JP2002047424A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which excels in storage stability while being quick curable or a resin composition which is quick curable and excels in storage stability, rubber elasticity and strength as well. SOLUTION: The curable resin composition comprises a compound having at least one dithiocarbonate group represented by the formula (wherein R1, R2, and R3 are each independently hydrogen atom or a 1-10C hydrocarbon group) in the molecule, an oxazolidine compound and/or a ketimine compound with a structure having a ketimine (C=N) bond derived from a ketone and an amine and a branched carbon or a ring member carbon bonded to at least one α-position of the ketimine carbon or the ketimine nitrogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition which is fast-curing and excellent in storage stability, and more particularly, a curable resin composition which is fast-curing and excellent in storage stability, rubber elasticity and strength. .

[0002]

2. Description of the Related Art A polymer having a five-membered ring dithiocarbonate (1,3-oxathiolane-2-thione) group has been proposed as a fast-curing epoxy resin in Japanese Patent Application Laid-Open No. H5-247027. WO 98/24849 discloses a one-pack type resin composition using a polymer having a 5-membered ring dithiocarbonate group and a latent curing agent such as ketimine. Further, a polymer having a 5-membered ring dithiocarbonate group and an alkoxysilyl group in one molecule, and a resin composition in which a known amine compound such as ketimine is blended with the polymer to adjust the curing rate. JP-A-11-246
No. 632. However, a polymer having a five-membered dithiocarbonate group has a high reactivity with an epoxy resin because a thiol group generated by opening of the five-membered dithiocarbonate group is highly reactive with the epoxy resin. A resin composition containing a commonly used ketimine has a problem of affecting storage stability. In addition, the one-pack type resin composition has high adhesive strength of a cured product due to rapid curing,
There is a problem that elongation is small. On the other hand, the invention of improving the storage stability of a one-pack type epoxy resin composition by using a ketimine compound having a large steric hindrance as a latent curing agent for an epoxy resin is disclosed in WO98 / 31722.
Is disclosed. However, this one-pack type epoxy resin composition has excellent storage stability but has room for improvement in curability.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resin composition which is fast-curing and excellent in storage stability, or which is fast-curing and excellent in storage stability, rubber elasticity and strength. It is to provide a resin composition.

[0004]

That is, the present invention relates to a compound having at least one dithiocarbonate group represented by the following formula (1) in a molecule, an oxazolidine compound, and / or a ketone and an amine. Curable resin composition having a ketimine (C = N) bond derived from a ketimine compound having a structure in which a branched carbon or a ring-membered carbon is bonded to at least one α-position of the ketimine carbon or nitrogen. I will provide a.

Embedded image (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

[0005] In the ketimine compound, it is preferable that the branched carbon or the ring member carbon is bonded to the ketimine carbon.

It is preferable that the ketimine compound is obtained using a ketone represented by the following formula (2).

Embedded image (Wherein, R ⁴ : hydrogen atom, methyl group or ethyl group, R ⁵ : methyl group or ethyl group R ⁶ : alkyl group having 1 to 6 carbon atoms R ⁷ : hydrogen atom or alkyl group having 1 to 6 carbon atoms, Alternatively, R ⁵ and R ⁶ may combine to form a ring,
R ⁴ , R ⁵ and R ⁶ may form an aromatic ring. )

Further, it is preferable to contain a compound having at least one epoxy group in the molecule.

Further, the present invention relates to a polymer having an isocyanate group in a molecule and / or a polymer having a reactive alkoxysilyl group in a molecule, and a dithiocarbonate group represented by the above formula (1). At least one in the molecule
Provided is a curable resin composition containing a compound having one and a latent curing agent.

Preferably, the isocyanate group of the polymer having an isocyanate group in the molecule is bonded to a secondary carbon or a tertiary carbon.

The latent curing agent is preferably an oxazolidine compound and / or a ketimine compound having a ketimine (CＣN) bond derived from a ketone and an amine.

The ketimine compound has a ketimine (C = N) bond derived from a ketone and an amine, and has a structure in which a branched carbon or a ring carbon is bonded to at least one α-position of the ketimine carbon or nitrogen. It is preferably a ketimine compound. Here, the ring member carbon refers to a carbon atom constituting a cycloalkyl ring or an aromatic ring.

In the ketimine compound, it is preferable that the branched carbon or the ring member carbon is bonded to the ketimine carbon.

The ketimine compound is preferably obtained by using a ketone represented by the above formula (2).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The curable resin composition of the present invention includes the following two embodiments. First Embodiment: A curable resin composition containing a compound having at least one dithiocarbonate group in a molecule, an oxazolidine compound, and / or a ketimine compound having a large steric hindrance. Second embodiment: a polymer having an isocyanate group in the molecule and / or a polymer having a reactive alkoxysilyl group in the molecule; a compound having at least one dithiocarbonate group in the molecule; A curable resin composition containing a curing agent.

First, the curable resin composition of the present invention (hereinafter referred to as “the curable resin composition”)
The components contained in the composition of the present invention) will be described.

<Compound having at least one dithiocarbonate group in the molecule> A compound having at least one dithiocarbonate group in the molecule used in the present invention (hereinafter referred to as "the compound having at least one dithiocarbonate group")
A dithiocarbonate compound) is a compound having at least one dithiocarbonate group represented by the following formula (1) in the molecule.

[0017]

Embedded image

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R ¹ , R ² and R ³ may be the same or different. The hydrocarbon group having 1 to 10 carbon atoms includes 1 to 10 carbon atoms.
And 10 hydrocarbon groups such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group and an arylalkyl group. Specifically, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl,
An alkyl group such as a decyl group; an alkenyl group, an alkadienyl group, and an alkynyl group corresponding to each of these alkyl groups;

A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group,
A cycloalkyl group such as a cyclooctyl group, a cyclononyl group, or a cyclodecyl group; a group in which at least one hydrogen atom of these cycloalkyl groups has been substituted with an alkyl group, an alkenyl group, or the like; and an unsaturated bond corresponding to each of these groups. A cycloalkyl group such as a group having;

Phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, o-cumenyl, m-cumenyl, p-cumenyl, Aryl groups such as mesityl group, 1-naphthyl group and 2-naphthyl group; arylalkyl groups such as benzyl group and phenethyl group; and aromatic hydrocarbon groups such as styryl group and cinnamyl group.

Dithiocarbonate compounds can be prepared by known methods, for example, as described in JP-A-5-247027, N. Kihar
According to the method described in a., J. Org. Chem., 60, 473 (1995), an epoxy compound having at least one oxirane group (epoxy group) in the molecule and carbon disulfide are combined with lithium bromide or the like. It can be obtained by reacting in the presence of an alkali halide.

The epoxy compound used to obtain the dithiocarbonate compound is, for example, bisphenol A
Glycidyl ether type epoxy resin and derivatives thereof, bisphenol F type glycidyl ether type epoxy resin, bisphenol S type glycidyl ether type epoxy resin, bisphenol AF type glycidyl ether type epoxy resin, etc .;
Novolak epoxy resins such as phenol novolak glycidyl ether epoxy resin and orthocresol novolak glycidyl ether epoxy resin; glycidyl ether epoxy resin of glycerin, glycidyl ether epoxy resin of polyalkylene oxide, and glycidyl ester epoxy resin of phthalic acid Resins and derivatives thereof, glycidyl ester type epoxy resins of dimer acid, those having an oxirane ring of polybutadiene, and those having an oxirane ring of liquid acrylonitrile-butadiene rubber are exemplified. Among these, bisphenol A type glycidyl ether type epoxy resin has high cured product strength of the composition of the present invention using the obtained dithiocarbonate compound.

The molecular weight of the dithiocarbonate compound is not particularly limited, but is preferably from 200 to 300,000, more preferably from 300 to 2 from the viewpoint of operability.
00,000 is more preferred.

<Oxazolidine compound> General-purpose oxazolidine compound The oxazolidine compound used in the present invention is not particularly limited as long as it is a compound having an oxazolidine ring which produces a secondary amine by hydrolysis, but is preferably represented by the following formula (3) or The compound represented by (4) is used.

[0025]

Embedded image

In the formula (3), R ⁸ represents a group obtained by removing an isocyanate group from a polyisocyanate having q isocyanate groups, and is preferably a compound serving as a skeleton of an isocyanate compound. Further, when the formula (3) represents a monooxazolidine compound, R ⁸ may be a hydrogen atom. R ⁹ is a divalent organic group, for example, a saturated or unsaturated C 1
10 to 10 divalent hydrocarbon groups. The hydrocarbon group may be any of aliphatic, alicyclic and aromatic. Also,
It may contain atoms such as N, S, O, and P. R ¹⁰ is a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹¹ and R ¹²
Are each independently a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, or
To 10 aryl groups. q is an integer of 1 to 4.
In the formula (4), R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² represent R in the formula (3)
^9, the same meaning as ^{R 10, R 11, R 12} . As the oxazolidine compound used in the present invention, the compound represented by the formula (3) or the compound represented by the formula (4) may be used alone, or both may be used in combination.

Oxazolidine compound having steric hindrance In the formula (4), the oxazolidine compound in which R ¹¹ is a hydrocarbon group having 3 to 10 carbon atoms, which is a branched carbon or a ring member carbon, has a nitrogen atom and an oxygen atom of a heterocyclic ring. The bulky group (R ¹¹ ) is bonded to the carbon atom between the two, and the nitrogen atom of the heterocyclic ring is sterically hindered by this group. Due to this steric hindrance, the nitrogen atom of the heterocyclic ring has a greatly reduced basicity of the nitrogen atom, and has a low reactivity, and thus has high storage stability.

As a method for producing the oxazolidine compound, for example, the oxazolidine compound represented by the formula (4) can be produced by a usual method such as a method by a dehydration condensation reaction of an alkanolamine with a ketone or an aldehyde. The oxazolidine compound represented by the formula (3) can be produced, for example, by an addition reaction of the oxazolidine compound represented by the formula (4) with a polyisocyanate compound. Oxazolidine compounds are hydrolyzed with water to form secondary amines, and act as latent curing agents such as dithiocarbonate compounds, epoxy compounds, and isocyanate compounds.

Specific examples include N-methyl-2-isopropyl-2,5-dimethyl-1,3-oxazolidine,
N-ethyl-2-isopropyl-2,5-dimethyl-
1,3-oxazolidine, N-methyl-2-isobutyl-2-methyl-1,3-oxazolidine, N-ethyl-
2-methyl-2- (3-methylbutyl) -1,3-oxazolidine and the like.

<Ketimine compound> General-purpose ketimine compound The ketimine compound used in the present invention is a compound having a ketimine (C = N) bond derived from a ketone and an amine. For example, ketones such as methyl ethyl ketone (MEK) and isobutyl methyl ketone (MIBK), diethylene triamine (DETA), triethylene triamine (T
Ketimines obtained from aliphatic polyamines such as ETA), propylene diamine (PDA) and meta-xylylenediamine (MXDA) are used as general-purpose latent curing agents.

Sterically hindered ketimine compound Structure having a ketimine (C = N) bond derived from a ketone and an amine, wherein a branched carbon or a ring member carbon is bonded to at least one α-position of the ketimine carbon or nitrogen. Is a ketimine compound having a bulky group at the α-position of the ketimine C ＝ N bond and having steric hindrance. Here, the ring member carbon may be a carbon constituting an aromatic ring or a carbon constituting an alicyclic ring.

The method for producing such ketimine compounds is as follows:
Although not particularly limited, for example, it can be obtained by reacting a ketone having a branched hydrocarbon group represented by the following formula (2) with a polyamine.

Embedded image In the formula, R ⁴ is a hydrogen atom, a methyl group or an ethyl group, R ⁵
Is a methyl group or an ethyl group, R ⁶ is an alkyl group having 1 to 6 carbon atoms, R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ are combined to form a ring R ⁴ , R ⁵ and R ⁶ may form an aromatic ring.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the ring formed by combining R ⁵ and R ⁶ include a cycloalkyl group having 4 to 6 carbon atoms such as a cyclobutyl group, a cycloheptyl group, and a cyclohexyl group. As the aromatic ring formed by combining R ⁴ , R ⁵ and R ⁶ , a phenyl group, a tolyl group,
Xylyl groups and the like.

As the ketone represented by the above formula (2),
Specific examples include methyl t-butyl ketone (MTBK), methyl isopropyl ketone (MIPK), methyl cyclohexyl ketone, methyl cyclohexanone, and the like.

The polyamine is not particularly limited.
However, because the curing speed is fast, aliphatic polyamines
preferable. For example, 2,5-dimethyl-2,5-hexa
Methylenediamine, mensendiamine, 1,4-bis
(2-amino-2-methylpropyl) piperazine, molecule
Polypropylene with amino groups bonded to propylene branched carbon at both ends
Propylene glycol (PPG) (eg, San Techno
Chemical Jeffamine D230, Jeffamine
D400, etc.), ethylenediamine, propylene diamine
, Butylene diamine, diethylene triamine, trie
Tylenetetramine, tetraethylenepentamine, penta
Ethylenehexamine, hexamethylenediamine, trime
Tylhexamethylenediamine, N-aminoethyl pipera
Gin, 1,2-diaminopropane, iminobispropyl
Amine, methyliminobispropylamine, H_TwoN (C
H_TwoCH _TwoO)_Two(CH_Two)_TwoNH_Two(For example, San Techno
Amy such as Jeffamine EDR148) manufactured by Chemical Co., Ltd.
Of a polyether skeleton in which a methylene group is bonded to the nitrogen
Min, 1,5-diamino-2-methylpentane (e.g.
For example, MPMD manufactured by DuPont Japan), Metaxile
Diamine (MXDA), polyamidoamine (for example,
X2000 manufactured by Sanwa Chemical Co., Ltd.), isophoronediamine,
1,3-bisaminomethylcyclohexane (for example,
1,3 BAC manufactured by Ryo Gas Chemical Co., Ltd., 1-cyclohexyl
Amino-3-aminopropane, 3-aminomethyl-3,
3,5-trimethyl-cyclohexylamine, norvol
A diamine having a skeleton of nan (for example, NBD manufactured by Mitsui Chemicals, Inc.)
A) and the like.

Among them, 1,3-bisaminomethylcyclohexane (1,3BAC), norbornanediamine (NBDA), metaxylylenediamine (MXD)
A), Jeffamine EDR148 (trade name) and polyamidoamine are preferred.

A preferred specific example of a ketimine compound having steric hindrance is obtained from methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK) and dimethyleneamine having a polyether skeleton (eg, Jeffamine EDR148). One obtained from methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK) and 1,3-bisaminomethylcyclohexane (1,3 BAC), methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK) ) And dimethyleneamine having a norbornane skeleton (for example, NBDA), methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK), and metaxylylenediamine (M
XDA), methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTB).
K) and polyamidoamine (for example, X2000). Among them, especially those obtained from MIPK and NBDA, MIPK
And 1,3BAC exhibit excellent curability. MIPK or MTBK and X2000
And so forth exhibit excellent adhesion to a wet surface.

The ketimine compound can be obtained by reacting a ketone with a polyamine by heating and refluxing in the absence of a solvent or in the presence of a solvent such as benzene, toluene, or xylene, and removing elimination water by azeotropic distillation. Can be.

<First Embodiment of the Present Invention> The first embodiment of the present invention will be described below. A first aspect of the present invention is a curable resin composition containing a compound having at least one dithiocarbonate group in a molecule, an oxazolidine compound, and / or a ketimine compound having a large steric hindrance. The composition according to the first aspect of the present invention can be prepared as a one-pack type composition, or a main component comprising an oxazolidine compound or a ketimine compound as a curing agent, a dithiocarbonate compound or further an epoxy compound. Store separately and mix when used 2
It may be adjusted as a liquid type. In addition, the composition is a one-part composition,
Further, a two-component type may be used by using another curing agent.

As the compound having at least one dithiocarbonate group in the molecule used in the first embodiment of the present invention, the above-mentioned dithiocarbonate compounds can be used. By containing the dithiocarbonate compound, the composition according to the first aspect of the present invention is excellent in quick-curing properties. Among them, the dithiocarbonate compounds that can be preferably used in the first aspect of the present invention include those in which R ¹ , R ² , and R ^{3 in} the formula (1) are each independently a hydrogen atom or a methyl group, and Or may be different. Specifically, a dithiocarbonate compound represented by the following formula (5) is exemplified. The dithiocarbonate compound represented by the following formula has a low viscosity at room temperature, so that it can be easily handled and the composition of the present invention can be easily adjusted. Since the composition of the present invention using such a dithiocarbonate compound has a low viscosity,
Good workability.

[0040]

Embedded image

As the oxazolidine compound used in the first embodiment of the present invention, the above-mentioned <oxazolidine compound> (including general-purpose compounds and those having steric hindrance) can be used. By containing the oxazolidine compound as a curing agent, the composition according to the first aspect of the present invention is excellent not only in storage stability as a two-part resin composition but also as a one-part resin composition. The one-pack type resin composition is excellent in storage stability. Among them, the oxazolidine compound described as “Oxazolidine compound having steric hindrance” can be preferably used. As the oxazolidine compound having such steric hindrance, in the above formula (3), in particular,
Compounds in which R ¹¹ is a hydrocarbon group having 3 to 10 carbon atoms in which a branched carbon or a ring member carbon is present, for example, an isopropyl group, a t-butyl group, or a cyclohexyl group are exemplified. Such an oxazolidine compound has a significantly reduced basicity of a nitrogen atom due to steric hindrance caused by a bulky group (R ¹¹ ) bonded between a nitrogen atom and an oxygen atom of a heterocyclic ring, and has low reactivity and low storage. High stability. As a result, the composition of the first aspect of the present invention containing such an oxazolidine compound having a large steric hindrance as a curing agent has particularly excellent storage stability. Is hydrolyzed to an active amine, and exhibits rapid curing properties when combined with a highly reactive dithiocarbonate compound. Preferred examples of the oxazolidine compound include a compound represented by the following formula (6).

[0042]

Embedded image

The ketimine compound used in the first embodiment of the present invention includes the following <ketimine compound>
The ketimine compound shown as "a ketimine compound having a large steric hindrance" is used. As such ketimine compounds, in particular, methyl isopropyl ketone (MIPK)
Or those obtained from methyl t-butyl ketone (MTBK) and dimethyleneamine having a polyether skeleton (eg, Jeffamine EDR148), methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK), and 1,3- Bisaminomethylcyclohexane (1,3BAC), methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK), and dimethyleneamine having a norbornane skeleton (for example, NBDA), methyl isopropyl Ketone (MIPK) or methyl t-butyl ketone (MTBK) and meta-xylylenediamine (M
XDA), methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTB).
Those obtained from K) and a polyamidoamine (for example, X2000) are preferable. Among them, especially MI
What is obtained from PK and NBDA, MIPK and 1,
Those obtained from 3BAC are preferred because they exhibit excellent curability.

The ketimine compound having a large steric hindrance has a bulky group at the α-position of a carbon atom or a nitrogen atom forming a ketimine bond, and has a structure in which a nitrogen atom is sterically hindered. The hindrance has greatly reduced the basicity of the nitrogen atom. Therefore, the first invention of the present invention containing such a ketimine compound as a latent curing agent.
The composition according to the embodiment exhibits excellent storage stability. Moreover, such a ketimine compound, when in use, comes into contact with moisture in the air, so that the ketimine nitrogen easily becomes an active amine, and exhibits excellent curability when combined with a highly reactive dithiocarbonate compound. .

In the composition according to the first aspect of the present invention,
As a latent curing agent, an oxazolidine compound and a ketimine compound may be contained. Such a composition exhibits properties such as excellent storage stability and excellent deep-section curability while maintaining fast curability.

The composition according to the first aspect of the present invention can further contain a compound having at least one epoxy group in the molecule. As such an epoxy compound, any of the compounds exemplified as the epoxy compounds that can be used in the synthesis of the above-described dithiocarbonate compound can be used. By containing the epoxy compound, the adhesive strength of the obtained composition can be increased. Among such epoxy compounds, the first of the present invention containing a bisphenol A type epoxy resin.
The composition according to the aspect of the present invention is excellent in cured product strength and has high adhesive strength of the cured product. In this case, as the dithiocarbonate compound, when a dithiocarbonate compound synthesized using a glycidyl ether type epoxy resin of a polyalkylene oxide as a raw material is used, such a dithiocarbonate compound is in a liquid state, and thus has a low temperature of about 5 ° C. By adjusting the composition together with the solid bisphenol A type epoxy resin, a liquid composition can be adjusted, and a composition having good workability can be obtained, which is preferable.

The content of the epoxy compound is preferably from 1 to 2,000 parts by weight, and more preferably from 5 to 10 parts by weight, based on 100 parts by weight of the dithiocarbonate compound, for the purpose of maintaining rapid curing.
00 parts by weight is more preferred.

In the composition according to the first aspect of the present invention, the compounding amount of the oxazolidine compound is determined based on the dithiocarbonate group of the dithiocarbonate compound, the epoxy group in the compound, or the first compound of the present invention. When the composition according to the embodiment contains an epoxy compound, the equivalent ratio of active hydrogen after hydrolysis of the oxazolidine compound (dithiocarbonate group and epoxy group / active hydrogen) to the total of epoxy groups of the epoxy compound is 0. The ratio is preferably 0.1 to 1.2, more preferably 0.2 to 0.8.
Within this range, excellent fast curability and adhesiveness can be obtained.

In the composition according to the first aspect of the present invention, the compounding amount of the ketimine compound is determined based on the dithiocarbonate group of the dithiocarbonate compound, the epoxy group in the compound, or the first compound of the present invention. When the composition according to the embodiment contains an epoxy compound, the equivalent ratio of the imino group of the ketimine compound (dithiocarbonate group to epoxy group / imino group) is 0.1 to 1 with respect to the total number of epoxy groups of the epoxy compound. .2, preferably 0.2.
2-0.8 is more preferred. Within this range, both fast-curing properties and storage stability are good.

When the composition according to the first aspect of the present invention contains both an oxazolidine compound and a ketimine compound as a curing agent, the mixing ratio thereof is not particularly limited, but active hydrogen derived from the oxazolidine compound and ketimine compound Of the active hydrogen: imino group =
The ratio is preferably 99.9: 0.1 to 0.1: 99.9. The compounding amount of the oxazolidine compound and the ketimine compound is preferably such that the ratio of (dithiocarbonate group and epoxy group / active hydrogen of the oxazolidine compound and imino group of the ketimine compound) is 0.1 to 1.2. , 0.2 to 0.8 are more preferred.

The composition according to the first aspect of the present invention comprises, in addition to the above components, other additives such as a filler, a plasticizer, a thixotropic agent, and a pigment within a range not to impair the object of the present invention. , A dye, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, an adhesion promoter, a dispersant, a solvent, and the like.

Fillers include organic and inorganic fillers of various shapes, such as fumed silica, calcined silica, precipitated silica, crushed silica, and fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, and barium oxide. Magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; limestone clay, kaolin clay, calcined clay; or carbon black, or their fatty acids, resin acids, fatty acid esters, urethane compounds, processed products, and the like.

As the plasticizer, dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester;
Butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester, and the like can be used.

Aerosil (manufactured by Nippon Aerosil Co., Ltd.) and Dispalon (manufactured by Kusumoto Kasei Co., Ltd.) are used as thixotropy-imparting agents, and quaternary ammonium salts, polyglycols, and ethylene oxide derivatives are used as antistatic agents. Can be used.

The pigment may be either an inorganic pigment or an organic pigment. For example, organic pigments such as titanium oxide, zinc oxide, ultramarine, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate inorganic pigments, azo pigments, and copper phthalocyanine pigments can be used. Examples of the anti-aging agent include hindered phenol compounds. As antioxidants,
Butylhydroxytoluene (BHT), butylhydroxyanisole (BHA) and the like. Flame retardants include chloroalkyl phosphate, dimethyl methylphosphonate, bromine / phosphorus compounds, ammonium polyphosphate, neopentyl bromide polyether,
Brominated polyethers and the like. Examples of the adhesion-imparting agent include a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, and a xylene resin. The above components may be used in combination as appropriate.

The method for preparing the composition according to the first aspect of the present invention as a one-pack type curable resin composition is not particularly limited, but preferably, the above components are prepared under reduced pressure or inert gas such as nitrogen. It is preferable to sufficiently knead the mixture in a gas atmosphere using a stirring device such as a mixing mixer and to uniformly disperse the mixture. The method for preparing the composition according to the first aspect of the present invention as a two-part curable resin composition is not particularly limited, but preferably comprises a dithiocarbonate compound, or further comprises an epoxy compound and other additives. The main ingredient,
An oxazolidine compound and / or a ketimine compound and, if necessary, a curing agent comprising other additives,
Each is sufficiently kneaded using a stirrer such as a mixing mixer, and a method of uniformly dispersing is exemplified.Each is separately stored in an airtight container and mixed at the above-mentioned predetermined ratio at the time of use according to the present invention. A composition according to the first aspect is obtained.

Since the curable resin composition according to the first aspect of the present invention having such a constitution is fast-curing and contains an oxazolidine compound or a ketimine compound having a large steric hindrance as a curing agent, Good storage stability. Further, the adhesiveness is good. The curable resin composition according to the first aspect of the present invention containing an epoxy compound is particularly excellent in adhesion without impairing storage stability. Therefore, the curable resin composition according to the present invention is useful as an adhesive for concrete, wood, metal, and the like.

<Second Embodiment of the Present Invention> The curable resin composition according to the second embodiment of the present invention will be described below. The curable resin composition according to the second aspect of the present invention,
Contains a polymer having an isocyanate group in the molecule and / or a polymer having a reactive alkoxysilyl group in the molecule, a compound having at least one dithiocarbonate group in the molecule, and a latent curing agent Is a curable resin composition.

<Polymer Having Isocyanate Group in Molecule> As the polymer having an isocyanate group in the molecule used in the second embodiment of the present invention, a polymer having at least one isocyanate group in the molecule is widely used. Can be used. Preferred examples of the main chain skeleton of such a polymer include polyether, polyester, and ether-ester block copolymer. The molecular weight of such polymers is between 500 and 100,
000 is preferred. As such a polymer, a urethane prepolymer derived from a polyisocyanate and a polyol can be used. Such a urethane prepolymer is a reaction product of a polyol and an excess of polyisocyanate, and is generally 0.5 to 10% by weight of an isocyanate, like the urethane prepolymer used in a general polyurethane resin composition. Those having a group at the molecular terminal can be used.

As the polyisocyanate, for example,
Aromas such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4-diisocyanate and modified products thereof, 2,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate and polymethylene polyphenylene polyisocyanate Aliphatic diisocyanates, such as hexamethylene diisocyanate; alicyclic diisocyanates, such as isophorone diisocyanate and norbornane diisocyanate; aryl aliphatic diisocyanates, such as xylylene diisocyanate; It is preferably exemplified, and one or more of these can be used in combination.

On the other hand, as the polyol, polyether polyol, polyester polyol, other polyols, and a mixed polyol thereof can be used. As the polyether polyol, ethylene oxide, propylene oxide, butylene oxide,
Alkylene oxides such as styrene oxide, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 4,4'-dihydroxyphenylmethane, 4,4'-dihydroxyphenyl Various products produced by addition polymerization with an active hydrogen compound such as propane, specifically, polyether diols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol;

Various compounds produced by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide with an active hydrogen compound such as glycerin, trimethylolpropane and hexanetriol, specifically, Polytetramethylene triol, polyethylene triol,
Polyether triols such as polypropylene triol, polyoxypropylene triol, and polyoxybutylene triol, and the like are included.

Examples of the polyester polyol include one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, and other low molecular weight diols, and glutaric acid, adipic acid, pimelic acid,
Condensation polymers with one or more of suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, and other low-molecular carboxylic acids or oligomeric acids; ring-opening polymers such as propionlactone, valerolactone, and caprolactone And the like.

Other polyols include (hydrogenated)
Examples thereof include polyolefin-based polyols such as polybutadiene polyol and polyisoprene polyol, polycarbonate polyols, and acrylic polyols.

In obtaining a urethane prepolymer comprising such a polyol and an excess of polyisocyanate,
The mixing ratio between the polyol and the polyisocyanate is usually 1.2 to 5 equivalents (NCO equivalent), preferably 1.5 to 3 equivalents, per equivalent (OH equivalent) of the polyol. In addition, urethane prepolymer is produced by mixing both compounds at a predetermined quantitative ratio, and usually mixing 30 to 12 times.
It can be carried out by heating and stirring at 0 ° C, preferably 50 to 100 ° C.

<Polymer in which isocyanate group in the molecule is bonded to secondary or tertiary carbon> The isocyanate group in the polymer having an isocyanate group in the molecule used in the present invention is The polymer bonded to the secondary or tertiary carbon is a polymer having an isocyanate group in the molecule represented by the following formula.

Embedded image In the formula, ^Ra is an organic group that may contain O, S, and N, and ^Rb is a hydrogen atom or the above organic group. Specific examples of the organic group include an alkyl group, an alicyclic group, an aromatic ring group,
Aralkyl groups, hydrocarbon groups such as alkylaryl groups,
A group having a hetero atom selected from O, S, and N, such as an ether, carbonyl, amide, urea group (carbamide group), and an organic group containing a urethane bond and the like can be given. Among them, a methyl group is preferred.

The polymer may have any structure in which the isocyanate group has the structure specified by the above formula. Examples of such a polymer include a urethane prepolymer in which the isocyanate group is derived from a polyisocyanate having the above structure and a polyol. Can be used. Specific examples of the polyisocyanate include m- or p-isopropenyl-
mono-isocyanate compounds such as α, α-dimethylbenzoyl isocyanate (TMI manufactured by Mitsui Cytec), m-
Or p-tetramethylxylylene diisocyanate (TMXDI), isophorone diisocyanate (IPD
And diisocyanate compounds such as I).

In the synthesis of the above polymer, it is preferable to use diisocyanate among polyisocyanates.
Examples of the polyol include the same polyols as those exemplified in the synthesis of the above-mentioned general urethane prepolymer. Specific examples of such urethane prepolymers include urethane prepolymers derived from diisocyanate, polyether polyol, polyester polyol, and the like.

Among urethane prepolymers obtained from such polyols and diisocyanates, polyols having a molecular weight of 500 to 100,000 such as polypropylene polyols, polyether polyols and polyester polyols, and tetramethylxylylene diisocyanate (TMXDI) Or from 1,
A TMXDI-TMP adduct derived from 1,1-trimethylolpropane (TMP) and tetramethylxylene diisocyanate (TMXDI) is preferably exemplified.

As the above-mentioned adduct, those commercially available under the trade name of, for example, SEISEN 3160 (Mitsui Cytec) can also be used. Such an adduct is not necessarily a complete OH: NCO adduct and may contain unreacted raw materials.

As the polyether polyol and the polyester polyol used as the polyol during the synthesis of the urethane prepolymer, those derived from aromatic diols are preferably used. Examples of the aromatic diols include dihydroxystyrene, bisphenol A structure (4,4′-dihydroxyphenylpropane),
Bisphenol F structures (4,4'-dihydroxyphenylmethane), brominated bisphenol A structures, hydrogenated bisphenol A structures, bisphenol S structures, and bisphenol AF structures having a bisphenol skeleton are exemplified.

[0072]

Embedded image

The polyether polyol specifically has one or more units selected from units derived from an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and styrene oxide, and a bisphenol skeleton. Things. Such a polyether polyol can be produced by ring-opening polymerization of a general alkylene oxide. For example, one or two or more of the above-mentioned polyhydric alcohols and / or aromatic diols may be prepared by adding one or more alkylene oxides. Seed or 2
It can be obtained by adding more than one kind.

More specific examples of the polyether polyol include polyethylene glycol, polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and sorbitol-based polyol. Examples of the polyether polyol having a bisphenol skeleton include a polyether polyol obtained from a diol having a bisphenol skeleton and an alkylene oxide, for example, a polyether polyol containing the bisphenol A structure and ethylene oxide and propylene oxide units.

The polyester polyol may be a condensate (condensed polyester) of one or more polyhydric alcohols and / or aromatic diols and one or more polybasic carboxylic acids. Polyol), lactone-based polyols, polycarbonate diols and the like. Examples of the polybasic carboxylic acid forming the condensation polyester polyol include glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, and other low molecular carboxylic acids. Examples include oligomeric acids, castor oil, and hydroxycarboxylic acids such as a reaction product of castor oil and ethylene glycol. Examples of the lactone-based polyol include ring-opened polymers such as propion lactone and valerolactone.

As the polyester polyol having a bisphenol skeleton, instead of the above-mentioned polyhydric alcohols,
Or a condensation-based polyester polyol obtained using a diol having a bisphenol skeleton together with a polyhydric alcohol, for example, a polyester polyol obtained from bisphenol A and castor oil, a polyester obtained from bisphenol A and castor oil, ethylene glycol and propylene glycol Polyols and the like.

In synthesizing the urethane prepolymer,
Further, polymer polyols having a carbon-carbon bond in the main chain skeleton, such as acrylic polyol, polybutadiene polyol, and hydrogenated polybutadiene polyol, can also be used. When synthesizing the urethane prepolymer, two or more of the above polyols can be used in combination.

Preferable examples of the urethane prepolymer as described above include, for example, as a polyol, difunctional or trifunctional, or a polyfunctional (OH) mixture of these.
And polyfunctional urethane prepolymers obtained using the above polypropylene glycol. This urethane prepolymer is more preferably obtained using a polyol having a molecular weight of about 500 to 100,000.

A urethane prepolymer having a bisphenol skeleton is also preferable, and a urethane prepolymer having a bisphenol A skeleton is particularly preferable. Specifically, as the polyol, a urethane prepolymer obtained by using a polyester polyol synthesized from bisphenol A and castor oil, a polyether polyol synthesized from bisphenol A and ethylene oxide, propylene oxide, or the like is preferably used. .

The urethane prepolymer may contain two or more kinds of polyol components, and may contain not only two or more kinds of bisphenol skeletons but also a polyol component having another structure together with the bisphenol skeleton. The content of the bisphenol structural portion in the urethane prepolymer is not particularly limited. However, if the bisphenol skeleton component is contained in the polyol in an amount of 1 to 50 mol%, the above-described properties can be sufficiently exhibited. Is preferred.

The composition according to the second aspect of the present invention obtained by containing the above-mentioned polymer in the curable resin composition according to the second aspect of the present invention exhibits rubber elasticity, Can show elongation and high strength. Further, by using a polymer having a bisphenol skeleton and having an isocyanate group in the molecule, the strength of the cured product and the adhesive strength of the obtained composition can be increased, which is preferable. In particular, in the curable resin composition according to the second aspect of the present invention using the above polymer in which an isocyanate group is bonded to a secondary carbon or a tertiary carbon in the molecule, Since the intermolecular hydrogen bond is weak due to the steric hindrance effect of the secondary or tertiary carbon, appropriate viscosity and modulus can be obtained without using a plasticizer, and further excellent storage stability can be obtained.

<Polymer Having Reactive Alkoxysilyl Group in Molecule> The polymer used in the curable resin composition according to the second embodiment of the present invention and having a reactive alkoxysilyl group in the molecule is a molecule. A polymer having at least one reactive alkoxysilyl group therein can be widely used, but the main chain skeleton of such a polymer is desirably composed of a rubber-based organic polymer, such as polyether or polyester. And ether-ester block copolymers. Further, vinyl or diene compounds, acrylates, and methacrylates may be mentioned.

In the above polyether, the divalent organic group R in the formula —RO— has substantially 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
It is preferably an alkylene oxide polymer which is a hydrocarbon group of No. 8. Specifically, R is methylene, ethylene,
Propylene, butylene, tetramethylene and the like are preferable, and propylene is particularly preferable. R may be one or a combination of two or more of these. Examples of the polyester include a polyester polymer obtained by condensation of a dibasic acid such as adipic acid or maleic anhydride with glycol, or ring-opening polymerization of a cyclic ester such as lactone.

Examples of the vinyl compound include polybutadiene, styrene-butadiene copolymer,
Acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, polyisoprene, styrene-isoprene copolymer, isobutylene- Examples include isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylate, and polymethacrylate.

The polymer having a reactive alkoxysilyl group in the molecule preferably has a polyether, polyester, ether-ester block copolymer or the like as the main chain skeleton among the above. It preferably contains an ether skeleton. Although the molecular weight of the main chain skeleton is not particularly limited, the molecular weight of polyether, polyester, ether-ester block copolymer, etc. is about 300 to 30,000, and more preferably 500 to 150.
It is preferably about 00.

The reactive alkoxysilyl group contained in the molecule causes a condensation reaction in the presence of moisture, a crosslinking agent, and if necessary, a catalyst. Examples of such an alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, and a propoxysilyl group. At least one alkoxy group may be bonded to the silicon atom to which the alkoxy group in the alkoxysilyl group is bonded, and a dialkoxysilyl or trialkoxysilyl group is more preferable. In addition to the alkoxy group, as a group that may be bonded to a silicon atom, a compound that imparts hydrolyzability, for example, a halogen atom, an alkoxy group, an acyloxy group, a ketoxime group,
An alkenyloxy group and the like can be mentioned.

The polymer having a reactive alkoxysilyl group in the molecule preferably used in the present invention will be described more specifically. Organic polymers having a polyether main chain skeleton and having at least one reactive alkoxysilyl group include, for example, trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1,3,3,5,5 , 7,7-heptamethyl-1,1-dimethoxytetrasiloxane and other alkoxysilanes, and a polyether containing a group having an ethylenic double bond represented by the following general formula, by producing an addition reaction Can be.

[0088]

Embedded image

In the above formula, R ¹³ is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom. Z is 2
It is a divalent group containing a divalent hydrocarbon group, an ether bond, an ester bond, a urethane bond, a carbonate bond, and a carbonyl group, and is specifically shown below.

[0090]

Embedded image

R ¹⁴ is selected from divalent hydrocarbon groups having 1 to 20 carbon atoms, and two or more R ¹⁴ may be the same or different. Z is preferably a methylene group among these. The polyether containing a group having an ethylenic double bond represented by the above general formula may be prepared by introducing an ethylenic double bond into a polyether side chain by a known method. Or a method of copolymerizing an epoxy compound such as ethylene oxide or propylene oxide with an olefin group-containing epoxy compound such as allyl glycidyl ether.

Examples of the addition reaction catalyst between the alkoxysilines and the polyether containing a group represented by the above general formula include platinum black, chloroplatinic acid, a platinum alcohol compound, a platinum olefin complex, a platinum aldehyde complex, and a platinum aldehyde complex. Platinum compounds such as ketone complexes can be used.

The polymer having a reactive alkoxysilyl group in the molecule may further contain a unit derived from a polymerizable compound other than the above having an ethylenic double bond in addition to the above. Specific examples of such other polymerizable compounds include ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, pyridine, styrene, chlorostyrene, -Methylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, isobutyl acrylate,
2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, glycidyl Examples thereof include methacrylate, acrylamide, methacrylamide, n-methylolacrylamide, and silicon-containing compounds described below.

[0094]

Embedded image

When producing a polymer having a reactive alkoxysilyl group in the molecule, one or two of the above alkoxysilanes, polyethers containing the group represented by the above general formula, and other polymerizable compounds are each independently used. The above may be used. Polymers using other polymerizable compounds are disclosed in
No. 78223, and the like. For example, in the presence of an addition reaction product of an alkoxysilane and a polyether containing a group represented by the above general formula, the other polymerizable compound described above can be used. It can be obtained by polymerizing a compound.

The molecular weight of such a polymer is 10
It is preferably about 100 to 100,000, and more preferably 200
More preferably, it is 0 to 50,000.

The composition according to the second aspect of the present invention may contain both the above-mentioned polymer having an isocyanate group in the molecule and the polymer having a reactive alkoxysilyl group in the molecule. The composition obtained together can impart rubber elasticity, and the obtained composition according to the second aspect of the present invention can exhibit high elongation and high strength. Furthermore, by using these polymers in combination, it is considered that they have an IPN structure in which the cured networks are different from each other while being compatible with each other, and there is an advantage that each polymer exhibits a performance that surpasses the physical properties of itself. In particular, when a polymer having an isocyanate group bonded to a secondary or tertiary carbon is used, the intermolecular hydrogen bond is weak due to the steric hindrance effect of the secondary or tertiary carbon bonded to the isocyanate group. An appropriate viscosity and modulus can be obtained without using an agent. The resulting curable resin composition shows excellent storage stability.

When these polymers are used in combination, the weight ratio of both polymers is not particularly limited, but the weight of the polymer having an isocyanate group in the molecule and the polymer having a reactive alkoxysilyl group in the molecule is not limited. The ratio (polymer having an isocyanate group in the molecule / polymer having a reactive alkoxysilyl group in the molecule) is preferably from 99/1 to 1/99, more preferably from 90/10 to 10/90. Is more preferred. If either one is too small, the physical properties will not be improved by the IPN structure, so this range is preferable.

As the dithiocarbonate compound used in the composition according to the second aspect of the present invention, those similar to the aforementioned dithiocarbonate compounds can be used. Particularly preferred dithiocarbonate compounds include
R ¹ , R ² , and R ^{3 in the} formula (1) each independently represent a hydrogen atom or a methyl group, and may be the same or different. Specifically, a dithiocarbonate compound represented by the above formula (5) is exemplified. Since the dithiocarbonate compound has a low viscosity at room temperature, it is easy to handle and the composition of the present invention is easily adjusted. Since the composition of the present invention using such a dithiocarbonate compound has a low viscosity, it has good workability.

The latent curing agents used in the curable resin composition according to the second aspect of the present invention include the above-mentioned <oxazolidine compounds> (including those of general use and those having steric hindrance), <ketimine compounds > (Including general-purpose ones and those with steric hindrance) can be used.

Among these latent curing agents, oxazolidine compounds and ketimine compounds having large steric hindrance are preferred. The curable resin composition according to the second aspect of the present invention may contain, as a latent curing agent, either an oxazolidine compound or a ketimine compound having a large steric hindrance, or may contain both. By including a latent curing agent, the obtained composition of the present invention has excellent storage stability.However, by including the oxazolidine compound and the ketimine compound as the latent curing agent, the composition can be further improved in storage stability. It is excellent and hardens at room temperature during use to show excellent adhesiveness. In particular, in the composition of the present invention containing a ketimine compound having a large steric hindrance, storage stability is particularly improved. The combined use of the oxazolidine compound and the ketimine compound has an advantage that the deep curing property of the epoxy resin is improved.

In the second embodiment of the present invention, the compounding amount of the latent curing agent depends on the functional group that contributes to the curing reaction of the latent curing agent. If active hydrogen, ketimine compound, imino group, or the total of these functional groups when using a plurality of curing agents, the equivalent ratio of the isocyanate group of the polymer having an isocyanate group in the molecule,
(Isocyanate group / functional group of latent curing agent) is 0.1
-2.0 is preferable, and 0.5-1.5 is more preferable.
Within this range, good storage stability can be obtained while being fast-curing.

When the composition according to the second aspect of the present invention contains a polymer having a reactive alkoxysilyl group in the molecule, a silanol condensation catalyst (curing catalyst) may be used within a range not to impair the object of the present invention. You may mix. Examples of the curing catalyst include metal carboxylate salts such as dibutyltin dilaurate, dibutyltin phthalate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin laurate, tin naphthenate, tin ferzaticate, and titanium naphthenate; Titanate,
Titanate such as tetraisopropyl titanate and triethanolamine titanate; reaction product of dibutyltin oxide and phthalate; dibutyltin diacetylacetonate; aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethyl acetoacetate Organoaluminum compounds; chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; iron naphthenate; bismuth-tris (neodecanoate), bismuth-tris (2-ethylhexoate) and the like Bismuth compound. These can be used in combination. When this curing catalyst is used, it can be used usually in an amount of about 0.1 to 20 parts by weight based on 100 parts by weight of the polymer having a reactive alkoxysilyl group in the molecule.

The composition according to the second aspect of the present invention may contain other additives in addition to the above-mentioned components, as long as the object of the present invention is not impaired. As such additives, those similar to the additives that can be blended in the composition according to the first embodiment of the present invention can be used.

The method for preparing the composition according to the second embodiment of the present invention as a one-pack type curable resin composition and the method for preparing the composition as a two-pack type curable resin composition are described in the first embodiment. A method similar to the method exemplified for the composition can be employed.

The curable resin composition according to the second aspect of the present invention having such a constitution is rapidly curable due to the use of a dithiocarbonate compound, and has a high molecular weight having an isocyanate group in the molecule. A one-pack type resin composition in which the elongation of the cured product is adjusted from a conventional dithiocarbonate compound and a latent curing agent, because the polymer contains a polymer having a reactive alkoxysilyl group in the molecule. Larger and show excellent rubber elasticity. In particular, in the curable resin composition according to the second aspect of the present invention using the above polymer in which an isocyanate group is bonded to a secondary carbon or a tertiary carbon in the molecule, Since the intermolecular hydrogen bond is weak due to the steric hindrance effect of the secondary or tertiary carbon, an appropriate viscosity and modulus can be obtained without using a plasticizer, and without using an adhesion improver such as epoxy. Excellent adhesiveness to mortar and the like can be exhibited, and therefore, excellent flexibility inherent to the urethane-based resin composition can be maintained after curing. Further excellent storage stability can be obtained. Further, an oxazolidine compound and / or
Alternatively, the composition of the present invention containing a ketimine compound having a large steric hindrance has particularly good storage stability. Further, the adhesiveness is good.

Accordingly, the curable resin composition according to the second aspect of the present invention can be used for concrete, tile,
Useful as an adhesive for wood, metal, etc.

[0108]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. <Examples of First Aspect> (Examples 1 to 3, Comparative Examples 1 and 2) The components shown in Table 1 were mixed at the ratios shown in Table 1 (each composition is parts by weight). The storage stability and surface curability (tack free time) of each of the obtained compositions were evaluated as follows. The results are shown in Table 1.

<Storage Stability> After each component was blended in a closed container and stored at 70 ° C. for 1 day, the composition flowing was indicated by “○”, and the cured one was indicated by “X”. <Surface hardening> After blending each component, 20 ° C, humidity 55
%, When a polyethylene film was attached to the surface of the composition, the time [hr] until the tack was almost eliminated was measured.

[0110]

[Table 1]

Dithiocarbonate: a compound represented by the above formula (5). Epoxy resin: EP4100E; Asahi Denka Kogyo Co., Ltd. Ketimine A (having steric hindrance): a compound represented by the following formula (7).

Embedded image Ketimine B (without steric hindrance): a compound represented by the following formula (8).

Embedded image Oxazolidine: a compound represented by the formula (6).

<Examples of Second Embodiment> (Examples 4 to 6, Comparative Example 3) The components shown in Table 2 were mixed at the ratios shown in Table 2 (each composition is parts by weight). The composition obtained was evaluated for storage stability, sheet elongation, adhesive strength, and fracture state. The method for evaluating storage stability was the same as in Example 1. Evaluation methods for sheet elongation, adhesive strength, and broken state are as follows. The results are shown in Table 2.

<Sheet Elongation> Each composition was prepared at 20 ° C. and 55%
Cured and cured for 10 days under RH conditions.
A dumbbell-shaped No. 2 test piece specified in IS K6251 was punched out. This test piece was pulled at a tensile speed of 200 mm /
The sample was pulled at a minimum for elongation at break. <Adhesive strength> 50 mg / cm of each composition between slate plates
^After applying ² and curing for 10 days under the conditions of 20 ° C. and 55% RH, a shear test was performed at a load rate of 3 MPa / min.
The breaking strength was measured. <Destruction state> In the shear test, the case where the slate plate itself was broken was defined as "base material failure".

[0114]

[Table 2]

Urethane prepolymer: Exenol 50
30 (PPG with a molecular weight of 5000) (manufactured by Asahi Glass Co., Ltd.) and TM
XDI (manufactured by Scitech) in a molar ratio of NCO / OH =
The resulting mixture was mixed at 2.0 and stirred at 80 ° C. for 20 hours to obtain a target urethane prepolymer. Modified silicone: Modified silicone S303 (Main chain PP
G, methyl dimethoxysilyl terminal) (manufactured by Kanegafuchi Chemical Co., Ltd., nominal molecular weight: 7000) dithiocarbonate: a compound represented by the above formula (5). Ketimine A (having steric hindrance): a compound represented by the formula (7). Ketimine B (without steric hindrance): a compound represented by the formula (8). Oxazolidine: a compound represented by the formula (6). Tin catalyst: dibutyltin laurate

[0116]

As is clear from the above, the first aspect of the present invention is as follows.
The curable resin composition according to the embodiment has good storage stability, cures at room temperature, and has a high curing rate. Further, the adhesiveness is good. The curable resin composition according to the second aspect of the present invention has good storage stability and cures at room temperature, has a fast curing speed, has good adhesiveness, and has excellent cured rubber with excellent rubber elasticity. Developed adhesive strength.
The curable resin composition according to the first aspect of the present invention is useful as an adhesive for concrete, wood, metal, and the like. The curable resin composition according to the second aspect of the present invention,
It is useful as an adhesive for concrete, wood, metal, etc., and a sealing material. Further, it is useful as an adhesive, a paint, a material for molding, a cast rubber material, a foam material, and the like.

Continued on the front page F term (reference) 4J002 AA011 BQ001 CK021 ER006 EU106 EV316 FD146 GJ00 4J034 AA02 BA08 CA11 CB02 CC33 CC44 CD08 DF14 DF15 DF16 DF17 DF19 DF20 DF21 DG03 DG04 DG05 HC12 HC06 HC07 HC12 KE02 RA08

Claims (8)

[Claims] 1. A compound having at least one dithiocarbonate group represented by the following formula (1) in a molecule and an oxazolidine compound and / or a ketimine (C = N) bond derived from a ketone and an amine. A curable resin composition comprising: a ketimine compound having a structure in which a branched carbon or a ring-membered carbon is bonded to at least one α-position of the ketimine carbon or nitrogen. Embedded image (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) 2. The curable resin composition according to claim 1, wherein in said ketimine compound, said branched carbon or ring member carbon is bonded to ketimine carbon. 3. The curable resin composition according to claim 1, wherein the ketimine compound is obtained using a ketone represented by the following formula (2). Embedded image (Wherein, R ⁴ : hydrogen atom, methyl group or ethyl group, R ⁵ : methyl group or ethyl group R ⁶ : alkyl group having 1 to 6 carbon atoms R ⁷ : hydrogen atom or alkyl group having 1 to 6 carbon atoms, Alternatively, R ⁵ and R ⁶ may combine to form a ring,
R ⁴ , R ⁵ and R ⁶ may form an aromatic ring. ) 4. The curable resin composition according to claim 1, further comprising a compound having at least one epoxy group in a molecule. 5. A polymer having an isocyanate group in a molecule and / or a polymer having a reactive alkoxysilyl group in a molecule, and a dithiocarbonate represented by the formula (1) according to claim 1. A curable resin composition comprising: a compound having at least one group in a molecule; and a latent curing agent. 6. The curable resin composition according to claim 5, wherein an isocyanate group of the polymer having an isocyanate group in the molecule is bonded to a secondary carbon or a tertiary carbon. 7. The curable resin according to claim 5, wherein the latent curing agent is an oxazolidine compound and / or a ketimine compound having a ketimine (C ＝ N) bond derived from a ketone and an amine. Composition. 8. The ketimine compound according to claim 1, wherein the ketimine compound is the ketimine compound according to claim 1.
3. The curable resin composition according to item 1.