefore in order to tackle the various uses of the various material that is cured, requirement prepares the specific solidifying agent under specific end use in advance in a large number.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 8-269203 publication.
Summary of the invention
The object of the invention is to, a kind of compound of novel sulfurized alcohol radical is provided, and the novel one-component epoxy resin solidifying agent of the compound containing thiol group containing this is provided.
Another object of the present invention is to, provide the epoxy resin cured product of this one-component epoxy resin composition solidification gained.
The present inventor etc. have carried out conscientiously studying to solve the problem, and result utilizes the compound of specific novel sulfurized alcohol radical to solve the problems referred to above.
That is, the present invention is as described below,
[1] formula (1) represent containing the compound of thiol group:
(in formula (1), R represents hydrogen atom, optionally has substituent alkyl or-CH
2-OC (O)-[CH
2]
l-SH (l represents the integer of 1 ~ 8),
X and Z represents optionally have substituent divalent aliphatic hydrocarbon independently of one another,
Y represent be selected from-OC (O)-,-C (O) O-,-NHC (O)-,-C (O) NH-,-SC (O)-and-C (O) S-in divalent group,
M represents the integer of 1 ~ 8,
N represents the integer of 1 ~ 8);
[2] [1] record containing the compound of thiol group, wherein, R represents the saturated or undersaturated straight or branched alkyl of hydrogen atom or carbonatoms 1 ~ 15,
X and Z represents the divalent alkyl optionally with substituent carbonatoms 1 ~ 20 independently of one another;
[3] [1] or [2] record containing the compound of thiol group, it be 2-ethyl-2-{{{3-[(3-mercapto radical propionyl group) sulfenyl] propionyl } oxygen base methyl propane-1,3-bis-base pair (3-mercaptopropionic acid ester);
[4] hardener for epoxy resin of the compound containing thiol group recorded any one of [1] to [3] is contained;
[5] one-component epoxy resin composition, it contains [1] has the epoxy resin (composition (2)) of more than 2 epoxy group(ing) to the compound (composition (1)) containing thiol group recorded any one of [3] and molecule;
[6] [5] one-component epoxy resin composition of recording, it is further containing solid dispersing On The Latent Accelerator (composition (3));
[7] [6] one-component epoxy resin composition of recording, wherein, when the content of composition (2) is set to 100 mass parts, the content of composition (3) is 0.1 ~ 100 mass parts;
[8] one-component epoxy resin composition recorded any one of [5] to [7], it is further containing more than one (composition (4)) of being selected from boric acid ester compound, titanate compound, Aluminate compound, zirconate compound, isocyanate compound, carboxylic acid, acid anhydrides and sulfydryl organic acid;
[9] [8] one-component epoxy resin composition of recording, wherein, when the content of composition (2) is set to 100 mass parts, the content of composition (4) is 0.001 ~ 50 mass parts;
[10] one-component epoxy resin composition recorded any one of [5] to [9], it contains compound (composition (5)) that is different from composition (1), that have more than 2 thiol groups in molecule further;
[11] [10] one-component epoxy resin composition of recording, wherein, composition (5) is trimethylolpropane tris (3-mercaptopropionic acid ester);
[12] [10] or [11] one-component epoxy resin composition of recording, wherein, the quality of composition (1) is 0.001 ~ 1.0 relative to composition (1) and the ratio [composition (1)/(composition (1)+composition (5))] of the total mass of composition (5);
[13] one-component epoxy resin composition recorded any one of [5] to [12], wherein, in composition (1), the total yield of mercaptan base is 0.2 ~ 2.0 relative to the ratio [thiol group total yield number/epoxy equivalent (weight) number] of the epoxy equivalent (weight) of the epoxy resin of composition (2);
[14] one-component epoxy resin composition recorded any one of [10] to [12], wherein, the total yield of composition (1) and the middle mercaptan base of composition (5) is 0.2 ~ 2.0 relative to the ratio [thiol group total yield number/epoxy equivalent (weight) number] of the epoxy equivalent (weight) of the epoxy resin of composition (2);
[15] epoxy resin cured product that the one-component epoxy resin composition by recording any one of [5] to [14] heats and obtains.
Invention effect
The compound of novel sulfurized alcohol radical of the present invention can make epoxy resin cure.And then, by combine the resin solidifying agent of the compound containing novel sulfurized alcohol radical of the present invention and composition (2) and arbitrary composition (3), composition (4) and/or composition (5) as resin combination, thus form the one-component epoxy resin composition playing low-temperature fast-curing property, storage stability also excellence.
Embodiment
[compound containing thiol group]
Formula (1) containing thiol group of the present invention represents,
Formula (1):
(in formula (1), R represents hydrogen atom, optionally has substituent alkyl or-CH
2-OC (O)-[CH
2]
l(l represents the integer of 1 ~ 8 to-SH.L is more preferably the integer of 1 ~ 6, and then is preferably the integer of 2 ~ 4.)。R is preferably hydrogen atom or optionally has substituent saturated or undersaturated straight or branched alkyl, is more preferably hydrogen atom or optionally has the saturated of substituent carbonatoms 1 ~ 30 or undersaturated straight or branched alkyl.
Saturated or the undersaturated straight or branched alkyl of R more preferably hydrogen atom or carbonatoms 1 ~ 15, especially be preferably the saturated or undersaturated straight or branched alkyl of hydrogen atom or carbonatoms 1 ~ 6, be particularly preferably the saturated or undersaturated straight or branched alkyl of hydrogen atom or carbonatoms 1 ~ 4.Be more preferably saturated straight chain alkyl.
Optionally there is substituent alkyl, include, for example out: methyl, ethyl, sec.-propyl, propyl group, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, isopentyl, hexyl, heptyl, octyl group, 2-ethylhexyl, tertiary octyl group, nonyl, different nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl and containing these substituent groups.
In formula (1), X and Z represents optionally have substituent divalent aliphatic hydrocarbon independently of one another.Divalent aliphatic hydrocarbon can be saturated hydrocarbyl also can be unsaturated alkyl, and its carbonatoms is preferably 1 ~ 20, is more preferably 1 ~ 10, more preferably 2 ~ 6.Above-mentioned carbonatoms does not comprise substituent carbonatoms.
As above-mentioned divalent aliphatic hydrocarbon, include, for example out: alkylidene group, cycloalkylidene, alkenylene, sub-cycloalkenyl group, alkynylene, sub-cycloalkynyl radical, sub-polyene-based (alkapolyenylene), sub-diynyl (alkadiynylene), sub-three alkynyls (alkatriynylene) etc., preferred alkylidene group, cycloalkylidene, alkenylene, alkynylene.Therefore, in a preferably embodiment, X and Z is independently of one another for optionally having the divalent alkyl of substituent carbonatoms 1 ~ 20.More preferably be the divalent alkyl of carbonatoms 1 ~ 20 independently of one another.
As above-mentioned alkylidene group, include, for example out: methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, octylene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl, sub-tridecyl, sub-tetradecyl, sub-pentadecyl, sub-hexadecyl, sub-heptadecyl, sub-octadecyl, sub-nonadecyl etc.
Y represent be selected from-OC (O)-,-C (O) O-,-NHC (O)-,-C (O) NH-,-SC (O)-and-C (O) S-in divalent group.Y be more preferably be selected from-OC (O)-,-C (O) O-,-SC (O)-and-C (O) S-in divalent group, be more preferably selected from-SC (O)-and-C (O) S-in divalent group.
M represents the integer of 1 ~ 8.Be more preferably the integer of 1 ~ 6, more preferably the integer of 2 ~ 4.
N represents the integer of 1 ~ 8.Be more preferably the integer of 1 ~ 6, more preferably the integer of 2 ~ 4.
In this specification sheets; unless otherwise noted; term " substituting group " refers to, is selected from the group in halogen atom, alkyl, cycloalkyl, alkoxyl group, cycloalkyloxy, aryl, aryloxy, aralkyl, alkoxy aryl, monovalence heterocyclic radical, amino, silyl, acyl group, acyloxy, carboxyl, cyano group, nitro, hydroxyl, sulfydryl and oxo base.
As being used as substituent halogen atom, such as, can exemplify out fluorine atom, chlorine atom, bromine atoms and atomic iodine.
Any one of straight-chain or branched is can be as substituent alkyl.The carbonatoms of this alkyl is preferably 1 ~ 20, is more preferably 1 ~ 14, and more preferably 1 ~ 12, be more preferably 1 ~ 6 further, be particularly preferably 1 ~ 3.As this alkyl, include, for example out methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl.As described later, as substituent alkyl, and then can there is substituting group (" secondary substituting group ").As having the substituent alkyl of described secondary, include, for example out the alkyl replaced by halogen atom, specifically, trifluoromethyl, trichloromethyl, four fluoro ethyls, four chloroethyls etc. can be listed.
Carbonatoms as substituent cycloalkyl is preferably 3 ~ 20, is more preferably 3 ~ 12, more preferably 3 ~ 6.As this cycloalkyl, include, for example out cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.
Any one of straight-chain or branched is can be as substituent alkoxyl group.The carbonatoms of this alkoxyl group is preferably 1 ~ 20, is more preferably 1 ~ 12, and more preferably 1 ~ 6.As this alkoxyl group, include, for example out methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, sec-butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base and the last of the ten Heavenly stems oxygen base.
Carbonatoms as substituent cycloalkyloxy is preferably 3 ~ 20, is more preferably 3 ~ 12, and more preferably 3 ~ 6.As this cycloalkyloxy, include, for example out ring propoxy-, cyclobutoxy group, cyclopentyloxy and cyclohexyloxy.
As the group that substituent aryl is from a hydrogen atom gained aromatic hydrocarbons removing aromatic nucleus.Carbonatoms as substituent aryl is preferably 6 ~ 24, is more preferably 6 ~ 18, and more preferably 6 ~ 12.As this aryl, include, for example out phenyl, naphthyl and anthryl.
Carbonatoms as substituent aryloxy is preferably 6 ~ 24, is more preferably 6 ~ 18, and more preferably 6 ~ 12.As being used as substituent aryloxy, include, for example out phenoxy group, 1-naphthyloxy and 2-naphthyloxy.
Carbonatoms as substituent aralkyl is preferably 7 ~ 25, is more preferably 7 ~ 19, and more preferably 7 ~ 13.As this aralkyl, include, for example out phenyl-C1 ~ C12 alkyl, naphthyl-C1 ~ C12 alkyl and anthryl-C1 ~ C12 alkyl.
Carbonatoms as substituent alkoxy aryl is preferably 7 ~ 25, is more preferably 7 ~ 19, and more preferably 7 ~ 13.As this alkoxy aryl, include, for example out phenyl-C1 ~ C12 alkoxyl group and naphthyl-C1 ~ C12 alkoxyl group.
Refer to as substituent monovalence heterocyclic radical, from the group of a hydrogen atom gained hetero ring type compound removing heterocycle.The carbonatoms of this monovalence heterocyclic radical is preferably 3 ~ 21, is more preferably 3 ~ 15, and more preferably 3 ~ 9.This monovalence heterocyclic radical also comprises monovalence aromatic heterocycle (heteroaryl).As this monovalence heterocycle, include, for example out thienyl, pyrryl, furyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, triazinyl, pyrrolidyl, piperidyl, quinolyl and isoquinolyl.
As substituent amino can be straight-chain or branched aliphatics or aromatic any one.The carbonatoms of this amino is preferably 1 ~ 20, is more preferably 1 ~ 12, and more preferably 1 ~ 6.As this amino, include, for example out amino methyl, amino-ethyl, aminopropyl, isopropylamino, Aminobutoxy, Zhong Ding amino, i-butylamino, tertiary fourth amino, Aminopentyl, Aminohexyl, Aminoheptyl, aminoheptyl, aminononyl and aminodecyl, aminophenyl etc.
Any one of straight-chain or branched is can be as substituent silyl.The carbonatoms of this silyl is preferably 1 ~ 20, is more preferably 1 ~ 12, and more preferably 1 ~ 6.As this silyl, include, for example out methyl-silicane base, ethyl silicane base, propylsilyl, isopropyl silyl, butoxy silyl, sec-butyl silyl, isobutyl-silyl, tert. butylsilyl-group, amyl group silyl, hexyl silyl, heptyl silyl, octyl group silyl, nonyl silyl and decyl silyl.
Formula is referred to: the group (in formula, R1 is alkyl or aryl) that-C (=O)-R1 represents as substituent acyl group.The alkyl that R1 represents can be any one of straight-chain or branched.As the aryl that R1 represents, include, for example out phenyl, naphthyl and anthryl.The carbonatoms of this acyl group is preferably 2 ~ 20, is more preferably 2 ~ 13, and more preferably 2 ~ 7.As this acyl group, include, for example out ethanoyl, propionyl, butyryl radicals, isobutyryl, valeryl and benzoyl.
Formula is referred to: the group (in formula, R2 is alkyl or aryl) that-O-C (=O)-R2 represents as substituent acyloxy.The alkyl that R2 represents can be any one of straight-chain or branched.As the aryl that R2 represents, include, for example out phenyl, naphthyl and anthryl.The carbonatoms of this acyloxy is preferably 2 ~ 20, is more preferably 2 ~ 13, and more preferably 2 ~ 7.As this acyloxy, include, for example out acetoxyl group, propionyloxy, butyryl acyloxy, isobutyl acyloxy, new pentane acyloxy and benzoyloxy.
Compound containing thiol group of the present invention desirably, in formula (1), R represents the saturated or undersaturated straight or branched alkyl of hydrogen atom or carbonatoms 1 ~ 15, preferably 1 ~ 6, X and Z represent independently of one another optionally have substituent carbonatoms 1 ~ 20, preferably 1 ~ 10 divalent alkyl, Y is-SC (O)-or-C (O) S-, m is the integer of 2 ~ 4, and n is the integer of 2 ~ 4.
And then; as the compound containing thiol group of the present invention; particularly preferably have with the 2-ethyl-2-{{{3-of the structural formula of following formula (2) [(3-mercapto radical propionyl group) sulfenyl] propionyl oxygen base methyl propane-1,3-bis-base two (3-mercaptopropionic acid ester).
[hardener for epoxy resin]
Compound containing thiol group of the present invention can make epoxy resin cure, therefore can be used as hardener for epoxy resin and uses.In the case, preferably the total yield of above-mentioned thiol group is adjusted to 0.2 ~ 2.0 relative to the ratio (thiol group total yield number/epoxy equivalent (weight) number) of the epoxy equivalent (weight) of epoxy resin, is more preferably 0.6 ~ 1.2.Herein, epoxy equivalent (weight) refers to the quality of the epoxy resin containing 1 equivalent epoxy group(ing), such as, can measure according to JISK7236 (2009).Thiol group total yield refers to the quality of the compound containing thiol group containing 1 equivalent thiol group.
As long as the compound containing thiol group of hardener for epoxy resin of the present invention containing the invention described above, also can further containing imidazoles, the amine as other compositions.Other compositions relative to hardener for epoxy resin, such as, can contain 0.01 ~ 10 quality %, are preferably 0.1 ~ 5 quality %.
[one-component epoxy resin composition]
One-component epoxy resin composition of the present invention is at least containing the epoxy resin (composition (2)) in above-claimed cpd (composition (1)) and molecule with more than 2 epoxy group(ing).One-component epoxy resin composition of the present invention is preferably arbitrarily containing solid dispersing On The Latent Accelerator (composition (3)).And then one-component epoxy resin composition of the present invention preferably contains arbitrarily: be selected from more than one (composition (4)) in boric acid ester compound, titanate compound, Aluminate compound, zirconate compound, isocyanate compound, carboxylic acid, acid anhydrides and sulfydryl organic acid; And/or, there is in the molecule different from composition (1) compound of more than 2 thiol groups, namely there are in molecule more than 2 thiol groups and not there is in molecule the compound (composition (5)) of hydroxyl.By containing above-mentioned each composition, one-component epoxy resin composition of the present invention can have low-temperature fast-curing property and storage stability concurrently.
Should illustrate, when the content of the epoxy resin of composition (2) is set to 100 mass parts, the content of the compound containing thiol group of composition (1) is preferably 0.1 ~ 100 mass parts, is more preferably 1 ~ 98 mass parts, more preferably 5 ~ 95 mass parts.
Composition (2)
Composition (2) used in the present invention as long as epoxy resin on average every 1 molecule there are more than 2 epoxy group(ing).Include, for example out the polyglycidyl ether that the polyphenol such as dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, catechol, Resorcinol or the polyvalent alcohol such as glycerine, polyoxyethylene glycol and Epicholorohydrin react gained; The hydroxycarboxylic acid of P-hydroxybenzoic acid, β oxynaphthoic acid and so on and Epicholorohydrin react the Racemic glycidol ether-ether of gained; The polycarboxylic acid of phthalic acid, terephthalic acid and so on and Epicholorohydrin react the poly glycidyl ester of gained; And then epoxidized phenol novolac resin, epoxidized cresol novolac resin, epoxidized polyolefin, ring type aliphatic epoxy resin, other urethane-modified epoxy resin etc. can be listed, but be not limited to this.
As the epoxy resin of composition (2), specifically, wherein from the view point of maintenance high heat resistance and low-moisture permeability etc., preferred bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, biphenyl aralkyl-type epoxy resin, phenol aralkyl type epoxy resin, aromatic series glycidyl amine type epoxy resin, there is the epoxy resin etc. of Dicyclopentadiene (DCPD) structure, more preferably bisphenol A type epoxy resin and bisphenol f type epoxy resin, further preferred bisphenol A type epoxy resin.
The epoxy resin of composition (2) can be liquid, also can be solid-state, can also use liquid and solid-state both.Herein, " liquid state " and " solid-state " refers to the state of epoxy resin under normal temperature (25 DEG C).From the view point of coating, processibility, cementability, more than at least 10 quality % of the whole epoxy resin preferably used are liquid.As the concrete example of this liquid-state epoxy resin, there is liquid bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) system " エ ピ コ ー ト 828EL ", " エ ピ コ ー ト 827 "), liquid bisphenol F type epoxy resin (Mitsubishi Chemical's (strain) system " エ ピ コ ー ト 807 "), (DIC (strain) makes " HP4032 " to naphthalene type bifunctional epoxy resin, " HP4032D "), liquid bisphenol AF type epoxy resin (Dongdu changes into (strain) makes " ZXlO59 "), the epoxy resin (Mitsubishi Chemical's (strain) system " エ ピ コ ー ト YX8000 ") of hydrogenation structure.Wherein preferably high heat-resisting and low viscous Mitsubishi Chemical (strain) Inc. " エ ピ コ ー ト 828EL ", " エ ピ コ ー ト 827 " and " エ ピ コ ー ト 807 ", more preferably " エ ピ コ ー ト 828EL ".In addition, as the concrete example of solid epoxy resin, naphthalene type 4 functional epoxy resins (DIC (strain) makes " HP4700 ") can be listed, dicyclopentadiene-type polyfunctional epoxy resin (DIC (strain) makes " HP7200 "), naphthol type epoxy resin (Dongdu changes into (strain) makes " ESN-475V "), there is the epoxy resin (Daicel (ダ イ セ Le) chemical industry (strain) system " PB-3600 ") of butadiene structure, there is epoxy resin (the Japanese chemical drug (strain) system " NC3000H " of biphenyl structural, " NC3000L ", Mitsubishi Chemical's (strain) system " YX4000 ") etc.
When being 100 quality % with the total mass of resin combination of the present invention, the content of the epoxy resin of composition (2) is such as preferably more than 5 quality %, be more preferably more than 10 quality %, more preferably more than 20 quality %, be more preferably more than 30 quality % further, especially be preferably more than 40 quality %, be particularly preferably more than 45 quality %.In addition, the content of the epoxy resin of composition (2) is preferably below 95 quality %, is more preferably below 90 quality %, more preferably below 85 quality %, be more preferably below 80 quality % further, be especially preferably below 75 quality %, be particularly preferably below 70 quality %.
Composition (3)
The solid dispersing On The Latent Accelerator of composition (3) used in the present invention refers to, for being insoluble to the solid of the epoxy resin of composition (2) under room temperature (25 DEG C), and by heating solubilized, as the compound that the curing catalyst of epoxy resin works, be imidazolium compounds and the solid dispersing amine adduct system On The Latent Accelerator of solid under can listing normal temperature, but be not limited to this.As the example of solid dispersing amine adduct system On The Latent Accelerator, the reaction product (urea type adduction system) etc. of the reaction product (amine-epoxy adduct system) of amine compound and epoxy compounds, amine compound and isocyanate compound or carbamide compound can be listed.Wherein, preferred solid dispersing amine adduct system On The Latent Accelerator.
As the imidazolium compounds under above-mentioned normal temperature being solid, include, for example out: 2-heptadecyl imidazole, 2-phenyl-4, 5-hydroxymethyl-imidazole, 2-undecyl imidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2-phenyl-4-benzyl-5-hydroxy methylimidazole, 2, 4-diamino-6-(glyoxal ethyline base-(1))-ethyl-s-triazine, 2, 4-diamino-6-(2 '-methylimidazolyl-(1) ')-ethyl-s-triazine-isocyanuric acid adduct, glyoxal ethyline, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-cyano ethyl-glyoxal ethyline-trimellitate, 1-cyano ethyl-2-phenylimidazole-trimellitate, N-(glyoxal ethyline base-1-ethyl)-urea, N, N '-(glyoxal ethyline base-(1)-ethyl)-hexanedioyl diamide (ア ジ ボ イ Le ジ ア ミ De) etc., but be not limited to this.
As the epoxy compounds of one of manufacture raw material being used as above-mentioned solid dispersing amine adduct system On The Latent Accelerator (amine-epoxy adduct system), include, for example out the polyglycidyl ether that the polyvalent alcohol of the polyphenol such as dihydroxyphenyl propane, Bisphenol F, catechol, Resorcinol or glycerine, polyoxyethylene glycol and so on and Epicholorohydrin react gained; The hydroxycarboxylic acid of P-hydroxybenzoic acid, β oxynaphthoic acid and so on and Epicholorohydrin react the Racemic glycidol ether-ether of gained; The polycarboxylic acid of phthalic acid, terephthalic acid and so on and Epicholorohydrin react the poly glycidyl ester of gained; 4,4 '-diaminodiphenyl-methane, Metha Amino Phenon etc. and Epicholorohydrin react the Racemic glycidol amine compound of gained; And then the mono-functional such as multi-functional epoxy compounds or butylglycidyl ether, phenyl glycidyl ether, the glycidyl methacrylate epoxy compounds etc. such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, epoxidized polyolefin can be listed, but be not limited to this.
As the amine compound of the manufacture raw material of above-mentioned solid dispersing amine adduct system On The Latent Accelerator, as long as there is more than 1 can carry out the active hydrogen of addition reaction with epoxy group(ing) in molecule, and at least there is more than 1 functional group be selected from primary amino, secondary amino group and tertiary amino in molecule.As such amine compound, include, for example out: diethylenetriamine, Triethylenetetramine (TETA), Tri N-Propyl Amine, 2-hydroxyethylamino propylamine, cyclo-hexylamine, 4, the aliphatics amine of 4 '-diamino-dicyclohexyl methyl hydride and so on; 4, the aromatic amines compound such as 4 '-diaminodiphenyl-methane, 2-aminotoluene; The heterogeneous ring compound etc. containing nitrogen-atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole quinoline, 2,4-methylimidazole quinolines, piperidines, piperazine, but be not limited to this.
In addition, the compound wherein particularly in molecule with tertiary amino is to provide the raw material of the On The Latent Accelerator with excellent solidification promotion ability, as the example of such compound, include, for example out: uncle or the secondary amine class in the molecule of imidazolium compounds such as amine compound or glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole such as dimethylaminopropylamine, diethylaminopropylamine, two n-propylamine base propylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylamino-ethylamine, N methyl piperazine and so on tertiary amino, DMAE, 1-methyl-DMAE, 1-phenoxymethyl-DMAE, 2-diethylaminoethanol, 1-butoxymethyl-DMAE, 1-(2-hydroxyl-3-phenoxy propyl)-glyoxal ethyline, 1-(2-hydroxyl-3-phenoxy propyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxyl-3-butoxypropyl)-glyoxal ethyline, 1-(2-hydroxyl-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxyl-3-phenoxy propyl)-2-benzylimidazoline, 1-(2-hydroxyl-3-butoxypropyl)-glyoxal ethyline quinoline, 2-(dimethylamino methyl) phenol, 2,4,6-tri-(dimethylamino methyl) phenol, N-beta-hydroxy ethyl morpholine, 2-dimethylamino sulfur alcohol, 2-mercaptopyridine, 2-benzoglyoxaline, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, DMG, nicotinic acid, γ-picolinic acid, pyridine carboxylic acid, DMG hydrazides, N, N-neopentanoic acid hydrazides, hydroxyacyl hydroxyacyl hydrazine, there is in the molecule that isonicotinic acid hydrazide etc. are such the alcohols of tertiary amino, phenols, thio-alcohol, carboxylic-acid and hydrazides class etc.
Make above-mentioned epoxy compounds and amine compound carry out addition reaction prepare On The Latent Accelerator time, the active dydrogen compounds with more than 2 active hydrogens can be added in molecule further.As such active dydrogen compounds, include, for example out the polycarboxylic acid classes, 1 such as the polyalcohols such as polyatomic phenol, TriMethylolPropane(TMP), hexanodioic acid, phthalic acid such as dihydroxyphenyl propane, Bisphenol F, bisphenol S, quinhydrones, catechol, Resorcinol, pyrogallol, phenol resol resins, 2-dimercaptoethane, 2 mercapto ethanol, 1-sulfydryl-3-phenoxy group-2-propyl alcohol, Thiovanic acid, anthranilic acid, lactic acid etc., but be not limited to this.
As the isocyanate compound of the manufacture raw material as above-mentioned solid dispersing amine adduct system On The Latent Accelerator, such as, can use the monofunctional isocyanates compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate ester; Hexamethylene diisocyanate, toluylene vulcabond, 1,5-naphthalene diisocyanate, ditan-4,4 '-vulcabond, isophorone diisocyanate, xylylene diisocyanate, to phenylene diisocyanate, 1, the polyfunctional isocyanate compound such as 3,6-hexa-methylene triisocyanate, norbornane triisocyanate; And then these polyfunctional isocyanate compound and active dydrogen compounds can also be used to react the compound etc. containing terminal isocyanate group of gained.As the example of such compound containing terminal isocyanate group, toluylene vulcabond and TriMethylolPropane(TMP) can be listed and react the addition compound etc. with terminal isocyanate group that the addition compound with terminal isocyanate group of gained, toluylene vulcabond and tetramethylolmethane react gained, but be not limited to this.
In addition, as the carbamide compound of the manufacture raw material as above-mentioned solid dispersing amine adduct system On The Latent Accelerator, include, for example out urea, thiocarbamide etc., but be not limited to this.
The solid dispersing On The Latent Accelerator of composition (3), such as by above-mentioned manufacture raw material is suitably mixed, after reacting at the temperature of room temperature to 200 DEG C, pulverize after cooling curing, or react in methyl ethyl ketone, diox, tetrahydrofuran (THF) equal solvent, after desolventizing, solids component pulverized and easily obtain.
As the typical example that the solid dispersing On The Latent Accelerator of composition (3) is commercially available, such as amine-epoxy adduct system (amine adduct system), can list " ア ミ キ ュ ア PN-23 " (Ajincomoto Co., Inc's trade(brand)name), " ア ミ キ ュ ア PN-H " (Ajincomoto Co., Inc's trade(brand)name), “ ハ ー ド ナ ー X-3661S " (エ ー シ ー ア ー Le (strain) trade(brand)name), “ ハ ー ド ナ ー X-3670S " (エ ー シ ー ア ー Le (strain) trade(brand)name), " ノ バ キ ュ ア HX-3742 " (Asahi Chemical Industry's (strain) trade(brand)name), " ノ バ キ ュ ア HX-3721 " (Asahi Chemical Industry's (strain) trade(brand)name) etc., in addition as urea type adduction system, " Off ジ キ ュ ア FXE-1000 " (Fuji changes into (strain) trade(brand)name) can be listed, " Off ジ キ ュ ア FXR-1030 " (Fuji changes into (strain)) etc., but be not limited to this.
When the content of the epoxy resin of composition (2) is set to 100 mass parts, the content of the solid dispersing On The Latent Accelerator of composition (3) is preferably 0.1 ~ 100 mass parts, be more preferably 1 ~ 60 mass parts, more preferably 5 ~ 30 mass parts.
Composition (4)
Composition of the present invention in order to realize excellent storage stability, preferably further containing more than one (composition (4)) of being selected from boric acid ester compound, titanate compound, Aluminate compound, zirconate compound, isocyanate compound, carboxylic acid, acid anhydrides and sulfydryl organic acid.
As above-mentioned boric acid ester compound, include, for example out: trimethyl borate, triethyl borate, boric acid three n-propyl, triisopropyl borate ester, tri-n-butyl borate, triamyl borate, boric acid triallyl, the own ester of boric acid three, tricyclohexyl borate, boric acid three monooctyl ester, boric acid three ester in the ninth of the ten Heavenly Stems, boric acid three ester in the last of the ten Heavenly stems, boric acid three (dodecyl) ester, boric acid three (hexadecyl) ester, boric acid three (octadecyl) ester, three (2-ethyl hexyl oxy) borine, two (1, 4, 7, 10-tetra-oxaundecyl) (1, 4, 7, 10, 13-five oxa-tetradecyl) (1, 4, 7-trioxaundecane base) borine, boric acid tribenzyl ester, boric acid triphenyl ester, boric acid tri-o-tolyl ester, boric acid three tolyl esters, triethanolamine borate etc.
As above-mentioned titanate compound, include, for example out tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate, tetrabutyl titanate, metatitanic acid four monooctyl ester etc.
As above-mentioned Aluminate compound, include, for example out aluminic acid triethyl, aluminic acid three propyl ester, aluminic acid three isopropyl ester, aluminic acid tri-n-butyl, aluminic acid three monooctyl ester etc.
As above-mentioned zirconate compound, include, for example out zirconic acid tetra-ethyl ester, zirconic acid orthocarbonate, zirconic acid four isopropyl ester, tetrabutyl zirconate etc.
As above-mentioned isocyanate compound, include, for example out n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, parachlorobenzyl isocyanic ester, benzyl isocyanate ester, hexamethylene diisocyanate, 2-ethylphenyl isocyanic ester, 2, 6-dimethylphenyl isocyanate, 2, 4-tolylene diisocyanate, toluylene vulcabond, 2, 6-tolylene diisocyanate, 1, 5-naphthalene diisocyanate, ditan-4, 4 '-vulcabond, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, to phenylene diisocyanate, norbornane triisocyanate etc.
As above-mentioned carboxylic acid, include, for example out: formic acid, acetic acid, propionic acid, butyric acid, caproic acid, the representative examples of saturated aliphatic monoprotic acid such as sad; The unsaturated aliphatic monoprotic acid such as vinylformic acid, methacrylic acid, β-crotonic acid; The acid of the halogenated aliphatic such as monochloro acetic acid, dichloro acetic acid; The acid of the monohydroxylic such as oxyacetic acid, lactic acid; The aliphatic aldehyde-acid such as oxoethanoic acid, racemic tartaric acid and ketone acid; The aliphatic polybasic acids such as oxalic acid, propanedioic acid, succsinic acid, toxilic acid; The aromatic series monoprotic acid such as phenylformic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, styracin, amygdalic acid; The aromatic polyvalent such as phthalic acid, trimesic acid acid etc.
As above-mentioned acid anhydrides, include, for example out: the aliphatics such as adducts, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride of succinyl oxide, dodecenyl succinic anhydride, maleic anhydride, methyl cyclopentadiene and maleic anhydride or aliphatic polybasic acid anhydrides etc.; Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, PMA (No water ピ ロ リ メ リ ッ ト acid) etc. aromatic polyvalent acid anhydrides etc.
As above-mentioned sulfydryl organic acid, include, for example out: the mercapto aliphatic monocarboxylic acids such as Thiovanic acid, thiohydracrylic acid, mercaptobutyric acid, mercaptosuccinic acid, dimercaptosuccinic acid(DMSA); By the mercapto aliphatic monocarboxylic acid of hydroxy organic acid and sulfydryl organic acid esterification gained; The sulfydryl aromatic monocarboxylates etc. such as Thiosalicylic acid.
As composition (4), wherein, storage stability high from the view point of versatility, security improves, preferred boric acid ester cpds, more preferably triethyl borate, boric acid three n-propyl, triisopropyl borate ester, tri-n-butyl borate, further preferred boric acid triethyl.Composition (4) if content resin storage stability improve then be not particularly limited, when the content of the epoxy resin of composition (2) is set to 100 mass parts, the content of composition (4) is preferably 0.001 ~ 50 mass parts, be more preferably 0.05 ~ 30 mass parts, more preferably 0.1 ~ 10 mass parts.
As composition (4) fitting method in composition epoxy resin of the present invention, except coordinating with each composition of composition (1) ~ (3), can also in advance the solid dispersing On The Latent Accelerator of composition (3) be mixed with composition (4) simultaneously.Blending means now, can, by methyl ethyl ketone, toluene equal solvent or in liquid-state epoxy resin, also or under condition of no solvent, make the two contact mix.
Composition (5)
Except above-mentioned composition, from the view point of curability at low temperatures, preferably coordinate the compound (composition (5)) in the molecule different from composition (1) with more than 2 thiol groups.
As the compound in molecule with more than 2 thiol groups, include, for example out the mercaptan compound by polyvalent alcohol and sulfydryl organic acid esterification gained such as trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris (mercaptoacetate), tetramethylolmethane four (mercaptoacetate), ethylene glycol dimercapto acetate, trimethylolpropane tris (β-mercaptopropionic acid ester), tetramethylolmethane four (β-mercaptopropionic acid ester), Dipentaerythritol many (β-mercaptopropionic acid esters).From the view point of storage stability, the compound that preferred alkaline foreign matter content is few, without the need to using the compound of alkaline matter on more preferably preparing, such as trimethylolpropane tris (3-mercaptopropionic acid ester).
In addition, as the compound in the molecule different from composition (1) with more than 2 thiol groups, also can use Isosorbide-5-Nitrae-succinimide mercaptans, 1,6-ethanthiol, 1,10-the last of the ten Heavenly stems two the alkyl multi-thioalcohol compound such as mercaptan; Containing the polyethers of terminal mercaptan base; Containing the polythioether of terminal mercaptan base; Epoxy compounds and hydrogen sulfide react the mercaptan compound of gained; Multi-thioalcohol compound and epoxy compounds react gained have mercaptan compound of terminal mercaptan base etc. such in its preparation section, use alkaline matter as the compound of catalysts, but preferably carry out dealkalize process, make alkalimetal ion concentration reach below 50ppm.
As the dealkalize treatment process of the multi-thioalcohol compound using alkaline matter to prepare as catalysts, include, for example out: the multi-thioalcohol compound carrying out processing is dissolved in the organic solvent such as acetone, methyl alcohol, add after the acid such as dilute hydrochloric acid, dilute sulphuric acid neutralizes, carried out the method for dealkalize by extraction, washing etc.; Or the method making spent ion exchange resin carry out adsorbing, carry out the method etc. of purifying by distillation, but be not limited to this.
When the content of the epoxy resin of composition (2) is set to 100 mass parts, the content of composition (5) is preferably 20 ~ 100 mass parts, is more preferably 30 ~ 90 mass parts, more preferably 45 ~ 80 mass parts.
When using composition (5) in the present invention, the quality of composition (1) is preferably 0.001 ~ 1.0 relative to composition (1) and the ratio [composition (1)/(composition (1)+composition (5))] of the total mass of composition (5).Lower value is more preferably 0.01, and more preferably 0.03, be more preferably 0.1 further.Higher limit is not particularly limited, and is more preferably 1.0, and more preferably 0.95, be more preferably 0.9 further.
The total yield of composition (1) and the middle mercaptan base of composition (5) is preferably 0.2 ~ 2.0 relative to the ratio [thiol group total yield number/epoxy equivalent (weight) number] of the epoxy equivalent (weight) of the epoxy resin of composition (2), be more preferably 0.4 ~ 1.6, more preferably 0.6 ~ 1.2.
Be that one-component epoxy resin composition of the present invention prepared by raw material using composition as above (1) and composition (2) and each composition as the composition (3) of any composition, composition (4) and composition (5), there is no special difficult point, can be prepared according to existing known method.Such as, the mixing machines such as Henschel mixer can be used to be mixed by each composition, prepare one-component epoxy resin composition of the present invention.
In addition, the solidification of gained one-component epoxy resin composition does not have special difficult point yet, and this also can be prepared according to existing known method.Such as, can solidify by heating gained one-component epoxy resin composition.Heating be suitable for such as 70 ~ 150 DEG C, be preferably 75 ~ 120 DEG C, at the temperature that is more preferably 80 ~ 100 DEG C, carry out such as 1 ~ 60 minute, be preferably 3 ~ 30 minutes, be more preferably time of 5 ~ 15 minutes.Particularly, if by 80 DEG C or 100 DEG C less than 10 minutes heating and solidify, then can be judged as the low-temperature fast-curing property with appropriateness.
In one-component epoxy resin composition of the present invention, the various additive such as weighting agent, thinner, solvent, pigment, flexible imparting agent, coupling agent, antioxidant, thixotropy conferring agents, dispersion agent conventional in the field of the invention can be added as required.
The present invention also comprises the epoxy resin cured product obtained by heating above-mentioned one-component epoxy resin composition, also comprises the functional product containing this epoxy resin cured product.As functional product, include, for example out caking agent, casting agent, encapsulant, sealing agent, fiber strengthening resin, coating agent or coating etc.
Embodiment
Below, according to embodiment, more specific description is carried out to the present invention, but the present invention is not limited to following examples.Should illustrate, " part " in below recording refers to " mass parts ".
< synthesis example 1>
As described below, prepare the compound containing thiol group of the present invention and 2-ethyl-2-{{{3-[(3-mercapto radical propionyl group) sulfenyl] propionyl } oxygen base } methyl } propane-1,3-bis-base two (3-mercaptopropionic acid ester).
Namely, first in reaction vessel, 1 is added, 1,1-tri-(methylol) propane 800g (5.96mol), 3-thiohydracrylic acid 569.6g (5.37mol), tosic acid monohydrate 8.0g (4.21mmol), stir.After confirming reaction, by gained reactants dissolved in acetone 8L, add tosic acid monohydrate 40g (21.05mmol), stir and obtain crude product.Gained crude product and then with silica column purification, obtains introducing 1 thiol group and 2 protected compounds of hydroxyl.
Then, in above-mentioned gained compound, add trityl as protecting group 3-thiohydracrylic acid 314.1g (0.90mol), acetonitrile 600ml, N-Methylimidazole (201.8g, 2.46mol) stir, and obtain crude product.Gained crude product and then with silica column purification, obtains the compound of thioesterification.
And then, in gained compound 400g (675mmol), add methyl alcohol 1.5L and water 267ml, and then add hydrochloric acid 41ml and stir, implement the deprotection of hydroxyl, obtain 380g crude product.In gained crude product, add trityl as protecting group 3-thiohydracrylic acid 189g (543mmol), acetonitrile 350ml, N-Methylimidazole (134g, 1.63mol) stir, and then keep 0 ~ 5 DEG C (average 3 DEG C) to drip having dissolved in acetonitrile 500ml the solution that Tosyl chloride 124g (651mmol) makes.Gained crude product purified by silica gel purifying, obtains the purified of the compound introducing thiol group in residual hydroxyl.
Trifluoroacetic acid is added in gained above-claimed cpd; carry out trityl removal; silica gel purification is carried out to the crude product after trityl removal; obtain 94g target product (2-ethyl-2-{{{3-[(3-mercapto radical propionyl group) sulfenyl] propionyl } oxygen base } methyl propane-1,3-bis-base two (3-mercaptopropionic acid ester)).The NMR data of gained target product are as follows,
。
The abbreviation of the raw material used in embodiment is as follows,
Composition (2): epoxy resin:
" エ ピ コ ー ト 828EL " (Mitsubishi Chemical Ind's trade(brand)name); Bisphenol A type epoxy resin
Epoxy equivalent (weight) 184 ~ 194
Composition (5): multi-thioalcohol compound:
" TMTP " (Sigma-Aldrich (Sigma-Aldrich) company trade(brand)name); Trimethylolpropane tris (3-mercaptopropionic acid ester)
Composition (3): solid dispersing curing catalyst:
" ア ミ キ ュ ア PN-23 " (aginomoto fine chemistry (monosodium glutamate Off ァ イ Application テ Network ノ) company's trade(brand)name)
Additive: thixotropy conferring agents:
Micropowder silicon-dioxide " AEROSIL200 " (Japanese ア エ ロ ジ Le Co., Ltd.).
The preparation method of embodiment 1 ~ 5
Mixing triethyl borate in bisphenol A type epoxy resin " エ ピ コ ー ト 828EL "; with the specified amount shown in the cooperation of table 1 add wherein gained in synthesis example 1 target product (2-ethyl-2-{{{3-[(3-mercapto radical propionyl group) sulfenyl] propionyl } oxygen base } methyl propane-1; 3-bis-base two (3-mercaptopropionic acid ester)) and " TMTP ", mix.Finally add " ア ミ キ ュ ア PN-23 " and thixotropy conferring agents micropowder silicon-dioxide " AEROSIL200 ", fully stir and make uniform one-component epoxy resin composition.Use level and evaluation result are shown in table 1.
(evaluation method)
[gelation time determination test]
According to JISC6521, hot plate type gelation trier (GT-D: day new science Inc.) is used the one-component epoxy resin composition of embodiment gained to be determined at respectively to the time (" 80 DEG C (second) " and " 100 DEG C (second) " with reference to table 1) becoming not wire drawing at 80 DEG C, 100 DEG C.Specifically, 0.5g one-component epoxy resin composition is placed in moment on the hot plate of the above-mentioned hot plate type gelation trier of the mensuration temperature being adjusted to 80 DEG C or 100 DEG C for starting point, on hot plate, the mode within the scope of diameter 25mm is limited according to one-component epoxy resin composition, with the scraper of nose width 5mm, contact picture circular motion (1 second rotated 1 circle) is carried out repeatedly to this resin combination, so that one-component epoxy resin composition is vertically mentioned when 30mm filament disconnects for terminal from hot plate, time till this origin-to-destination was measured as the time reaching gelation.Mensuration repeats 3 times, adopts its mean value (" 80 DEG C of evaluations " and " 100 DEG C of evaluations " with reference to table 1).
The time reaching gelation is that the resin combination of less than 5 minutes is evaluated as zero, and the resin combination of less than 15 minutes is evaluated as △, more than the resin combination of 15 minutes be evaluated as ×.If solidified below 15 minutes at measuring temperature 80 DEG C or 100 DEG C, then can be judged as that there is low-temperature fast-curing property.
[storage stability test]
According to JISK-6870, use E type viscometer under 20rpm, the condition of 25 DEG C, measure the initial viscosity of the one-component epoxy resin composition of embodiment gained.In addition, these one-component epoxy resin compositions are preserved in the thermostatic chamber of 25 DEG C, is taken out after 4 days, by E type viscometer determining viscosity under 20rpm, the condition of 25 DEG C, compare with initial viscosity and evaluate storage stability.The resin combination that [viscosity after 4 days]/[initial viscosity] is less than 1.2 is evaluated as zero, more than 1.2 and the resin combination being less than 2.0 be evaluated as △, more than 2.0 resin combination be evaluated as ×.
[bonding strength]
According to JISK-6850, the bonding portion of 100mm × 25mm size is made between 2 slice lapping iron (thickness 1.6mm), the one-component epoxy resin composition of embodiment gained is used for this bonding portion, implement the heating of 120 DEG C in 60 minutes, make this resin composition, by bonding for 2 slice lapping iron.The thickness of resin cured matter is 3mm.Used TENSILON universal testing machine (Toyo Seiki (strain) TENSILONUTM-ST processed) with 25 DEG C, the condition of draw speed 1mm/ minute measures the tensile shear power of above-mentioned resin cured matter.
[stripping test]
According to JISK-6854, the bonding portion of 150mm × 300mm size is made between 2 slice lapping iron (thickness 1.6mm), the one-component epoxy resin composition of embodiment gained is used for this bonding portion, implement the heating of 120 DEG C in 60 minutes, make this resin composition, by bonding for 2 slice lapping iron.The thickness of resin cured matter is 3mm.Used TENSILON universal testing machine (オ リ エ Application テ ッ Network (strain) RTM-500 processed) with 25 DEG C, the condition of draw speed 50mm/ minute carries out stripping test.
[table 1]
。
Confirm that the resin combination of embodiment 1 ~ 4 all solidified at 80 DEG C, 100 DEG C within 5 minutes, the resin combination of embodiment 5 solidified at 100 DEG C within 5 minutes, showed that the mercaptan compound of the application is useful as the solidifying agent of epoxy resin.Bonding strength, stripping test result are also good, and known is the resin combination that can fully use.
Should illustrate, the total yield of the thiol group contained by composition (1) is 1.0 relative to the ratio [thiol group total yield number/epoxy equivalent (weight) number] of the epoxy equivalent (weight) of the epoxy resin of composition (2).
Can be clear and definite, as long as the quality of composition (1) is 0.1 ~ 1.0 relative to composition (1) and the mass ratio [composition (1)/(composition (1)+composition (5))] of the total mass of composition (5), is then formed and have good storage stability and the one-component epoxy resin composition of rapidly-curable concurrently.
Even if solidifying agent of the present invention keeps the storage stability of more than 4 days at 25 DEG C, and demonstrates low-temperature fast-curing property.
Industrial applicability
According to the present invention, neo-epoxy resin solidifying agent can be provided.By combine resin solidifying agent of the present invention and composition (2) and arbitrary composition (3), composition (4) and/or composition (5) as resin combination, thus form the one-component epoxy resin composition playing low-temperature fast-curing property, storage stability also excellence.
Be suitable for the low-temperature fast-curing property of requirement with the caking agent of the electronic industry association area all areas that is representative, casting agent, encapsulant, sealing agent, fiber strengthening resin, the purposes such as coating agent or coating.
Claims (15)
1. formula (1) represent containing the compound of thiol group:
In formula (1), R represents hydrogen atom, optionally has substituent alkyl or-CH
2-OC (O)-[CH
2]
l-SH, wherein l represents the integer of 1 ~ 8,
X and Z represents optionally have substituent divalent aliphatic hydrocarbon independently of one another,
Y represent be selected from-OC (O)-,-C (O) O-,-NHC (O)-,-C (O) NH-,-SC (O)-and-C (O) S-in divalent group,
M represents the integer of 1 ~ 8,
N represents the integer of 1 ~ 8.
2. the compound containing thiol group according to claim 1, wherein, R represents the saturated or undersaturated straight or branched alkyl of hydrogen atom or carbonatoms 1 ~ 15,
X and Z represents the divalent alkyl optionally with substituent carbonatoms 1 ~ 20 independently of one another.
3. the compound containing thiol group described in claim 1 or 2, it is 2-ethyl-2-{{{3-[(3-mercapto radical propionyl group) sulfenyl] propionyl } oxygen base } methyl } propane-1,3-bis-base two (3-mercaptopropionic acid ester).
4. hardener for epoxy resin, it contains the compound containing thiol group according to any one of claims 1 to 3.
5. one-component epoxy resin composition, it contains composition (1) and composition (2),
The compound containing thiol group of described composition (1) according to any one of claims 1 to 3,
Described composition (2) is for having the epoxy resin of more than 2 epoxy group(ing) in molecule.
6. one-component epoxy resin composition according to claim 5, it is further containing composition (3), and this composition (3) is solid dispersing On The Latent Accelerator.
7. one-component epoxy resin composition according to claim 6, wherein, when the content of composition (2) is set to 100 mass parts, the content of composition (3) is 0.1 ~ 100 mass parts.
8. the one-component epoxy resin composition according to any one of claim 5 ~ 7, it is further containing composition (4), more than one for being selected from boric acid ester compound, titanate compound, Aluminate compound, zirconate compound, isocyanate compound, carboxylic acid, acid anhydrides and sulfydryl organic acid of this composition (4).
9. one-component epoxy resin composition according to claim 8, wherein, when the content of composition (2) is set to 100 mass parts, the content of composition (4) is 0.001 ~ 50 mass parts.
10. the one-component epoxy resin composition according to any one of claim 5 ~ 9, it is further containing composition (5), and this composition (5) is compound that is different from composition (1), that have more than 2 thiol groups in molecule.
11. one-component epoxy resin compositions according to claim 10, wherein, composition (5) is trimethylolpropane tris (3-mercaptopropionic acid ester).
One-component epoxy resin composition described in 12. claims 10 or 11, wherein, the quality of composition (1) is relative to the ratio of composition (1) with the total mass of composition (5), that is, composition (1)/(composition (1)+composition (5)) is 0.001 ~ 1.0.
One-component epoxy resin composition according to any one of 13. claims 5 ~ 12, wherein, the total yield of mercaptan base is relative to the ratio of the epoxy equivalent (weight) of the epoxy resin of composition (2) in composition (1), that is, thiol group total yield number/epoxy equivalent (weight) number is 0.2 ~ 2.0.
One-component epoxy resin composition according to any one of 14. claims 10 ~ 12, wherein, in composition (1) and composition (5), the total yield of mercaptan base is relative to the ratio of the epoxy equivalent (weight) of the epoxy resin of composition (2), that is, thiol group total yield number/epoxy equivalent (weight) number is 0.2 ~ 2.0.
15. are heated by the one-component epoxy resin composition according to any one of claim 5 ~ 14 and the epoxy resin cured product obtained.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013141656 | 2013-07-05 | ||
| JP2013-141656 | 2013-07-05 | ||
| PCT/JP2014/067927 WO2015002301A1 (en) | 2013-07-05 | 2014-07-04 | Thiol-group-containing compound and single-liquid epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105324363A true CN105324363A (en) | 2016-02-10 |
| CN105324363B CN105324363B (en) | 2018-07-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201480035301.6A Active CN105324363B (en) | 2013-07-05 | 2014-07-04 | Compound containing mercapto and one-component epoxy resin composition |
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| JP (1) | JP6493764B2 (en) |
| KR (1) | KR102182890B1 (en) |
| CN (1) | CN105324363B (en) |
| DE (1) | DE112014003163T5 (en) |
| TW (1) | TWI607989B (en) |
| WO (1) | WO2015002301A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054760A (en) * | 2018-01-18 | 2019-07-26 | 味之素株式会社 | One-component resin composition |
| CN111019093A (en) * | 2019-12-10 | 2020-04-17 | 武汉市科达云石护理材料有限公司 | Room-temperature rapid epoxy curing agent and application thereof in preparation of epoxy dry-hanging adhesive |
| CN112752783A (en) * | 2019-08-21 | 2021-05-04 | 纳美仕有限公司 | Epoxy resin composition |
| CN112778501A (en) * | 2020-12-24 | 2021-05-11 | 艾勒可新材料(佛山)有限公司 | Solid mercaptan curing agent, powder coating and preparation method thereof |
| CN114437314A (en) * | 2022-03-10 | 2022-05-06 | 韦尔通(厦门)科技股份有限公司 | Polythiol curing agent, single-component epoxy adhesive and preparation method thereof |
| CN115926580A (en) * | 2023-01-13 | 2023-04-07 | 江苏恒美幕墙材料有限公司 | Light curtain wall aluminum plate and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6531400B2 (en) * | 2015-01-22 | 2019-06-19 | 日油株式会社 | Curable resin composition |
| JP6467946B2 (en) * | 2015-01-28 | 2019-02-13 | 日油株式会社 | Curable resin composition |
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- 2014-07-04 JP JP2015525298A patent/JP6493764B2/en active Active
- 2014-07-04 CN CN201480035301.6A patent/CN105324363B/en active Active
- 2014-07-04 DE DE112014003163.1T patent/DE112014003163T5/en active Pending
- 2014-07-04 WO PCT/JP2014/067927 patent/WO2015002301A1/en active Application Filing
- 2014-07-04 TW TW103123150A patent/TWI607989B/en active
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054760A (en) * | 2018-01-18 | 2019-07-26 | 味之素株式会社 | One-component resin composition |
| CN110054760B (en) * | 2018-01-18 | 2023-05-05 | 味之素株式会社 | One-component resin composition |
| CN112752783A (en) * | 2019-08-21 | 2021-05-04 | 纳美仕有限公司 | Epoxy resin composition |
| CN111019093A (en) * | 2019-12-10 | 2020-04-17 | 武汉市科达云石护理材料有限公司 | Room-temperature rapid epoxy curing agent and application thereof in preparation of epoxy dry-hanging adhesive |
| CN111019093B (en) * | 2019-12-10 | 2022-05-03 | 武汉市科达云石护理材料有限公司 | Room-temperature rapid epoxy curing agent and application thereof in preparation of epoxy dry-hanging adhesive |
| CN112778501A (en) * | 2020-12-24 | 2021-05-11 | 艾勒可新材料(佛山)有限公司 | Solid mercaptan curing agent, powder coating and preparation method thereof |
| CN114437314A (en) * | 2022-03-10 | 2022-05-06 | 韦尔通(厦门)科技股份有限公司 | Polythiol curing agent, single-component epoxy adhesive and preparation method thereof |
| CN114437314B (en) * | 2022-03-10 | 2024-01-23 | 韦尔通科技股份有限公司 | Polythiol curing agent, single-component epoxy adhesive and preparation method thereof |
| CN115926580A (en) * | 2023-01-13 | 2023-04-07 | 江苏恒美幕墙材料有限公司 | Light curtain wall aluminum plate and preparation method thereof |
| CN115926580B (en) * | 2023-01-13 | 2024-03-19 | 江苏恒美幕墙材料有限公司 | Light curtain wall aluminum plate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6493764B2 (en) | 2019-04-03 |
| TW201518268A (en) | 2015-05-16 |
| JPWO2015002301A1 (en) | 2017-02-23 |
| DE112014003163T5 (en) | 2016-03-31 |
| CN105324363B (en) | 2018-07-17 |
| WO2015002301A1 (en) | 2015-01-08 |
| TWI607989B (en) | 2017-12-11 |
| KR20160030237A (en) | 2016-03-16 |
| KR102182890B1 (en) | 2020-11-25 |
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