CN102985461B - Curable resin composition - Google Patents

Curable resin composition Download PDF

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CN102985461B
CN102985461B CN201280000439.3A CN201280000439A CN102985461B CN 102985461 B CN102985461 B CN 102985461B CN 201280000439 A CN201280000439 A CN 201280000439A CN 102985461 B CN102985461 B CN 102985461B
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chemical formula
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CN102985461A (en
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藤村俊伸
田上安宣
幸田一洋
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NOF Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/40Macromolecules 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
    • C08G59/66Mercaptans
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
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Abstract

The invention provides a kind of curable resin composition to inorganic substrate adhesivity excellence.This curable resin composition contain multi-functional thiol's compound (A) that molecular weight is 200 ~ 2000, molecular weight for 200 ~ 50000 and the epoxy equivalent (weight) polyfunctional epoxy resin (B) that is 80 ~ 6000g/mol, the alkoxyl silicone alkane derivatives (C) of the Sulfide-containing Hindered shown in general formula (1), molecular weight be 90 ~ 700 aminated compounds (D).(A) weight ratio of/(B) is 0.05 ~ 30.Be 100 parts by weight with (A+B), containing 0.5 ~ 50 weight part (C), 0.01 ~ 50 weight part (D).

Description

Curable resin composition
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, by various coatings in inorganic substrates such as glass time, in order to improve adhesivity, in composition epoxy resin of being everlasting, add silane coupling agent (such as patent documentation 1).In addition, as existing epoxy curing agent, can mercaptan compound be used, as the catalyzer reacted between activation epoxy group(ing) and thiol group, the alkaline matter (such as non-patent literature 1) of amine and so on can be used.Further, well-known mercaptan compound and the mixture of multifunctional polyene with multiple double bond, can form the curable resin composition (such as patent documentation 2) using up to be cured.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 7-300491 publication
Patent documentation 2: Japanese Unexamined Patent Publication 6-306172 publication
Non-patent literature
Non-patent literature 1: epoxy resin is summarized, the 1st volume, basic section I, P204-205, Epoxy Resin Technology association compiles.
Summary of the invention
Technical problem to be solved by this invention
But in technology as described in patent document 1, which, the most boiling point of silane coupling agent is lower, need to make an addition in thermosetting resin in a large number.In addition, adhesivity improves effect can not say it is abundant, such as, sometimes needs to add the salt such as titanium, zirconium or the sticking power such as phosphoric acid ester, urethane resin auxiliary agent simultaneously, just starts to reach required adhesivity on realistic scale.In this case, add these sticking power auxiliary agents, not only increase operation number of times, but also also exist and need selected not damage the problems such as the sticking power auxiliary agent kind of coating characteristic, tight test optimum addition.
On the other hand, take mercaptan compound as the cured film of the solidification compound of solidifying agent as described in non-patent literature 1, excellent to organic adhesivity.But, abundant not to the adhesivity of the inorganicss such as glass, ITO, aluminium.Especially, take mercaptan compound as the cured film poor water resistance of the solidification compound of solidifying agent, if therefore there is in hot and humid lower exposure the problem that adhesivity declines greatly.
In addition, the curable resin composition being mixed with the light solidity of mercaptan compound and multifunctional polyene as described in patent documentation 2, the cured article obtained is also abundant not to the adhesivity of inorganics.
Further, take mercaptan compound as the solidification compound of solidifying agent, if be catalyzer with amine, even if at room temperature also can be cured, be therefore expected to obtain the long curing composition of a kind of usable time (under environment for use spendable time).
Therefore, the present invention completes in view of the foregoing, its objective is and provides a kind of curable resin composition to the adhesivity excellence of the inorganic substrates such as glass, tin indium oxide (ITO), aluminium.
The means of technical solution problem
The present inventor is in order to solve the problem, conduct in-depth research, found that, replace existing silane coupling agent or mercaptan compound, alkoxyl silicone alkane derivatives containing specific Sulfide-containing Hindered is the curable resin composition of effective constituent, to inorganic substrate, there is excellent adhesivity, and then complete the present invention.
Namely, the present invention is the curable resin composition containing following (A), (B), (C) and (D) composition, described (A) composition to be molecular weight be 200 ~ 2000 multi-functional thiol's compound, described (B) composition is that molecular weight is 200 ~ 50000 and epoxy equivalent (weight) is the polyfunctional epoxy resin of 80 ~ 6000g/mol, described (C) composition is the alkoxyl silicone alkane derivatives of the Sulfide-containing Hindered shown in following general formula (1), described (D) composition to be molecular weight be 90 ~ 700 aminated compounds.And, the weight ratio ((A)/(B)) of described (A) composition and described (B) composition is 0.05 ~ 30, be 100 parts by weight with the gross weight of described (A) composition and described (B) composition, be mixed into (D) composition described in (C) composition, 0.01 ~ 50 weight part described in 0.5 ~ 50 weight part.
Chemical formula 1
Wherein, a and b is the integer of 0 ~ 2, and c is the integer of 1 ~ 3, a+b+c=3.R is the trivalent radical shown in following general formula (2), R 1and R 2be-CH independently of one another 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 3for methyl or ethyl.
Chemical formula 2
Wherein, m is 1 or 2.
Like this, as sticking power auxiliary agent, with the alkoxyl silicone alkane derivatives (C) of specific Sulfide-containing Hindered for effective constituent, equilibrium adds (A) ~ (D) composition, thus the adhesivity to inorganic substrate excellence can be shown.
In addition, in the present invention, the weight of chemical substance required when " equivalent " refers to the functional group's number in order to form 1mol chemical substance, can pass through (molecular weight)/number of functional group (in 1 molecule) try to achieve.In addition, in the case of polymers, " molecular weight " represents weight-average molecular weight.
Curable resin composition of the present invention, except described (A) ~ (D) composition, can also contain following (E) composition.Curable resin composition described of the present invention not containing (E) composition is thermoset, if but add (E) composition wherein, then can give curable resin composition light solidity or photo-thermal two-stage solidity, curing reaction can be selected according to operating environment or application target etc.Specifically, as (E) composition, also can be 200 ~ 50000 containing molecular weight and (methyl) acrylate equivalent is multifunctional (methyl) acrylic compound of 80 ~ 6000g/mol.Be 100 parts by weight with the gross weight of described (A) composition and described (B) composition, can be mixed into 2 ~ 300 weight parts should (E) composition.In addition, in the present invention, " (methyl) acrylate " represents the general name comprising acrylate and methacrylic ester.
As described aminated compounds (D), preferably use with the imidazolium compounds shown in following general formula (2).Therefore, although be difficult to be cured reaction in the use of curable resin composition below 35 DEG C, storage temperature range, usable time extends, but it can be cured reaction at 60 DEG C, therefore can take into account usable time, stability in storage and low-temperature curing two aspect.
Chemical formula 3
Wherein, R 5for the alkyl of cyano group, carbonatoms 1 ~ 10, with the alkyl of carbonatoms 1 ~ 10 of 2,4-diamino triazine replacement, the alkoxyl group of carbonatoms 1 ~ 4 or hydrogen atom, R 4, R 6, R 7for the alkyl of carbonatoms 1 ~ 20, the alkoxyl group of carbonatoms 1 ~ 4 or hydrogen atom, work as R 4~ R 7when bonding forms ring, R 4, R 6, R 7for carbonatoms is the alkyl of 2 ~ 8.
Imidazolium compounds shown in described chemical formula 3 is the compound shown in following chemical formula 46.
Chemical formula 46
In addition, as described multi-functional thiol's compound (A), preferably use the multi-functional thiol's compound shown in following general formula (4).
Chemical formula 4
Wherein, n is the integer of 2 ~ 5, and p is the integer of 2 ~ 10, R 8for any one in the group (α 2) be made up of ether oxygen (-O-) and alkyl of the alkyl (α 1) of carbonatoms 2 ~ 30, carbonatoms 2 ~ 40, isocyanurate ring (α 3) or the group (α 4) that is made up of isocyanurate ring and alkyl.If this kind of multi-functional thiol's compound, then the stability in storage of curable resin composition is excellent.
In addition, as described polyfunctional epoxy resin (B), preferably use diglycidyl ether type epoxy resin or glycidyl ester type epoxy resin.If this kind of polyfunctional epoxy resin, the reactivity under room temperature is slow, more can extend usable time.
In addition, represent " the 00 ~ ×× " of numerical range in the present invention, its concept comprises its lower value (" 00 ") and higher limit (" ×× ").That is, clearly below more than 00 ××s are represented.
Beneficial effect
According to the present invention, by with the alkoxyl silicone alkane derivatives (C) of specific Sulfide-containing Hindered for effective constituent, and balanced mixture is (A) ~ (D) of neccessary composition, other sticking power auxiliary agents are added without the need to the situation as existing use silane coupling agent, and suppress the addition becoming the effective constituent (C) of sticking power auxiliary agent, excellent adhesivity can be obtained simultaneously.In addition, abundant not to inorganic substrate adhesivityes such as glass, tin indium oxide, aluminium when 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 do not had so far.
In addition, curable resin composition of the present invention, because usable time (serviceable time under environment for use) is long, therefore operability is also good, and stability in storage is also excellent.Further, when making its thermofixation, it compared with prior art can be made at low temperature and solidify in the short period of time.That is, solidification is at room temperature difficult to, when heat cured, even if reactive (solidified nature) is also excellent under the low temperature of about 60 DEG C.In addition, the obdurability of the cured film after curable resin composition of the present invention is solidified, water tolerance, thermotolerance, flexibility and homogeneity etc. can be improved.Therefore, after inorganic substrate forms cured film, even if be exposed in the severe rugged environment as (such as 120 DEG C × 100RH% × 90 hours) under high temperature and humidity condition, also sufficient adhesivity can be maintained.
Embodiment
Below, the present invention is described in detail.Curable resin composition of the present invention is with following (A), (B), (C) and (D) composition for neccessary composition, can also contain the curable resin composition of (E) composition as required.
(multi-functional thiol's compound ((A) composition))
Multi-functional thiol's compound (A) in curable resin composition of the present invention refers to the organic compound with two or more thiol group (-SH base).The molecular weight of multi-functional thiol's compound is 200 ~ 2000, preferably 300 ~ 1800, be more preferably 350 ~ 1600.Even if molecular weight is less than 200, also no problem about adhesivity, but the volatility of multi-functional thiol's compound is high, has the tendency that stink strengthens.On the other hand, if molecular weight is greater than 2000, reduces relative to the solvability of polyfunctional epoxy resin described later (B), may decline to the adhesivity of inorganic substrate.
As multi-functional thiol's compound (A), the multi-functional thiol's compound as shown in following general formula (4) can be exemplified.In addition, multi-functional thiol's compound (A), namely only can be used alone one, two or more may be used in combination.
Chemical formula 5
Wherein, n is the integer of 2 ~ 5, and p is the integer of 2 ~ 10, R 8for any one in the group (α 2) be made up of ether oxygen (-O-) and alkyl of the alkyl (α 1) of carbonatoms 2 ~ 30, carbonatoms 2 ~ 40, isocyanurate ring (α 3) or the group (α 4) that is made up of isocyanurate ring and alkyl.
In above-mentioned general formula (3), even the compound of n=1 does not have large problem yet, how much can use, but the multi-functional thiol's compound reactivity obtained is higher, there is the tendency of variation in the stability in storage of the curable resin composition therefore containing this compound.Corresponding thereto, if the compound in the scope of n=2 ~ 5, stability in storage is excellent, simultaneously in the low temperature of about 60 DEG C, can it be made to solidify in the short period of time.In addition, along with the increase of n numerical value, the reactivity of the multi-functional thiol's compound obtained reduces, and the set time during thermofixation of the curable resin composition containing this compound has elongated tendency.Therefore, in the compound shown in above-mentioned general formula (3), the most preferably compound of n=2.If n=2, the reactivity of multi-functional thiol's compound is all best to the set time both when stability in storage and shortening heat solidification.
The multi-functional thiol's compound shown in above-mentioned general formula (4) can be obtained by the esterification of the polyfunctional alcohol shown in the mercaptan carboxylic acid shown in following general formula (5) and following general formula (6).
Chemical formula 6
Wherein, n is the integer of 1 ~ 5.
Chemical formula 7
Wherein, p is the integer of 2 ~ 10, R 8for any one in the group (α 2) be made up of ether oxygen (-O-) and alkyl of the alkyl (α 1) of carbonatoms 2 ~ 30, carbonatoms 2 ~ 40, isocyanurate ring (α 3) or the group (α 4) that is made up of isocyanurate ring and alkyl.
In the compound shown in above-mentioned general formula (6), be preferably 2 ~ 4 and R by P 8compound (α 1-1), the P of the group formed for the alkyl of carbonatoms 2 ~ 20 are 2 ~ 6 and R 8for the compound (α 2-1) of the group be made up of ether oxygen (-O-) and alkyl of carbonatoms 2 ~ 30 or P are 3 and R 8for the compound (α 4-1) of group be made up of the alkyl of isocyanurate ring and carbonatoms 1 ~ 3.This is because, if such compound, high with the solvability of polyfunctional epoxy resin (B).
As (α 1-1), can exemplify as the alkylene glycol of carbonatoms 2 ~ 20, glycerine, tetramethylolmethane or TriMethylolPropane(TMP) etc.Can exemplify as polyoxyethylene glycol, polypropylene glycol, Dipentaerythritol etc. as (α 2-1).As (α 4-1), can exemplify as three (2-hydroxyethyl) isocyanuric acid ester etc.
< polyfunctional epoxy resin ((B) composition) >
Polyfunctional epoxy resin (B) in curable resin composition of the present invention is the organic compound with two or more epoxy group(ing) (oxyethane ring).The molecular weight of polyfunctional epoxy resin is 200 ~ 50000, preferably 200 ~ 48000, be more preferably 200 ~ 46000.Even if it is also no problem that molecular weight is 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 is greater than 50000, reduce relative to the solvability of other compositions, may cause declining to the adhesivity of inorganic substrate.
The epoxy equivalent (weight) of polyfunctional epoxy resin is 80 ~ 6000g/mol, preferably 85 ~ 5500g/mol, is more preferably 90 ~ 5000g/mol.If epoxy equivalent (weight) is less than 80g/mol, epoxy group(ing) in unit volume is too much, the epoxy group(ing) of not reacting with the thiol group of multi-functional thiol's compound (A) remains in a large number, the toughness of the cured film be therefore made up of curable resin composition may decline, and when being exposed to high temperature and humidity environment, adhesivity may decline.On the other hand, if epoxy equivalent (weight) is greater than 6000g/mol, epoxy group(ing) concentration significantly reduces, therefore reduce with the reaction efficiency of the thiol group of multi-functional thiol's compound (A), the toughness of the cured film be made up of curable resin composition may decline, and when being exposed under high temperature and humidity environment, adhesivity may decline.
As polyfunctional epoxy resin (B), can exemplify as diglycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin or with peroxide oxidation containing the double bond of double bond compound the oxidized form epoxy resin etc. that obtains.Wherein, because reactivity is at room temperature slow and usable time extends, therefore preferred diglycidyl ether type epoxy resin or glycidyl ester type epoxy resin.Especially diglycidyl ether type epoxy resin, owing to not having the functional group can reacted with multi-functional thiol's compound (A), can not rely on reaction conditions and obtain homogeneous curable resin composition even cured film.In addition, polyfunctional epoxy resin (B) only can be used alone one, and two or more may be used in combination.
< diglycidyl ether type epoxy resin >
As diglycidyl ether type epoxy resin, the reaction product shown in preferred epoxy chloropropane and following general formula (7) between compound.
Chemical formula 8
Wherein, q is the integer of 2 ~ 30, R 9for the group (β 4) that the alkyl (β 1) of carbonatoms 2 ~ 200, the group (β 2), isocyanurate ring (β 3), isocyanurate ring and the alkyl that are made up of ether oxygen (-O-) and alkyl of carbonatoms 2 ~ 300 are formed.
In the compound shown in above-mentioned general formula (7), because high with the solvability of other compositions, therefore preferably q is 2 ~ 20 and R 9for the compound (β 1-1) of the group be made up of alkyl of carbonatoms 2 ~ 150, or q is 2 ~ 20 and R 9for the compound (β 2-1) of the group be made up of alkyl and ether oxygen (-O-) of carbonatoms 2 ~ 150.The alkylene glycol, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), phenol novolac, dihydroxyphenyl propane etc. as carbonatoms 2 ~ 10 can be exemplified as (β 1-1).Can exemplify as polyoxyethylene glycol, polypropylene glycol or Dipentaerythritol etc. as (β 2-1).
Reaction between the compound shown in above-mentioned epoxy chloropropane and general formula (7) is as follows, make the hydroxyl generation addition reaction of the compound shown in epoxy chloropropane and general formula (7), obtain chloropharin, make the chloropharin obtained close ring with alkali such as sodium oxides, obtained epoxy resin.In addition, diglycidyl ether type epoxy resin also can be the epoxy resin that the PART EPOXY base ring-opening polymerization of the epoxy resin obtained after making described ring closure reaction obtains.
The reaction product of the compound shown in epoxy chloropropane and general formula (7), has the structure as shown in following general formula (8).
Chemical formula 9
Wherein, q is the integer of 2 ~ 30, R 9for the group (β 2) be made up of ether oxygen (-O-) and alkyl of the alkyl (β 1) of carbonatoms 2 ~ 200, carbonatoms 2 ~ 300, isocyanurate ring (β 3) or the group (β 4) that is made up of isocyanurate ring and alkyl.
< glycidyl ester type epoxy resin >
Glycidyl ester type epoxy resin, it is the monomer (methyl) glycidyl acrylate etc. with epoxy group(ing), separately or be the polymkeric substance of 3000 ~ 20000 with the weight-average molecular weight that (methyl) alkyl acrylate copolymer of carbonatoms 4 ~ 25 obtains, or the reaction product etc. of the compound shown in epoxy chloropropane and following general formula (9).
Chemical formula 10
Wherein, r is the integer of 2 ~ 8, R 10for any one in the group (β 6) be made up of ether oxygen (-O-) and alkyl of the alkyl (β 5) of carbonatoms 2 ~ 20, carbonatoms 2 ~ 30, isocyanurate ring (β 7) or the group (β 8) that is made up of isocyanurate ring and alkyl.
Reaction shown in epoxy chloropropane and general formula (9) between compound is as follows, the carboxyl addition reaction of compound shown in epoxy chloropropane and general formula (9) is made to obtain chloropharin, the chloropharin obtained is made to close ring with alkali such as sodium hydroxide, obtained glycidyl ester type epoxy resin.In addition, the epoxy resin that the PART EPOXY base ring-opening polymerization of glycidyl ester type epoxy resin is obtained can also be used.
In the compound shown in above-mentioned general formula (9), because solvability is high, therefore preferably r is 2 ~ 4 and R 10for the compound (β 5-1) of the group be made up of alkyl of carbonatoms 2 ~ 10, or r is 2 ~ 6 and R 10for the compound (β 6-1) of the group be made up of ether oxygen (-O-) and alkyl of carbonatoms 2 ~ 30, or r is 3 and R 10for the compound (β 8-1) of group be made up of isocyanurate ring and alkyl.
As (β 5-1), can exemplify as hydrogenation phthalic acid or trimellitic acid etc.As (β 6-1), the reaction product as tetramethylolmethane and trimellitic acid 1,2-anhydride can be exemplified.As (β 8-1), can exemplify as 1,3,5-tri-(2-propyloic) isocyanuric acid ester etc.
The reaction product of the compound shown in epoxy chloropropane and general formula (9), has structure shown in following general formula (10).
Chemical formula 11
Wherein, r is the integer of 2 ~ 8, R 10for any one in the group (β 6) be made up of ether oxygen (-O-) and alkyl of the alkyl (β 5) of carbonatoms 2 ~ 20, carbonatoms 2 ~ 30, isocyanurate ring (β 7) or the group (β 8) that is made up of isocyanurate ring and alkyl.
Alkoxyl silicone alkane derivatives (C) the composition > of < Sulfide-containing Hindered
The alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered, when being solidification curable resin composition of the present invention, in order to improve the adhesion promoter added the adhesivity of inorganic substrate.The alkoxyl silicone alkane derivatives (C) of this Sulfide-containing Hindered has thioether group, with disulfide linkage and the thioether group generation chemical bonding generated by multi-functional thiol's compound (A) and polyfunctional epoxy resin (B) crosslinking reaction.Now, due to the alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered and the intermiscibility of multi-functional thiol's compound (A) is high and reaction efficiency is high, the sticking power facilitation effect therefore obtained is high.Further, it is silica-based that the alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered has alcoxyl, can react the hydroxyl reaction generated with by multi-functional thiol's compound (A) and polyfunctional epoxy resin (B).As a result, the resin cured matter cross-linking density obtained improves, and forms the tough crosslinked (cured article) with enhanced water resistance.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 sticking power between inorganic substrate.
The alkoxyl silicone alkane derivatives (C) of the Sulfide-containing Hindered in curable resin composition of the present invention is the compound shown in following general formula (1).In addition, the alkoxyl silicone alkane derivatives (C) of Sulfide-containing Hindered only can be used alone one, and two or more may be used in combination.
Chemical formula 12
Wherein, a and b is the integer of 0 ~ 2, and c is the integer of 1 ~ 3, a+b+c=3.R is the trivalent radical shown in following general formula (2), R 1and R 2for being 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 3for methyl or ethyl.
Chemical formula 13
Wherein, m is 1 or 2.
The alkoxyl silicone alkane derivatives (C) of this Sulfide-containing Hindered, can by making at least have the silica-based (-Si (OR of alcoxyl 4) 3) and the compound (being often called X composition below) of double bond react with containing the multi-thiol compound (being often called Y composition below) of thiol group (-SH) and obtain.Specifically, b is the compound of 0, can react obtained by making the compound (X) silica-based containing alcoxyl at least Ru shown in following general formula (11) with the multi-thiol compound (Y) shown in following general formula (12).In addition, b is not the compound of 0, can by make at least Ru shown in following general formula (11) containing the multi-thiol compound (Y) shown in the silica-based compound (X) of alcoxyl, following general formula (12) and the reaction of (methyl) glycidyl acrylate obtained.In addition, if make (X) composition and (Y) composition react, then the double bond of (X) composition and the thiol group of (Y) composition react.
Chemical formula 14
Wherein, R 3for methyl or ethyl, R 14for hydrogen atom or methyl.
Chemical formula 15
Wherein, m is the integer of 1 or 2.
As the compound (X) silica-based containing alcoxyl shown in above-mentioned general formula (11), can exemplify as 3-methacryloxypropyl trimethoxy silane, 3-acryloxypropyl Trimethoxy silane, 3-methacryloxypropyl, 3-acryloxypropyl Trimethoxy silane.
As the multi-thiol compound (Y) shown in above-mentioned general formula (12), three ((the 3-mercaptopropionyl oxygen base)-ethyl) isocyanuric acid ester as m=2 can be exemplified.As the compound (Y) of m=1, the synthetics as isocyanic acid three (2-hydroxyethyl) ester and Thiovanic acid can be exemplified.In above-mentioned general formula (12), when using the compound of m >=3, hydrophobicity and nonpolar hydrocarbon number increase, thus the orientation of thioether group to base material is weakened, and are difficult to obtain adhesivity.
Under the effect of catalyzer or radical initiator, preferably make (X) composition and (Y) composition react.This is because, if add catalyzer or radical initiator, can it be made to react in shorter time and more expeditiously.
As catalyzer, be preferably the basic catalyst of amine, primary amine, secondary amine or tertiary amines can be used, or use glyoxaline compound.Such as can exemplify methylamine, ethamine, propylamine, butylamine, quadrol etc. as primary amine; Dimethylamine, diethylamine, dipropyl amine, methylethyl amine, diphenylamine etc. can be exemplified as secondary amine; Trimethylamine 99, triethylamine, tripropyl amine, triphenylamine, 1,8-diazabicyclo (5,4,0)-ten one carbon-7-alkene, 2,4,6-tri-(dimethylamino methyl) phenol etc. can be exemplified as tertiary amine.As glyoxaline compound, such as, can exemplify the imidazoles homologue of 1-Methylimidazole, 1,2 dimethylimidazole, Isosorbide-5-Nitrae-dimethyl-2-ethyl imidazol(e), 1-phenylimidazole etc.; The oxyalkyl derivatives such as 1-methyl-2-oxygen Methylimidazole, 1-methyl-2-oxygen ethyl imidazol(e); Nitro and the aminoderivatives such as 1-methyl-4 (5)-nitroimidazole, 1,2-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, can exemplify dibenzoyl peroxide, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation two dodecanoyl, tertbutyl peroxide etc.As azo-compound, such as, 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, it at the temperature more than 5 DEG C, just can be made to react, but in order to make it react at short notice, preferably 30 ~ 120 DEG C, especially preferably 60 ~ 80 DEG C.
In the preparation method of the alkoxyl silicone alkane derivatives of Sulfide-containing Hindered, reaction also can be made to carry out even if solvent-free, but if when making it react at low temperatures or under wanting to fall low viscous situation, also can add solvent and make it react.The now preferred solvent that reacts of not silica-based with alcoxyl, double bond, thiol group, preference is as alcohols, ketone, ester class or the fragrant same clan.
As described alcohols, the primary alconol of preferred carbonatoms less than 3, in addition, the alcohol that preferred boiling point is higher than temperature of reaction.The alcohols high at temperature range interior reaction temperature is better.In addition, in the reaction, alcohol and alcoxyl is silica-based likely transesterification reaction occurs, may causing the yield of target product to decline, therefore in order to suppress yield to decline, preferably having R 2the material of OH structure.As the reaction solvent meeting above-mentioned condition, can exemplify as methyl alcohol or ethanol etc.In addition, as ketone, the ketone that preferred boiling point is higher than temperature of reaction, in addition from the viewpoint of solvability, the ketone of preferred carbonatoms less than 6.As the ketone meeting above-mentioned condition, can exemplify as methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.In addition, as ester class, the ester class that preferred boiling point is higher than temperature of reaction, in addition from the viewpoint of solvability, preferred straight chain and carbonatoms are the ester class of less than 6.As the ester class meeting above-mentioned condition, can exemplify as N-BUTYL ACETATE, vinyl acetic monomer etc.
As the ester class that not silica-based with alcoxyl, double bond, thiol group react, the ester class that preferred boiling point is higher than temperature of reaction, in addition from the viewpoint of solvability, preferred straight chain and carbonatoms are the ester class of less than 6.As the ester class meeting above-mentioned condition, can exemplify as vinyl acetic monomer, ritalin, N-BUTYL ACETATE, acetic acid methoxybutyl, acetic acid ethylene glycol ethyl ether, amyl acetate-n, methyl lactate, ethyl lactate, n-Butyl lactate etc.
< aminated compounds (D) composition >
Aminated compounds in curable resin composition of the present invention, for promoting that (catalysis) reaction between thiol group and epoxy group(ing) is added.As aminated compounds (D), can exemplify as molecular weight be 90 ~ 700, the monofunctional amines of preferably 100 ~ 690, especially preferably 110 ~ 680 or there is the polyamines of multiple amino.If the molecular weight of aminated compounds (D) is less than 90, then the volatility of amine uprises, and not only has the defect such as foul smell or hole, and during owing to being heating and curing, the concentration reduction of amine is difficult to carry out crosslinking reaction, and adhesivity easily declines.If the molecular weight of aminated compounds (D) is more than 700, then water tolerance decline adhesivity is easily caused easily to decline.
As simple function amine, can exemplify as primary amine, secondary amine or tertiary amine.As polyamines, can exemplify as primary amine, secondary amine, tertiary amine, varies.Varies refers to have amine two or more in primary amine groups, secondary amine, tertiary amine groups.As these variess, can exemplify as imidazolinium compounds, imidazolium compounds, N substituted piperazine like compound, N, N-dimethyl urea derivative etc.In addition, aminated compounds (D) only can be used alone one, and two or more may be used in combination.
In addition, in order to adjust catalytic activity, aminated compounds (D) can form salt with organic acid in advance.As the organic acid reacted with aminated compounds (D) in advance, can exemplify as carbonatoms 1 ~ 20 and there is in molecule the aliphatic carboxylic acid such as stearic acid or 2 ethyl hexanoic acid of 1 ~ 5 carboxyl, carbonatoms 1 ~ 20 and have aromatic carboxylic acid or the tricarbimide such as Pyromellitic Acid, trimellitic acid, M-nitro benzoic acid of 1 ~ 10 carboxyl in molecule.In addition, in order to adjust catalytic activity, aminated compounds (D) can also be mixed into after forming affixture with polyfunctional epoxy resin (B).
< imidazolium compounds >
In aminated compounds (D), imidazolium compounds is most suitable for getting both the solidified nature under stability in storage and low temperature.In addition, can also use with the imidazolium compounds of phenolic resin coating.
This imidazolium compounds is the compound represented with following general formula (3).
Chemical formula 16
Wherein, R 5for the alkyl of cyano group, carbonatoms 1 ~ 10, with the alkyl of carbonatoms 1 ~ 10 of 2,3-diamino triazine replacement, the alkoxyl group of carbonatoms 1 ~ 4 or hydrogen atom, R 4, R 6, R 7for the alkyl of carbonatoms 1 ~ 20, the alkoxyl group of carbonatoms 1 ~ 4 or hydrogen atom, work as R 4~ R 7bonding is the alkyl of carbonatoms 2 ~ 8 when forming ring.
Specifically, glyoxal ethyline can be exemplified, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 1,2 dimethylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyano ethyl)-glyoxal ethyline, 1-(2-cyano ethyl)-2-undecyl imidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 1-(2-cyano ethyl)-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo-(1,2-a) benzoglyoxaline, 2,4-diamino-6-(glyoxal ethyline-(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-bishydroxymethyl imidazoles, 2-phenyl-4-methyl-5-hydroxymethylimidazole.
< multifunctional (methyl) acrylic compound ((E) composition) >
If have multi-functional thiol's compound (A), polyfunctional epoxy resin (B) and aminated compounds (D) in curable resin composition of the present invention, then can be cured by heat.On the other hand, when wanting to give curable resin composition light solidity of the present invention or photo-thermal two-stage solidified nature, then multifunctional (methyl) acrylic compound (E) can be added.
As everyone knows, heat or light exciting under, mercaptan and double bond generation addition reaction.Therefore, multi-functional thiol's compound (A) and the mixture of the compound containing multifunctional double bond, can form curable resin composition.In the present invention, in above-mentioned double bond, preferably there is multifunctional (methyl) acrylic compound (E) of the compound of two or more acryloxy or methacryloxy.Contain in the compound of double bond numerous, the reason of multifunctional (methyl) acrylate is selected to be, at room temperature be difficult to react with the multi-functional thiol's compound (A) in curable resin composition of the present invention, can long usable time be set; When reacting with multi-functional thiol's compound (A), tough cured article can be formed; Be difficult to the reaction by aminated compounds (D) catalysis and multi-functional thiol's compound (A), and do not react with polyfunctional epoxy resin (B).
As this multifunctional (methyl) acrylate (E), can exemplify to be preferably as follows and state the compound shown in general formula (13).In addition, multifunctional (methyl) acrylate (E) only can be used alone one, and two or more may be used in combination.
Chemical formula 17
Wherein, s is the integer of 2 ~ 30, R 12for the group (ε 2) be made up of ether oxygen (-O-) and alkyl of the alkyl (ε 1) of carbonatoms 2 ~ 200, carbonatoms 2 ~ 300, isocyanurate ring (ε 3) or the group (ε 4) that is made up of isocyanurate ring and alkyl, R 13for hydrogen atom or methyl.
In addition, as multifunctional (methyl) acrylate (E), the compound using polymer class can be suitable for.As multifunctional (methyl) acrylate (E) of polymer class, can exemplify as in: (methyl) acrylic compound homopolymer that there is epoxy group(ing) at (methyl) glycidyl acrylate etc. or multipolymer, make to react obtained polymkeric substance with (methyl) acrylic compound of the group of epoxy reaction as (methyl) vinylformic acid etc. has; In (methyl) the acrylic compound homopolymer that there is hydroxyl in (methyl) hydroxyethyl acrylate etc. or multipolymer, make to react obtained polymkeric substance with (methyl) acrylic compound of the group of hydroxyl reaction as 2-methacrylic acid 2-isocyanatoethyl methacrylate etc. has; In (methyl) the acrylic compound homopolymer that there is carboxyl at (methyl) vinylformic acid etc. or multipolymer, make to react obtained polymkeric substance etc. with (methyl) acrylic compound of carboxyl reaction as (methyl) glycidyl acrylate etc. has.
The molecular weight of multifunctional (methyl) acrylic compound (E) is 200 ~ 50000, preferably 220 ~ 40000, be more preferably 240 ~ 30000.Multifunctional (methyl) acrylic compound (E) though molecular weight be less than 200, also no problem about adhesivity, but there is volatility uprises, the tendency of foul smell grow.On the other hand, if be greater than 50000, may decline relative to the solvability of other compositions.
In addition, (methyl) acrylate equivalent of multifunctional (methyl) acrylate (E) is 80 ~ 6000g/mol, preferably 80 ~ 4500, be more preferably 85 ~ 3000.If (methyl) acrylate equivalent is less than 80g/mol, then in unit volume, (methyl) acryloxy is too much, (methyl) acryloxy do not reacted with the thiol group of multi-functional thiol's compound (A) remains in a large number, the toughness of the cured film be therefore made up of curable resin composition may decline, when exposing under high temperature and humidity condition, adhesivity may decline.On the other hand, if (methyl) acrylate equivalent is greater than 6000g/mol, then (methyl) acryloxy concentration significantly reduces, therefore decline with the reaction efficiency of the thiol group of multi-functional thiol's compound (A), the toughness of the cured film be made up of curable resin composition may be caused to decline, and when exposing under high temperature and humidity environment, adhesivity declines.
< ratio of components (balanced proportioning) >
Curable resin composition of the present invention, is mixed into multi-functional thiol's compound (A) and polyfunctional epoxy resin (B), makes its weight ratio (A)/(B) be 0.05 ~ 30.This place, " (A)/(B) " refers to the weight of the weight of polyfunctional epoxy resin (B) except multi-functional thiol's compound (A).Best (A)/(B) value, because of the characteristic required by curable resin composition, multi-functional thiol's compound (A) or polyfunctional epoxy resin (B) and the structure of multifunctional (methyl) acrylic compound (E) of according to circumstances adding different and different.Characteristic after curable resin composition solidification, the strict value impact by (mercaptan radix)/(epoxy radix+(methyl) acryloyl-oxy radix) (hereinafter referred to as mercaptan/(epoxy+alkene) ratio) in curable resin composition unit weight.Such as, mercaptan/(epoxy+alkene), than in the scope of 0.5 ~ 1.5, is easily formed closely crosslinked, and easily forms tough cured article.On the other hand, if mercaptan/(epoxy+alkene) than be more than 0.1 less than 0.5 or less than 2.0 more than 1.5 time, soft stickiness cured article can be obtained.If mercaptan/(epoxy+alkene), than during less than 0.1 or more than 2.0, is difficult to gelation, has adhesivity downward trend.
In addition, curable resin composition of the present invention, be 100 parts by weight with the gross weight (A+B) of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B), add the alkoxyl silicone alkane derivatives (C) of 0.5 ~ 50 weight part Sulfide-containing Hindered, preferably add 0.5 ~ 45 weight part.Relative to (A+B), when the proportional quantity of (C) composition is less than 0.5 weight part, be difficult to obtain excellent adhesivity, if more than 50 weight parts, the cross-linking density of cured article reduces, and obdurability declines, and therefore adhesivity may decline.
In addition, curable resin composition of the present invention, be 100 parts by weight with the gross weight (A+B) of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B), be mixed into the aminated compounds (D) of 0.01 ~ 50 weight part, preferably add 0.01 ~ 45 weight part.Relative to (A+B), when the proportional quantity of (D) composition is less than 0.01, due to the reaction needing the time to carry out thiol group and epoxy group(ing), therefore solidify bad, during more than 50 weight part, then cross-linking density may reduce, and adhesivity may decline.
In addition, when being also mixed into multifunctional (methyl) acrylic compound (E) in curable resin composition of the present invention, be 100 parts by weight with the gross weight (A+B) of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B), be mixed into 2 ~ 300 weight parts multifunctional (methyl) acrylic compound (E), preferably add 2 ~ 250 weight parts.Relative to (A+B), when the proportional quantity of (E) composition is less than 2, be difficult to give its light solidity, if more than 300 weight part time, have adhesivity decline tendency.
< curable resin composition >
If the epoxy reaction of the thiol group of multi-functional thiol's compound (A) and polyfunctional epoxy resin (B), then generate thioether group or hydroxyl.The organoalkoxysilane (C) of Sulfide-containing Hindered also has thioether group, is cross-linked with the thioether that disulfide linkage generates with above-mentioned thiol group and epoxy reaction.In addition, it is silica-based that the alkoxysilane compound containing trialkylsilyl group in molecular structure (C) of Sulfide-containing Hindered also has alcoxyl simultaneously, and the hydroxyl reaction generated with above-mentioned thiol group and epoxy reaction is cross-linked.As a result, crosslinked closely can be formed.Cured article after curable resin composition of the present invention is solidified, because define crosslinked closely, the therefore raising such as thermotolerance, obdurability and water tolerance.Further, it is the cured article formed with thioether group or disulfide bond crosslinking, is also rich in snappiness, therefore has high adhesivity.And, the alkoxysilane compound containing trialkylsilyl group in molecular structure (C) of Sulfide-containing Hindered, also there are three alcoxyls silica-based simultaneously, therefore especially can form chemical bond with the inorganic substrate of glass and so on, and then the adhesivity of curable resin composition of the present invention to inorganic substrate significantly improves.
In addition; in curable resin composition of the present invention, (methyl) acryl of multifunctional (methyl) acrylic compound (E) that optionally add and the thiol group also reaction under the exciting of light 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 with the solidification of light and heat two-stage.Further, by controlling respective moiety amount, the degree of photocuring and thermofixation can be controlled.
At present, multiple mercaptan compound is used as solidifying agent (compound added for making the host such as epoxy resin or (methyl) acrylic compound solidify).In addition, as everyone knows, 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, in order to reaction system is homogeneous, easy coating etc., also can use with after organic solvent diluting.As this organic solvent, can exemplify as alcoholic solvent, aromatic hydrocarbon solvent, ether solvent, esters solvent and solvent of ether ester type, ketones solvent, phosphoric acid ester solvent.Relative to 100 weight part curable resin compositions, the proportional quantity of these organic solvents preferably controls as being less than 10000 weight parts, but substantially formed cured film time solvent volatilize, therefore can not cause large impact to the physical properties of cured film.But, when being used as solvent with the compound and aminated compounds with the functional group can reacted with thiol group, epoxy group(ing) or (methyl) acryl, likely can damage effect of the present invention.
In addition, in order to adjusting viscosity, curable resin composition of the present invention also can be mixed into the viscosity modifiers such as SiO 2 powder.Relative 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 is more than 300 weight parts, adhesivity may decline.
In addition, curable resin composition of the present invention also can add in common coating or binding agent the various additives used.As these additives, can exemplify as the tensio-active agent for making coating surface level and smooth, for extend usable time aluminium salt, for improving photoreactive optical free radical initiator, photoproduction alkaline agent, photo-acid agent etc.Relative 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 is more than 80 weight parts, adhesivity may decline.
Embodiment
Exemplify embodiment below and comparative example carries out more specific description to the present invention, but the present invention is not limited thereto.Reagent used in the present embodiment and 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 component) >
(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 (with hexane to the reppd white solid of 50wt% methyl isobutyl ketone solution) of glycidyl methacrylate and cyclohexyl methacrylate.
(B-8, Mw:45000, epoxy equivalent (weight): 250)
The multipolymer (with hexane to the reppd white solid of 50wt% methyl isobutyl ketone solution) of glycidyl methacrylate and cyclohexyl methacrylate.
Alkoxyl silicone alkane derivatives (C composition) > of < Sulfide-containing Hindered
(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 the integer of 1 ~ 5, the mixture of average 3.5.
(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, double bond equivalent: 123)
Chemical formula 48
(E-2, Mw:352, double bond equivalent: 88)
Chemical formula 49
(E-3, Mw:376, double bond equivalent: 183)
Chemical formula 50
(E-4, Mw:5000, double bond equivalent: 3000)
Chemical formula 51
N average out to 13
(E-5, Mw:1200, double bond equivalent: 180)
Chemical formula 52
N average out to 5
(E-6, Mw:586, double bond equivalent: 195)
Chemical formula 53
(E-7, Mw:22000, double bond equivalent: 320)
Take D-3 as mole addition (methyl) acrylic acid polymkeric substance (with hexane to the reppd white solid of 50wt% methyl isobutyl ketone solution) such as catalyzer, the multipolymers of glycidyl methacrylate and cyclohexyl methacrylate.
Other reagent of < >
(F-1, ≒ A composition)
Chemical formula 54
(F-2, ≒ C composition)
Chemical formula 55
As shown in table 1,2, be mixed into (A) ~ (E) composition respectively with balanced proportioning, be stirred to evenly with scraper.Carry out following evaluation to the sample after stirring, its result is as shown in table 1,2.
< adhesivity evaluation >
Be 100 μm with rod coater at non-alkali glass (OA-10, NEG company produce, thickness 0.7mm) and aluminium sheet (A5052P, Japanese Testpanel company produce, thickness 2.0mm) upper coating Examples and comparative example to thickness, heat 1 hour at 140 DEG C, each base material obtains cured film.Under the condition of 121 DEG C × 100RH% × 90 hour, process obtains the base material of cured film, then evaluates with the film of JISK5600-5-6 defined mechanical properties-adhesivity (cross-section method) test method.Be designated as ◎ without peeling off completely, peel off account for entire area 1 one-tenth and be designated as zero below, be in addition designated as ×.Adhesivity 1 in table is the result on non-alkali glass base material, and adhesivity 2 is the result on aluminium sheet base material.
< confirms light solidity >
On non-alkali glass, each embodiment is coated with and comparative example to thickness is 100 μm, with high-pressure mercury light irradiation 500mJ/cm with rod coater 2the light of (being scaled i ray).When suppressing with scraper the film irradiated, situation scraper not attaching coating fluid is designated as zero.
< confirms stability in storage (preservation stability) >
With each embodiment of following viscometer determining and the firm mixed viscosity of comparative example.After each embodiment and comparative example are heated 12 hours at 30 DEG C, then measure viscosity.With mixed viscosity except the thickening rate that obtains of viscosity after heating be 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 DEG C.
From the result of table 1 and table 2, whole embodiment all has high adhesivity.In addition, can to confirm in embodiment 2-1 ~ 2-8, because with the addition of (E) composition, light solidity can be given.In addition, clearly in embodiment 1-3 ~ 1-7,2-3 ~ 2-8, amine can be defined as imidazolium compounds, thus improve stability in storage (preservation stability).On the other hand, as shown in each comparative example, containing any one in neccessary composition (A) ~ (D) in the present invention or be different materials, the adhesivity to inorganic substrate excellence can not be obtained.

Claims (6)

1. a curable resin composition, is characterized in that, containing following (A), (B), (C) and (D) composition,
Described (A) composition to be molecular weight be 200 ~ 2000 multi-functional thiol's compound;
Described (B) composition is that molecular weight is 200 ~ 50000 and epoxy equivalent (weight) is the polyfunctional epoxy resin of 80 ~ 6000g/mol;
Described (C) composition is for the alkoxyl silicone alkane derivatives of the Sulfide-containing Hindered shown in following general formula (1);
Described (D) composition to be molecular weight be 90 ~ 700 aminated compounds;
Weight ratio (A)/(B) of described (A) composition and described (B) composition is 0.05 ~ 30;
Be 100 parts by weight with the gross weight of described (A) composition and described (B) composition, be mixed into described (C) composition of 0.5 ~ 50 weight part, be mixed into described (D) composition of 0.01 ~ 50 weight part;
Chemical formula 1
Wherein, a and b is the integer of 0 ~ 2, and c is the integer of 1 ~ 3, a+b+c=3; R is the trivalent radical shown in following general formula (2), R 1and R 2for respective 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 3for 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 be mixed with (E) composition, be molecular weight 200 ~ 50000 as (E) composition and (methyl) acrylate equivalent is multifunctional (methyl) acrylic compound of 80 ~ 6000g/mol; The gross weight of described (A) composition and described (B) composition is 100 parts by weight, and being mixed 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 following general formula (3);
Chemical formula 3
Wherein, R 5for the alkyl of cyano group, carbonatoms 1 ~ 10, with the alkyl of carbonatoms 1 ~ 10 of 2,4-diamino triazine replacement, the alkoxyl group of carbonatoms 1 ~ 4 or hydrogen atom, R 4, R 6, R 7for the alkyl of carbonatoms 1 ~ 20, the alkoxyl group of carbonatoms 1 ~ 4 or hydrogen atom, work as R 4~ R 7when bonding forms ring, R 4, R 6, R 7for carbonatoms is the alkyl of 2 ~ 8.
4. curable resin composition according to claim 3, is characterized in that, the imidazolium compounds shown in described chemical formula 3 is the compound shown in following chemical formula 46,
Chemical formula 46
5. curable resin composition according to claim 1, is characterized in that, described multi-functional thiol's compound (A) is the multi-functional thiol's compound shown in following general formula (4);
Chemical formula 4
Wherein, n is the integer of 2 ~ 5, and p is the integer of 2 ~ 10, R 8for any one in the group (α 2) be made up of ether oxygen and alkyl of the alkyl (α 1) of carbonatoms 2 ~ 30, carbonatoms 2 ~ 40, isocyanurate ring (α 3) or the group (α 4) that is made up of isocyanurate ring and alkyl.
6. curable resin composition according to claim 1, is characterized in that, described polyfunctional epoxy resin (B) is diglycidyl ether type epoxy resin or glycidyl ester type epoxy resin.
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