CN102985461A - Curable resin composition - Google Patents
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- CN102985461A CN102985461A CN2012800004393A CN201280000439A CN102985461A CN 102985461 A CN102985461 A CN 102985461A CN 2012800004393 A CN2012800004393 A CN 2012800004393A CN 201280000439 A CN201280000439 A CN 201280000439A CN 102985461 A CN102985461 A CN 102985461A
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
Provided is a curable resin composition that adheres well to an inorganic substrate. Said curable resin composition contains the following: a multifunctional thiol compound (A) having a molecular weight of 200 to 2,000; a multifunctional epoxy resin (B) having a molecular weight of 200 to 50,000 and an epoxy equivalent of 80 to 6,000 g/mol; a thioether-containing alkoxysilane derivative (C) represented by general formula (1); and an amine compound (D) having a molecular weight of 90 to 700. The weight of component (A) is 0.05 to 30 times the weight of component (B). The curable resin composition contains 0.5 to 50 weight parts of component (C) and 0.01 to 50 weight parts of component (D) per 100 total weight parts of components (A) and (B).
Description
Technical field
The present invention relates to the curable resin composition to inorganic substrate adhesivity excellences such as glass, tin indium oxide (ITO), aluminium.
Background technology
At present, when various coating being coated the inorganic substrates such as glass, in order to improve adhesivity, add silane coupling agent (for example patent documentation 1) in the composition epoxy resin of being everlasting.In addition, as existing epoxy curing agent, mercaptan compound can be used, as the catalyzer that reacts between activation epoxy group(ing) and the thiol group, the alkaline matter (for example non-patent literature 1) of amine and so on can be used.And well-known mercaptan compound and the mixture with multifunctional polyene of a plurality of pairs of keys can form the curable resin composition (for example patent documentation 2) of using up to be cured.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 7-300491 communique
Patent documentation 2: Japanese kokai publication hei 6-306172 communique
Non-patent literature
Non-patent literature 1: the Resins, epoxy summary, the 1st volume, basis piece of writing I, P204-205, Resins, epoxy technological associations compile.
Summary of the invention
Technical problem to be solved by this invention
But in patent documentation 1 described technology, the most boiling point of silane coupling agent is lower, need to make an addition in the thermosetting resin in a large number.In addition, adhesivity is improved effect and can not be said fully, for example, sometimes needs to add simultaneously salt or the sticking power auxiliary agents such as phosphoric acid ester, urethane resin such as titanium, zirconium, just begins to reach required adhesivity on the realistic scale.In this case, add these sticking power auxiliary agents, not only increased the operation number of times, need selectedly not damage the sticking power auxiliary agent kind of coating characteristic, tightly to test the problem such as optimum addition but also exist.
On the other hand, such as the cured film of non-patent literature 1 described solidification compound take mercaptan compound as solidifying agent, excellent to organic adhesivity.But, abundant not to the adhesivity of the inorganicss such as glass, ITO, aluminium.Especially, therefore the cured film poor water resistance of the solidification compound take mercaptan compound as solidifying agent if exist the problem that adhesivity descends greatly in hot and humid lower exposure.
In addition, such as the patent documentation 2 described curable resin compositions that mixed the light solidity of mercaptan compound and multifunctional polyene, resulting cured article is also abundant not to the adhesivity of inorganics.
And if the solidification compound take mercaptan compound as solidifying agent take amine as catalyzer, even at room temperature also can be cured, therefore is expected to obtain the long curing composition of a kind of usable time (spendable time under environment for use).
Therefore, the present invention In view of the foregoing finishes, and its objective is the curable resin composition that a kind of adhesivity excellence to inorganic substrates such as glass, tin indium oxide (ITO), aluminium is provided.
The means of technical solution problem
The inventor is in order to address the above problem, conduct in-depth research, found that, replace existing silane coupling agent or mercaptan compound, the alkoxyl silicone alkane derivatives that contains specific Sulfide-containing Hindered is the curable resin composition of effective constituent, inorganic substrate is had excellent adhesivity, and then finished the present invention.
Namely, the present invention is for containing following (A), (B), (C) and (D) curable resin composition of composition, described (A) composition is that molecular weight is multi-functional thiol's compound of 200 ~ 2000, described (B) composition be molecular weight be 200 ~ 50000 and epoxy equivalent (weight) be the polyfunctional epoxy resin of 80 ~ 6000g/mol, described (C) composition is the alkoxyl silicone alkane derivatives of the Sulfide-containing Hindered shown in the following general formula (1), and described (D) composition is that molecular weight is 90 ~ 700 aminated compounds.And, the weight ratio ((A)/(B)) of described (A) composition and described (B) composition is 0.05 ~ 30, take the gross weight of described (A) composition and described (B) composition as 100 weight parts, sneak into 0.5 ~ 50 weight part described (C) composition, 0.01 ~ 50 weight part described (D) composition.
Chemical formula 1
Wherein, a and b are 0 ~ 2 integer, and c is 1 ~ 3 integer, a+b+c=3.R is the trivalent group shown in the following general formula (2), R
1And R
2Be independently of one another-CH
2-CH (CH
3)-,-C (CH
3)
2-,-CH
2-CH
2-or-CH (CH
3)-in the divalent group shown in any one, R
3Be methyl or ethyl.
Chemical formula 2
Wherein, m is 1 or 2.
Like this, as the sticking power auxiliary agent, take the alkoxyl silicone alkane derivatives (C) of specific Sulfide-containing Hindered as effective constituent, balancedly add (A) ~ (D) composition, thereby can show the adhesivity to the inorganic substrate excellence.
In addition, in the present invention, " equivalent " refers to the weight of chemical substance required when forming the functional group number of 1mol chemical substance, can try to achieve by (molecular weight)/(number of functional group in 1 molecule).In addition, in the situation of polymkeric substance, " molecular weight " expression weight-average molecular weight.
Curable resin composition of the present invention except described (A) ~ (D) composition, can also contain following (E) composition.The curable resin composition described of the present invention that does not contain (E) composition is thermoset, if but to wherein adding (E) composition, then can give curable resin composition light solidity or photo-thermal two-stage solidity, can select curing reaction according to operating environment or application target etc.Specifically, as (E) composition, also can contain molecular weight and be 200 ~ 50000 and (methyl) acrylate equivalent be multifunctional (methyl) acrylic compound of 80 ~ 6000g/mol.Take the gross weight of described (A) composition and described (B) composition as 100 weight parts, can sneak into 2 ~ 300 weight parts should (E) composition.In addition, in the present invention, " (methyl) acrylate " expression comprises the general name of acrylate and methacrylic ester.
As described aminated compounds (D), preferably use with the imidazolium compounds shown in the following general formula (2).Therefore, although curable resin composition is difficult to be cured reaction in the use below 35 ℃, storage temperature range, usable time prolongs, but it can be cured reaction under 60 ℃, therefore can take into account usable time, stability in storage and low-temperature curing two aspects.
Chemical formula 3
Wherein, R
5The alkyl of the carbonatoms 1 ~ 10 that replaces for the alkyl of cyano group, carbonatoms 1 ~ 10, with 2,3-diamino triazine, alkoxyl group or the hydrogen atom of carbonatoms 1 ~ 4, R
4, R
6, R
7For the alkyl of carbonatoms 1 ~ 20, alkoxyl group or the hydrogen atom of carbonatoms 1 ~ 4, work as R
4~ R
7It is the alkyl of carbonatoms 2 ~ 8 that bonding forms in the situation about encircling.
In addition, as described multi-functional thiol's compound (A), preferably use the multi-functional thiol's compound shown in the following general formula (3).
Chemical formula 4
Wherein, n is 2 ~ 5 integer, and p is 2 ~ 10 integer, R
8For the alkyl (α 1) of carbonatoms 2 ~ 30, carbonatoms 2 ~ 40 by ether oxygen (any in group (α 2), the isocyanurate ring (α 3) that O-) consists of with alkyl or the group (α 4) that is consisted of by isocyanurate ring and alkyl.If this class multi-functional thiol compound, then the stability in storage of curable resin composition is excellent.
In addition, as described polyfunctional epoxy resin (B), preferably use Racemic glycidol ether type epoxy or glycidyl ester type epoxy resin.If this class polyfunctional epoxy resin, the reactivity under the room temperature slowly more can prolong usable time.
In addition, represent in the present invention " 00 ~ * * " of numerical range, its concept is to comprise its lower value (" 00 ") and higher limit (" * * ").Namely, clearly represent more than 00 * * below.
Beneficial effect
According to the present invention, by take the alkoxyl silicone alkane derivatives (C) of specific Sulfide-containing Hindered as effective constituent, and balanced being mixed is (A) ~ (D) of neccessary composition, need not as the situation of existing use silane coupling agent, to add other sticking power auxiliary agents, and inhibition becomes the addition of the effective constituent (C) of sticking power auxiliary agent, can obtain excellent adhesivity simultaneously.In addition, abundant not to inorganic substrate adhesivityes such as glass, tin indium oxide, aluminium in the situation of existing use mercaptan compound, and the present composition is excellent to inorganic substrate adhesivityes such as glass, tin indium oxide, aluminium, can be used as the curable resin composition of the novelty that does not have so far.
In addition, curable resin composition of the present invention, because usable time (serviceable time under the environment for use) is long, so operability is also good, stability in storage is also excellent.And, when making its thermofixation, it is solidified at low temperature and in the short period of time.That is, at room temperature be difficult to solidify, when thermofixation, even reactive (solidified nature) is also excellent under the low temperature about 60 ℃.In addition, can improve obdurability, water tolerance, thermotolerance, flexibility and the homogeneity etc. that make the cured film after curable resin composition of the present invention solidifies.Therefore, after inorganic substrate forms cured film, even be exposed to the image height temperature how under the wet condition in (for example 120 ℃ * 100RH% * 90 hour about) such severe rugged environment, also can keep sufficient adhesivity.
Embodiment
Below, the present invention is described in detail.Curable resin composition of the present invention be take following (A), (B), (C) and (D) composition can also contain as required the curable resin composition of (E) composition as neccessary composition.
(multi-functional thiol's compound ((A) composition))
Multi-functional thiol's compound (A) in the curable resin composition of the present invention refers to have the organic compound of two above thiol groups (SH yl).The molecular weight of multi-functional thiol's compound is 200 ~ 2000, and is preferred 300 ~ 1800, is more preferably 350 ~ 1600.Even molecular weight is also no problem about adhesivity less than 200, but the volatility of multi-functional thiol's compound is high, has the tendency that stink strengthens.On the other hand, if molecular weight greater than 2000, reduces with respect to the solvability of polyfunctional epoxy resin described later (B), may descend to the adhesivity of inorganic substrate.
As multi-functional thiol's compound (A), can exemplify the multi-functional thiol's compound shown in following general formula (4).In addition, multi-functional thiol's compound (A) namely can only be used alone, and also can two or more mixing use.
Chemical formula 5
Wherein, n is 2 ~ 5 integer, and p is 2 ~ 10 integer, R
8For the alkyl (α 1) of carbonatoms 2 ~ 30, carbonatoms 2 ~ 40 by ether oxygen (any in group (α 2), the isocyanurate ring (α 3) that O-) consists of with alkyl or the group (α 4) that is consisted of by isocyanurate ring and alkyl.
In above-mentioned general formula (3), even the compound of n=1 does not have large problem yet, can use, but the multi-functional thiol's compound reactivity that obtains is higher, how many stability in storagies that therefore contains the curable resin composition of this compound exists the tendency of variation.Relative with it, if the compound in n=2 ~ 5 scopes, stability in storage is excellent, in the low temperature about 60 ℃, can make its curing in the short period of time simultaneously.In addition, along with the increase of n numerical value, the reactivity of resulting multi-functional thiol's compound reduces, and has elongated tendency the set time when containing the thermofixation of curable resin composition of this compound.Therefore, in the compound shown in the above-mentioned general formula (3), the compound of n=2 most preferably.If n=2, the set time the when reactivity of multi-functional thiol's compound is solidified stability in storage and shortening heat, the two was all best.
Can obtain the multi-functional thiol's compound shown in the above-mentioned general formula (4) by the esterification of the polyfunctional alcohol shown in the mercaptan carboxylic acid shown in the following general formula (5) and the following general formula (6).
Chemical formula 6
Wherein, n is 1 ~ 5 integer.
Chemical formula 7
Wherein, p is 2 ~ 10 integer, R
8For the alkyl (α 1) of carbonatoms 2 ~ 30, carbonatoms 2 ~ 40 by ether oxygen (any in group (α 2), the isocyanurate ring (α 3) that O-) consists of with alkyl or the group (α 4) that is consisted of by isocyanurate ring and alkyl.
In the compound shown in the above-mentioned general formula (6), be 2 ~ 4 and R by P preferably
8Compound (α 1-1), the P of the group that consists of for the alkyl of carbonatoms 2 ~ 20 is 2 ~ 6 and R
8For carbonatoms 2 ~ 30 (compound (α 2-1) of the group that O-) consists of with alkyl or P are 3 and R by ether oxygen
8Compound (α 4-1) for the group that consisted of by the alkyl of isocyanurate ring and carbonatoms 1 ~ 3.This is because compound if so is with the solvability height of polyfunctional epoxy resin (B).
As (α 1-1), can exemplify alkylene glycol, glycerine, tetramethylolmethane or TriMethylolPropane(TMP) etc. such as carbonatoms 2 ~ 20.Can exemplify such as polyoxyethylene glycol, polypropylene glycol, Dipentaerythritol etc. as (α 2-1).As (α 4-1), can exemplify such as three (2-hydroxyethyl) isocyanuric acid ester etc.
＜polyfunctional epoxy resin ((B) composition) 〉
Polyfunctional epoxy resin in the curable resin composition of the present invention (B) is the organic compound with two above epoxy group(ing) (oxyethane ring).The molecular weight of polyfunctional epoxy resin is 200 ~ 50000, and is preferred 200 ~ 48000, is more preferably 200 ~ 46000.Even molecular weight is also no problem less than 200 adhesivityes, but the volatility of polyfunctional epoxy resin is higher, has the tendency that foul smell strengthens.On the other hand, if molecular weight greater than 50000, with respect to the solvability reduction of other compositions, may cause the adhesivity of inorganic substrate is descended.
The epoxy equivalent (weight) of polyfunctional epoxy resin is 80 ~ 6000g/mol, and preferred 85 ~ 5500g/mol is more preferably 90 ~ 5000g/mol.If epoxy equivalent (weight) is less than 80g/mol, epoxy group(ing) in the unit volume is too much, the epoxy group(ing) with the reaction of the thiol group of multi-functional thiol's compound (A) does not remain in a large number, the toughness of the cured film that therefore is made of curable resin composition may descend, and adhesivity may descend in the situation that is exposed to the many wet environments of high temperature.On the other hand, if epoxy equivalent (weight) is greater than 6000g/mol, epoxy group(ing) concentration significantly reduces, therefore the reaction efficiency with the thiol group of multi-functional thiol's compound (A) reduces, the toughness of the cured film that is made of curable resin composition may descend, and may descend being exposed to the many wet environments of high temperature adhesivity of lower time.
As polyfunctional epoxy resin (B), can exemplify such as Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin or with peroxide oxidation and contain two keys of double bond compound and oxidized form Resins, epoxy of obtaining etc.Wherein, because slowly reactive and usable time at room temperature prolongs therefore preferred Racemic glycidol ether type epoxy or glycidyl ester type epoxy resin.Especially Racemic glycidol ether type epoxy and since do not have can with the functional group of multi-functional thiol's compound (A) reaction, can not rely on curable resin composition even cured film that reaction conditions obtains homogeneous.In addition, polyfunctional epoxy resin (B) can only be used alone, and also can two or more mixing use.
＜Racemic glycidol ether type epoxy 〉
As the Racemic glycidol ether type epoxy, the reaction product shown in preferred epoxy chloropropane and the following general formula (7) between the compound.
Chemical formula 8
Wherein, q is 2 ~ 30 integer, R
9For the alkyl (β 1) of carbonatoms 2 ~ 200, carbonatoms 2 ~ 300 by the ether oxygen (group (β 4) of the group (β 2) that O-) consists of with alkyl, isocyanurate ring (β 3), isocyanurate ring and alkyl formation.
In the compound shown in the above-mentioned general formula (7), because high with the solvability of other compositions, therefore preferred q is 2 ~ 20 and R
9Be the compound (β 1-1) of the group that is consisted of by alkyl of carbonatoms 2 ~ 150, or q is 2 ~ 20 and R
9For carbonatoms 2 ~ 150 by alkyl and the ether oxygen (compound (β 2-1) of the group that O-) consists of.Can exemplify alkylene glycol such as carbonatoms 2 ~ 10, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), phenol phenolic aldehyde, dihydroxyphenyl propane etc. as (β 1-1).Can exemplify such as polyoxyethylene glycol, polypropylene glycol or Dipentaerythritol etc. as (β 2-1).
Reaction between the compound shown in above-mentioned epoxy chloropropane and the general formula (7) is as follows, makes the hydroxyl generation addition reaction of the compound shown in epoxy chloropropane and the general formula (7), obtains chloropharin, makes the chloropharin that obtains close ring with alkali such as sodium oxides, makes Resins, epoxy.In addition, the Racemic glycidol ether type epoxy also can be the Resins, epoxy that the part epoxy ring-opening polymerization of the Resins, epoxy that obtains behind the described ring closure reaction is obtained.
The reaction product of the compound shown in epoxy chloropropane and the general formula (7) has the structure shown in following general formula (8).
Chemical formula 9
Wherein, q is 2 ~ 30 integer, R
9For the alkyl (β 1) of carbonatoms 2 ~ 200, carbonatoms 2 ~ 300 by ether oxygen (group (β 2), the isocyanurate ring (β 3) that O-) consists of with alkyl or the group (β 4) that is consisted of by isocyanurate ring and alkyl.
＜glycidyl ester type epoxy resin 〉
Glycidyl ester type epoxy resin, that (methyl) glycidyl acrylate etc. is had the monomer of epoxy group(ing), separately or with weight-average molecular weight that (methyl) alkyl acrylate copolymer of carbonatoms 4 ~ 25 obtains be 3000 ~ 20000 polymkeric substance, or the reaction product of the compound shown in epoxy chloropropane and the following general formula (9) etc.
Chemical formula 10
Wherein, r is 2 ~ 8 integer, R
10For the alkyl (β 5) of carbonatoms 2 ~ 20, carbonatoms 2 ~ 30 by ether oxygen (any in group (β 6), the isocyanurate ring (β 7) that O-) consists of with alkyl or the group (β 8) that is consisted of by isocyanurate ring and alkyl.
Reaction shown in epoxy chloropropane and the general formula (9) between compound is as follows, makes the carboxyl addition reaction of compound shown in epoxy chloropropane and the general formula (9) make chloropharin, makes the chloropharin that makes close ring with alkali such as sodium hydroxide, makes glycidyl ester type epoxy resin.The Resins, epoxy that in addition, also can use the part epoxy ring-opening polymerization of glycidyl ester type epoxy resin to make.
Therefore in the compound shown in the above-mentioned general formula (9), because solvability is high, preferred r is 2 ~ 4 and R
10Be the compound (β 5-1) of the group that is consisted of by alkyl of carbonatoms 2 ~ 10, or r is 2 ~ 6 and R
10For carbonatoms 2 ~ 30 by the ether oxygen (compound (β 6-1) of the group that O-) consists of with alkyl, or r is 3 and R
10Compound (β 8-1) for the group that consisted of by isocyanurate ring and alkyl.
As (β 5-1), can exemplify such as hydrogenation phthalic acid or trimellitic acid etc.As (β 6-1), can exemplify the reaction product such as tetramethylolmethane and trimellitic acid 1,2-anhydride.As (β 8-1), can exemplify such as 1,3,5-three (2-propyloic) isocyanuric acid ester etc.
The reaction product of the compound shown in epoxy chloropropane and the general formula (9) has structure shown in the following general formula (10).
Chemical formula 11
Wherein, r is 2 ~ 8 integer, R
10For the alkyl (β 5) of carbonatoms 2 ~ 20, carbonatoms 2 ~ 30 by ether oxygen (any in group (β 6), the isocyanurate ring (β 7) that O-) consists of with alkyl or the group (β 8) that is consisted of by isocyanurate ring and alkyl.
Alkoxyl silicone alkane derivatives (C) composition of＜Sulfide-containing Hindered 〉
The alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered is when solidifying curable resin composition of the present invention, in order to improve the adhesion promoter that the adhesivity of inorganic substrate is added.The alkoxyl silicone alkane derivatives (C) of this Sulfide-containing Hindered has thioether group, with disulfide linkage and the thioether group generation chemical bonding that is generated by multi-functional thiol's compound (A) and polyfunctional epoxy resin (B) crosslinking reaction.At this moment, because the alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered is high with intermiscibility height and the reaction efficiency of multi-functional thiol's compound (A), the sticking power facilitation effect that therefore obtains is high.And it is silica-based that the alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered has alcoxyl, can with the hydroxyl reaction that is generated by the reaction of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B).As a result, resulting resin cured matter cross-linking density improves, and forms the tough crosslinked with enhanced water resistance (cured article).In addition, the alcoxyl of the alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered is silica-based, can with inorganic substrate generation chemical bonding, can increase substantially and inorganic substrate between sticking power.
The alkoxyl silicone alkane derivatives (C) of the Sulfide-containing Hindered in the curable resin composition of the present invention is the compound shown in the following general formula (1).In addition, the alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered can only be used alone, and also can two or more mixing use.
Chemical formula 12
Wherein, a and b are 0 ~ 2 integer, and c is 1 ~ 3 integer, a+b+c=3.R is the trivalent group shown in the following general formula (2), R
1And R
2For independently being separately-CH
2-CH (CH
3)-,-C (CH
3)
2-,-CH
2-CH
2-or-CH (CH
3)-in the divalent group shown in any one, R
3Be methyl or ethyl.
Chemical formula 13
Wherein, m is 1 or 2.
The alkoxyl silicone alkane derivatives (C) of this Sulfide-containing Hindered can have the silica-based (Si (OR of alcoxyl at least by making
4)
3) and the compound (the following X composition that often is called) of two keys with contain thiol group (multi-thiol compound SH) (the following Y composition that often is called) reaction and making.Specifically, b is 0 compound, can make with multi-thiol compound (Y) reaction shown in the following general formula (12) by making at least the silica-based compound of alcoxyl (X) that contains shown in following general formula (11).In addition, b is not 0 compound, can by make at least shown in following general formula (11) contain the multi-thiol compound (Y) shown in the silica-based compound of alcoxyl (X), the following general formula (12) and the reaction of (methyl) glycidyl acrylate makes.In addition, if make (X) composition and (Y) composition reaction, then two keys of (X) composition and (Y) the thiol group reaction of composition.
Chemical formula 14
Wherein, R
3Be methyl or ethyl, R
14Be hydrogen atom or methyl.
Chemical formula 15
Wherein, m is 1 or 2 integer.
As containing the silica-based compound of alcoxyl (X) shown in the above-mentioned general formula (11), can exemplify such as 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl trimethoxy silicane.
As the multi-thiol compound (Y) shown in the above-mentioned general formula (12), can exemplify three ((the 3-sulfydryl propionyloxy)-ethyl) isocyanuric acid ester such as m=2.As the compound (Y) of m=1, can exemplify the synthetics such as isocyanic acid three (2-hydroxyethyl) ester and Thiovanic acid.In above-mentioned general formula (12), in the situation of the compound of use m 〉=3, hydrophobicity and nonpolar hydrocarbon number increase, thereby thioether group is weakened the orientation of base material, are difficult to obtain adhesivity.
Preferably under the effect of catalyzer or radical initiator, make (X) composition and (Y) composition reaction.This be because, if add catalyzer or radical initiator, can be in shorter time and it is reacted.
As catalyzer, be preferably the basic catalyst of amine, can use primary amine, secondary amine or tertiary amines, perhaps use glyoxaline compound.Such as exemplifying methylamine, ethamine, propylamine, butylamine, quadrol etc. as primary amine; Can exemplify dimethylamine, diethylamine, dipropyl amine, methylethyl amine, diphenylamine etc. as secondary amine; Can exemplify Trimethylamine 99, triethylamine, tripropyl amine, triphenylamine, 1 as tertiary amine, 8-diazabicyclo (5,4,0)-11 carbon-7-alkene, 2,4,6-three (dimethylamino methyl) phenol etc.As glyoxaline compound, such as the imidazoles homologue that can exemplify 1-Methylimidazole, 1,2 dimethylimidazole, Isosorbide-5-Nitrae-dimethyl-2-ethyl imidazol(e), 1-phenylimidazole etc.; 1-methyl-2-oxygen Methylimidazole, the 1-methyl-oxyalkyl derivatives such as 2-oxygen ethyl imidazol(e); 1-methyl-4 (5)-nitroimidazole, 1, nitro and the aminoderivatives such as 2-dimethyl-5 (4)-aminooimidazole; Benzoglyoxaline, 1-tolimidazole, 1-methyl-2-phenmethyl benzoglyoxaline etc.
As the preferred superoxide of radical initiator or azo-compound.As superoxide, such as exemplifying dibenzoyl peroxide, peroxide-2-ethyl hexanoic acid tert-butyl, the two dodecanoyl of peroxidation, tertbutyl peroxide etc.As azo-compound, for example can exemplify Diisopropyl azodicarboxylate and 2,2 '-azo two (2-methylbutyronitrile) etc.
In the preparation method of the alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered, under the temperature more than 5 ℃, just can make its reaction, but in order to make at short notice its reaction, preferred 30 ~ 120 ℃, especially preferred 60 ~ 80 ℃.
In the preparation method of the alkoxyl silicone alkane derivatives of Sulfide-containing Hindered, even solvent-free reaction is carried out, if but make at low temperatures in the situation of its reaction or want to fall in the low viscous situation, also can add solvent and make its reaction.This moment preferred not with the solvent of silica-based, the two key of alcoxyl, thiol group reaction, preference such as alcohols, ketone, ester class or the fragrant same clan.
As described alcohols, the preferred primary alconol of carbonatoms below 3, in addition, the preferred boiling point alcohol higher than temperature of reaction.Better at the alcohols that the temperature range interior reaction temperature is high.In addition, in reaction, transesterification reaction might occur with alcoxyl is silica-based in alcohol, may cause the yield of target product to descend, and therefore descends in order to suppress yield, preferably has R
2The material of OH structure.As the reaction solvent that satisfies above-mentioned condition, can exemplify such as methyl alcohol or ethanol etc.In addition, as ketone, the preferred boiling point ketone higher than temperature of reaction considered from the solvability aspect in addition, the preferred ketone of carbonatoms below 6.As the ketone that satisfies above-mentioned condition, can exemplify such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.In addition, as the ester class, the preferred boiling point ester class higher than temperature of reaction considered from the solvability aspect in addition, and preferred straight chain and carbonatoms are the ester class below 6.Ester class as satisfying above-mentioned condition can exemplify such as N-BUTYL ACETATE, vinyl acetic monomer etc.
As not with the ester class of silica-based, the two key of alcoxyl, thiol group reaction, the preferred boiling point ester class higher than temperature of reaction considered from the solvability aspect in addition, preferred straight chain and carbonatoms are the ester class below 6.As the ester class that satisfies above-mentioned condition, can exemplify such as vinyl acetic monomer, ritalin, N-BUTYL ACETATE, acetic acid methoxyl group butyl ester, acetic acid ethylene glycol ethyl ether, amyl acetate-n, methyl lactate, ethyl lactate, n-Butyl lactate etc.
＜aminated compounds (D) composition 〉
Aminated compounds in the curable resin composition of the present invention is for promoting the reaction between (catalysis) thiol group and epoxy group(ing) to add.As aminated compounds (D), can exemplify as molecular weight be 90 ~ 700, preferred 100 ~ 690, especially preferred 110 ~ 680 monofunctional amines or have the polyamines of a plurality of amino.If the molecular weight less than 90 of aminated compounds (D), then the volatility of amine uprises, and not only has the defectives such as foul smell or hole, and since when being heating and curing the concentration of amine reduce and be difficult to carry out crosslinking reaction, adhesivity easily descends.If the molecular weight of aminated compounds (D) surpasses 700, then cause easily water tolerance decline adhesivity easily to descend.
As the simple function amine, can exemplify such as primary amine, secondary amine or tertiary amine.As polyamines, can exemplify such as primary amine, secondary amine, tertiary amine, varies.Varies refers to have primary amine groups, two or more amine in the secondary amine, tertiary amine groups.As these variess, can exemplify such as imidazolinium compounds, imidazolium compounds, N substituted piperazine like compound, N N-dimethyl urea derivative etc.In addition, aminated compounds (D) can only be used alone, and also can two or more mixing use.
In addition, in order to adjust catalytic activity, aminated compounds (D) can form salt with organic acid in advance.As in advance with the organic acid of aminated compounds (D) reaction, can exemplify such as aromatic carboxylic acid or tricarbimides such as the Pyromellitic Acid that has 1 ~ 10 carboxyl in aliphatic carboxylic acid, carbonatoms 1 ~ 20 and the molecules such as the stearic acid that has 1 ~ 5 carboxyl in carbonatoms 1 ~ 20 and the molecule or 2 ethyl hexanoic acid, trimellitic acid, M-nitro benzoic acids.In addition, in order to adjust catalytic activity, aminated compounds (D) can also be sneaked into after forming affixture with polyfunctional epoxy resin (B).
＜imidazolium compounds 〉
In aminated compounds (D), the imidazolium compounds solidified nature under stability in storage and the low temperature that is suitable for most getting both.In addition, can also use the imidazolium compounds that applies with phenolic resin.
This imidazolium compounds is the compound with following general formula (3) expression.
Chemical formula 16
Wherein, R
5The alkyl of the carbonatoms 1 ~ 10 that replaces for the alkyl of cyano group, carbonatoms 1 ~ 10, with 2,3-diamino triazine, alkoxyl group or the hydrogen atom of carbonatoms 1 ~ 4, R
4, R
6, R
7For the alkyl of carbonatoms 1 ~ 20, alkoxyl group or the hydrogen atom of carbonatoms 1 ~ 4, work as R
4~ R
7It is the alkyl of carbonatoms 2 ~ 8 that bonding forms in the situation about encircling.
Specifically, can exemplify glyoxal ethyline, the 2-undecyl imidazole, 2-heptadecyl imidazoles, the 2-phenylimidazole, 1, the 2-methylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, the 1-(2-cyano ethyl)-glyoxal ethyline, the 1-(2-cyano ethyl)-the 2-undecyl imidazole, the 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, the 1-(2-cyano ethyl)-the 2-phenylimidazole, the 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo-(1,2-a) benzoglyoxaline, 2,4-diamino-6-(2-Methylimidazole-(1))-ethyl-s-triazine, 2,4-diamino-6-(2 '-undecyl imidazole-(1 '))-ethyl-s-triazine, 2,4-diamino-6-(2 '-ethyl-4 ' Methylimidazole-(1 '))-ethyl-s-triazine, 2-phenyl-4,5-dihydroxyl Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazoles.
＜multifunctional (methyl) acrylic compound ((E) composition) 〉
If multi-functional thiol's compound (A), polyfunctional epoxy resin (B) and aminated compounds (D) are arranged in the curable resin composition of the present invention, then can be cured by heat.On the other hand, give in the situation of curable resin composition light solidity of the present invention or photo-thermal two-stage solidified nature wanting, then can add multifunctional (methyl) acrylic compound (E).
As everyone knows, under the exciting of heat or light, mercaptan and two key generation addition reactions.Therefore, multi-functional thiol's compound (A) and the mixture that contains the compound of multifunctional pair of key can form curable resin composition.In the present invention, in above-mentioned pair of key, preferably has multifunctional (methyl) acrylic compound (E) of the compound of two above acryloxies or methacryloxy.In numerous compounds that contain two keys, selects the reason of multifunctional (methyl) acrylate to be, at room temperature with curable resin composition of the present invention in multi-functional thiol's compound (A) be difficult to react, can set long usable time; When reacting with multi-functional thiol's compound (A), can form tough cured article; Be difficult to the reaction by aminated compounds (D) catalysis and multi-functional thiol's compound (A), and not with polyfunctional epoxy resin (B) reaction etc.
As this multifunctional (methyl) acrylate (E), can exemplify to be preferably as follows and state the compound shown in the general formula (13).In addition, multifunctional (methyl) acrylate (E) can only be used alone, and also can two or more mixing use.
Chemical formula 17
Wherein, s is 2 ~ 30 integer, R
12For the alkyl (ε 1) of carbonatoms 2 ~ 200, carbonatoms 2 ~ 300 by ether oxygen (group (ε 2), the isocyanurate ring (ε 3) that O-) consists of with alkyl or the group (ε 4) that is consisted of by isocyanurate ring and alkyl, R
13Be hydrogen atom or methyl.
In addition, as multifunctional (methyl) acrylate (E), can suit to use the compound of polymer class.Multifunctional (methyl) acrylate (E) as polymer class, can exemplify as: have in (methyl) acrylic compound homopolymer or multipolymer of epoxy group(ing) at (methyl) glycidyl acrylate etc., make such as (methyl) vinylformic acid etc. to have the polymkeric substance that can make with (methyl) acrylic compound reaction of the group of epoxy reaction; Have in (methyl) acrylic compound homopolymer or multipolymer of hydroxyl in (methyl) hydroxyethyl acrylate etc., make such as 2-methacrylic acid 2-isocyanato ethyl ester etc. to have the polymkeric substance that can make with (methyl) acrylic compound reaction of the group of hydroxyl reaction; Have in (methyl) acrylic compound homopolymer or multipolymer of carboxyl at (methyl) vinylformic acid etc., make such as (methyl) glycidyl acrylate etc. to have the polymkeric substance that can make with (methyl) acrylic compound reaction of carboxyl reaction etc.
The molecular weight of multifunctional (methyl) acrylic compound (E) is 200 ~ 50000, and is preferred 220 ~ 40000, is more preferably 240 ~ 30000.Multifunctional (methyl) acrylic compound (E) though molecular weight less than 200, also no problem about adhesivity, but exist volatility to uprise, the tendency of foul smell grow.On the other hand, if greater than 50000, may descend with respect to the solvability of other compositions.
In addition, (methyl) acrylate equivalent of multifunctional (methyl) acrylate (E) is 80 ~ 6000g/mol, and is preferred 80 ~ 4500, is more preferably 85 ~ 3000.If (methyl) acrylate equivalent is less than 80g/mol, then (methyl) acryloxy is too much in the unit volume, (methyl) acryloxy with the reaction of the thiol group of multi-functional thiol's compound (A) does not remain in a large number, the toughness of the cured film that therefore is made of curable resin composition may descend, in the situation about exposing under high temperature wets condition more, adhesivity may descend.On the other hand, if (methyl) acrylate equivalent is greater than 6000g/mol, then (methyl) acryloxy concentration significantly reduces, therefore the reaction efficiency with the thiol group of multi-functional thiol's compound (A) descends, may cause the toughness of the cured film that is made of curable resin composition to descend, adhesivity descends when exposing under the many wet environments of high temperature.
＜ratio of components (balanced proportioning) 〉
Curable resin composition of the present invention is sneaked into multi-functional thiol's compound (A) and polyfunctional epoxy resin (B), and making its weight ratio (A)/(B) is 0.05 ~ 30.This place, " (A)/(B) " refers to remove with the weight of polyfunctional epoxy resin (B) weight of multi-functional thiol's compound (A).Best (A)/(B) value, because of the structure of the desired characteristic of curable resin composition, multi-functional thiol's compound (A) or polyfunctional epoxy resin (B) and multifunctional (methyl) acrylic compound (E) that according to circumstances adds different.Characteristic after curable resin composition solidifies strictly is subjected to the value impact of (mercaptan radix)/(the epoxy radix+(methyl) acryloyl-oxy radix) (hereinafter referred to as mercaptan/(epoxy+alkene) ratio) in the curable resin composition unit weight.For example, mercaptan/(epoxy+alkene) is than in 0.5 ~ 1.5 scope, and easily formation is closely crosslinked, and forms easily tough cured article.On the other hand, if mercaptan/(epoxy+alkene) can access soft stickiness cured article than being to surpass at 1.5 o'clock below 0.1 above less than 0.5 or 2.0.If mercaptan/(epoxy+alkene) is than less than 0.1 or surpass at 2.0 o'clock, be difficult to gelation, the adhesivity downward trend is arranged.
In addition, curable resin composition of the present invention, take the gross weight (A+B) of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B) as 100 weight parts, add the alkoxyl silicone alkane derivatives (C) of 0.5 ~ 50 weight part Sulfide-containing Hindered, preferably add 0.5 ~ 45 weight part.With respect to (A+B), (C) during proportional quantity less than 0.5 weight part of composition, be difficult to obtain excellent adhesivity, if surpass 50 weight parts, the cross-linking density of cured article reduces, obdurability descends, so adhesivity may descend.
In addition, curable resin composition of the present invention, take the gross weight (A+B) of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B) as 100 weight parts, sneak into the aminated compounds (D) of 0.01 ~ 50 weight part, preferably add 0.01 ~ 45 weight part.With respect to (A+B), (D) during the proportional quantity less than 0.01 of composition, owing to need the time to carry out the reaction of thiol group and epoxy group(ing), therefore to solidify badly, during above 50 weight part, then cross-linking density may reduce, and adhesivity may descend.
In addition, in curable resin composition of the present invention, also sneak in the situation of multifunctional (methyl) acrylic compound (E), take the gross weight (A+B) of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B) as 100 weight parts, sneak into 2 ~ 300 weight parts multifunctional (methyl) acrylic compound (E), preferably add 2 ~ 250 weight parts.With respect to (A+B), (E) during the proportional quantity less than 2 of composition, be difficult to give its light solidity, if when surpassing 300 weight part, have the tendency that adhesivity descends.
＜curable resin composition 〉
If the epoxy reaction of the thiol group of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B) then generates thioether group or hydroxyl.The organoalkoxysilane of Sulfide-containing Hindered (C) also has thioether group, and is crosslinked with the thioether that above-mentioned thiol group and epoxy reaction generate with disulfide linkage.In addition, it is silica-based that the alkoxysilane compound containing trialkylsilyl group in molecular structure of Sulfide-containing Hindered (C) also has alcoxyl simultaneously, crosslinked with the hydroxyl reaction that above-mentioned thiol group and epoxy reaction generate.As a result, can form closely crosslinked.Make the cured article after curable resin composition of the present invention solidifies, because formed closely crosslinked, so the raisings such as thermotolerance, obdurability and water tolerance.And it is the cured article that forms with thioether group or disulfide bond crosslinking, also is rich in snappiness, therefore has high adhesivity.And, the alkoxysilane compound containing trialkylsilyl group in molecular structure of Sulfide-containing Hindered (C), it is silica-based also to have simultaneously three alcoxyls, therefore especially can form chemical bond with the inorganic substrate of glass and so on, and then curable resin composition of the present invention significantly improves the adhesivity of inorganic substrate.
In addition, in curable resin composition of the present invention, (methyl) acryl of multifunctional (methyl) acrylic compound (E) that optionally adds and the also reaction under the exciting of light of thiol group of multi-functional thiol's compound (A).Therefore, the mixture of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B), multifunctional (methyl) acrylic compound (E) is the curable resin that solidifies with the light and heat two-stage.And, can by control moiety amount separately, control the degree of photocuring and thermofixation.
At present, multiple mercaptan compound is used as solidifying agent (being used for making the hosts such as Resins, epoxy or (methyl) acrylic compound to solidify and the compound of interpolation).In addition, well-known, in arbitrary reaction of thiol group and epoxy group(ing) or thiol group and (methyl) acryl, the alkaline matters such as amine have the effect of reduction reaction activity (catalysis).
In addition, curable resin composition of the present invention, for reaction system homogeneous, easy coating etc., also can be with using behind the organic solvent diluting.As this organic solvent, can exemplify such as alcoholic solvent, aromatic hydrocarbon solvent, ether solvent, esters solvent and solvent of ether ester type, ketones solvent, phosphoric acid ester solvent.With respect to 100 weight part curable resin compositions, the proportional quantity of these organic solvents preferably is controlled to be and is less than 10000 weight parts, but basically when forming cured film solvent volatilize, therefore can not cause on the physical properties of cured film large impact.But, can be with the compound of the functional group of thiol group, epoxy group(ing) or the reaction of (methyl) acryl and aminated compounds during as solvent to have, might damage effect of the present invention.
In addition, for adjusting viscosity, curable resin composition of the present invention also can be sneaked into the viscosity modifiers such as SiO 2 powder.With respect to 100 weight part curable resin compositions, the proportional quantity of these viscosity modifiers is preferably less than 300 weight parts.If the proportional quantity of viscosity modifier surpasses 300 weight parts, adhesivity may descend.
In addition, curable resin composition of the present invention also can add the various additives that use in common coating or the binding agent.As these additives, can exemplify such as the aluminium salt that is used for making the level and smooth tensio-active agent of coating surface, being used for prolonging usable time, be used for improving photoreactive optical free radical initiator, photoproduction alkaline agent, photo-acid agent etc.With respect to 100 weight part curable resin compositions, the proportional quantity of these additives is preferably less than 80 weight parts.If the proportional quantity of these additives surpasses 80 weight parts, adhesivity may descend.
Embodiment
The below exemplifies embodiment and comparative example carries out more specific description to the present invention, but the present invention is not limited thereto.Reagent used in present embodiment and the comparative example is as follows.In addition, Mw represents weight-average molecular weight.
＜multi-functional thiol compound (A composition) 〉
（A-1、Mw：372）
Chemical formula 18
（A-2、Mw：399）
Chemical formula 19
（A-3、Mw：526）
Chemical formula 20
（A-4、Mw：488）
Chemical formula 21
（A-5、Mw：784）
Chemical formula 22
（A-6、Mw：416）
Chemical formula 23
（A-7、Mw：785）
Chemical formula 24
（A-8、Mw：1584）
Chemical formula 25
＜polyfunctional epoxy resin (B composition) 〉
(B-1, Mw:220, epoxy equivalent (weight): 110)
Chemical formula 26
(B-2, Mw:360, epoxy equivalent (weight): 90)
Chemical formula 27
(B-3, Mw:350, epoxy equivalent (weight): 175)
Chemical formula 28
(B-4, Mw:5500, epoxy equivalent (weight): 3000)
Chemical formula 29
N average out to 15.
(B-5, Mw:1500, epoxy equivalent (weight): 186)
Chemical formula 30
N average out to 7.
(B-6, Mw:220, epoxy equivalent (weight): 110)
Chemical formula 31
(B-7, Mw:18000, epoxy equivalent (weight): 250)
The multipolymer of glycidyl methacrylate and cyclohexyl methacrylate (with hexane to the reppd white solid of 50wt% methyl isobutyl ketone solution).
(B-8, Mw:45000, epoxy equivalent (weight): 250)
The multipolymer of glycidyl methacrylate and cyclohexyl methacrylate (with hexane to the reppd white solid of 50wt% methyl isobutyl ketone solution).
The alkoxyl silicone alkane derivatives of＜Sulfide-containing Hindered (C composition) 〉
（C-1）
Chemical formula 32
（C-2）
Chemical formula 33
（C-3）
Chemical formula 34
（C-4）
Chemical formula 35
（C-5）
Chemical formula 36
（C-6）
Chemical formula 37
（C-7）
Chemical formula 38
＜aminated compounds (D composition) 〉
（D-1、Mw：136）
Chemical formula 39
（D-2）
1,8-diazabicyclo (5,4,0), 11 carbon-7-alkene and stearic 1:1 equivalent reaction thing
（D-3、Mw：680）
Chemical formula 40
N1, n2, n3 are 1 ~ 5 integer, average 3.5 mixture.
（D’-1、Mw：110）
Chemical formula 41
（D’-2、Mw：144）
Chemical formula 42
（D’-3、Mw：163）
Chemical formula 43
（D’-4、Mw：219）
Chemical formula 44
（D’-5）
Chemical formula 45
The salt of 2-phenylimidazole and Pyromellitic Acid
（D’-6、Mw：158）
Chemical formula 46
（D’-7、Mw：306）
Chemical formula 47
＜multifunctional (methyl) acrylic compound (E composition) 〉
(E-1, Mw:246, two key equivalent: 123)
Chemical formula 48
(E-2, Mw:352, two key equivalent: 88)
Chemical formula 49
(E-3, Mw:376, two key equivalent: 183)
Chemical formula 50
(E-4, Mw:5000, two key equivalent: 3000)
Chemical formula 51
N average out to 13
(E-5, Mw:1200, two key equivalent: 180)
Chemical formula 52
N average out to 5
(E-6, Mw:586, two key equivalent: 195)
Chemical formula 53
(E-7, Mw:22000, two key equivalent: 320)
Take D-3 as catalyzer, the acrylic acid polymkeric substance of the multipolymer of glycidyl methacrylate and cyclohexyl methacrylate etc. moles addition (methyl) (with hexane to the reppd white solid of 50wt% methyl isobutyl ketone solution).
＜other reagent 〉
(F-1,
The A composition)
Chemical formula 54
(F-2,
The C composition)
Chemical formula 55
Shown in table 1,2, sneak into respectively (A) ~ (E) composition with balanced proportioning, be stirred to evenly with scraper.Sample after stirring is carried out following evaluation, and its result is shown in table 1,2.
＜adhesivity evaluation 〉
Take rod coater non-alkali glass (OA-10, NEG company produce, thickness 0.7mm) and aluminium sheet (A5052P, Japanese Testpanel company produce, thickness 2.0mm) be coated with embodiment and comparative example to thickness as 100 μ m, in 140 ℃ of lower heating 1 hour, obtain cured film at each base material.Under the condition of 121 ℃ * 100RH% * 90 hour, process the base material that obtains cured film, then estimate with the mechanical properties-adhesivity of filming (cross-section method) test method of JIS K5600-5-6 defined.Fully be designated as ◎ without peeling off, peel off account for entire area and be designated as zero below 1 one-tenth, in addition be designated as *.Adhesivity 1 in the table is the result on the non-alkali glass base material, and adhesivity 2 is the result on the aluminium sheet base material.
＜affirmation light solidity 〉
Take rod coater each embodiment of non-alkali glass coating and comparative example to thickness as 100 μ m, with high-pressure mercury light irradiation 500mJ/cm
2The light of (being scaled the i ray).With scraper suppressed to shine film the time, the situation that does not attach coating fluid on the scraper is designated as zero.
＜affirmation stability in storage (preservation stability) 〉
With each embodiment of following viscometer determining and the firm mixed viscosity of comparative example.Each embodiment and comparative example after 12 hours, are measured viscosity 30 ℃ of lower heating again.Take the viscosity tackify rate that obtain of mixed viscosity after except heating as 1.0 ~ 1.8 be designated as ◎, 1.8 ~ 10 be designated as zero, being designated as in addition *.Machine: eastern machine industry (strain) system (R type viscometer), temperature: 25 ℃.
From the result of table 1 and table 2 as can be known, all embodiment all have high adhesivity.In addition, can confirm in embodiment 2-1 ~ 2-8 can to give the light solidity because having added (E) composition.In addition, can clearly in embodiment 1-3 ~ 1-7,2-3 ~ 2-8, amine be defined as imidazolium compounds, thereby improve stability in storage (preservation stability).On the other hand, shown in each comparative example, do not contain in the neccessary composition among the present invention (A) ~ (D) any or for different materials, can not obtain the adhesivity to the inorganic substrate excellence.
Claims (5)
1. a curable resin composition is characterized in that, contains following (A), (B), (C) and (D) composition,
Described (A) composition is that molecular weight is multi-functional thiol's compound of 200 ~ 2000;
Described (B) composition be molecular weight be 200 ~ 50000 and epoxy equivalent (weight) be the polyfunctional epoxy resin of 80 ~ 6000g/mol;
Described (C) composition is the alkoxyl silicone alkane derivatives with the Sulfide-containing Hindered shown in the following general formula (1);
Described (D) composition is that molecular weight is 90 ~ 700 aminated compounds;
The weight ratio (A)/(B) of described (A) composition and described (B) composition is 0.05 ~ 30;
Take the gross weight of described (A) composition and described (B) composition as 100 weight parts, sneak into described (C) composition of 0.5 ~ 50 weight part, sneak into described (D) composition of 0.01 ~ 50 weight part;
Chemical formula 1
Wherein, a and b are 0 ~ 2 integer, and c is 1 ~ 3 integer, a+b+c=3; R is the trivalent group shown in the following general formula (2), R
1And R
2For separately independently-CH
2-CH (CH
3)-,-C (CH
3)
2-,-CH
2-CH
2-or-CH (CH
3)-in the divalent group shown in any one, R
3Be methyl or ethyl;
Chemical formula 2
Wherein, m is 1 or 2.
2. curable resin composition according to claim 1, it is characterized in that, also being mixed with (E) composition, is that molecular weight 200 ~ 50000 and (methyl) acrylate equivalent are multifunctional (methyl) acrylic compound of 80 ~ 6000g/mol as (E) composition; The gross weight of described (A) composition and described (B) composition is 100 weight part meters, and sneaking into 2 ~ 300 weight parts should (E) composition.
3. curable resin composition according to claim 1 and 2 is characterized in that, described aminated compounds (D) is the imidazolium compounds shown in the following general formula (3);
Chemical formula 3
Wherein, R
5The alkyl of the carbonatoms 1 ~ 10 that replaces for the alkyl of cyano group, carbonatoms 1 ~ 10, with 2,3-diamino triazine, alkoxyl group or the hydrogen atom of carbonatoms 1 ~ 4, R
4, R
6, R
7For the alkyl of carbonatoms 1 ~ 20, alkoxyl group or the hydrogen atom of carbonatoms 1 ~ 4, work as R
4~ R
7It is the alkyl of carbonatoms 2 ~ 8 that bonding forms in the situation about encircling.
4. arbitrary described curable resin composition is characterized in that according to claim 1 ~ 3, and described multi-functional thiol's compound (A) is the multi-functional thiol's compound shown in the following general formula (3);
Chemical formula 4
Wherein, n is 2 ~ 5 integer, and p is 2 ~ 10 integer, R
8Be in the group (α 2), the isocyanurate ring (α 3) that are consisted of by ether oxygen and alkyl of the alkyl (α 1) of carbonatoms 2 ~ 30, carbonatoms 2 ~ 40 or the group (α 4) that consisted of by isocyanurate ring and alkyl any.
5. arbitrary described curable resin composition is characterized in that according to claim 1 ~ 4, and described polyfunctional epoxy resin (B) is Racemic glycidol ether type epoxy or glycidyl ester type epoxy resin.
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| JP2011120422A JP5790155B2 (en) | 2011-05-30 | 2011-05-30 | Curable resin composition |
| JP2011-120422 | 2011-05-30 | ||
| PCT/JP2012/003334 WO2012164870A1 (en) | 2011-05-30 | 2012-05-22 | Curable resin composition |
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| CN105765009A (en) * | 2013-11-28 | 2016-07-13 | 捷恩智株式会社 | Photocurable inkjet ink |
| CN108484880A (en) * | 2014-02-13 | 2018-09-04 | 图茨技术股份有限公司 | The amine catalysis of epoxy resin is thiol-cured |
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| JP5732362B2 (en) * | 2011-09-26 | 2015-06-10 | 富士フイルム株式会社 | Polymerizable compound and polymerizable composition |
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| US9534075B2 (en) | 2011-11-01 | 2017-01-03 | Korea Institute Of Industrial Technology | Isocyanurate epoxy compound having alkoxysilyl group, method of preparing same, composition including same, cured product of the composition, and use of the composition |
| WO2013137663A1 (en) | 2012-03-14 | 2013-09-19 | 한국생산기술연구원 | Epoxy compound having alkoxy silyl group, composition comprising same, cured product, use thereof and method for preparing epoxy compound having alkoxy silyl group |
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| EP2935392B1 (en) * | 2012-12-21 | 2020-01-22 | Dow Global Technologies LLC | Phase-segmented non-isocyanate elastomers |
| JP5949674B2 (en) * | 2013-06-12 | 2016-07-13 | 信越化学工業株式会社 | Novel organosilicon compound, process for producing the same and adhesion improver |
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Also Published As
| Publication number | Publication date |
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| CN102985461B (en) | 2016-04-27 |
| TWI481660B (en) | 2015-04-21 |
| JP2012246422A (en) | 2012-12-13 |
| JP5790155B2 (en) | 2015-10-07 |
| TW201247769A (en) | 2012-12-01 |
| WO2012164870A1 (en) | 2012-12-06 |
| KR20140022912A (en) | 2014-02-25 |
| KR101528737B1 (en) | 2015-06-15 |
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