JPH0959324A - Copolymer containing thiocarbonate group and resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copolymer containing a specific five-membered thiocarbonate ring, excellent in hardness, strength, adhesion property, water proof, chemical resistance and anti-oxidation property, and useful for paint, adhesive, ink, etc. SOLUTION: This copolymer contains one or more five-membered thiocarbonate rings expressed by formula I (R<1> to R<3> are each H or a lower alkyl) or a structural unit expressed by formula II [R<4> , R<5> are each H or methyl; (n) is 1-4]. Further, it is preferable that the copolymer is a polyester resin and synthesized from a hydroxy compound expressed by formula III [R<6> is a (Br substituted) phenylene or cyclohexylene; R<7> is methylene, C(CH3 )2 or S; (m) is 1-40].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thiocarbonate group-containing copolymer, and a resin composition containing the same and useful in applications such as paints, adhesives, inks, sealants for construction, and sealants for semiconductors.

[0002]

Reactive polymers having functional groups in their molecules are useful in a variety of applications. For example, when a composition containing such a polymer is used as an active ingredient of a paint, an adhesive, an ink, a sealant for construction, a sealant for semiconductors, etc., a crosslinking reaction or the like may occur under specific conditions after being used for the intended purpose. Hardness, strength, adhesion, water resistance,
It is possible to improve chemical resistance, oxidation resistance and heat resistance.

As a reactive polymer, a polymethacrylic acid derivative having a 5-membered carbonate group (N. Kihara et a
L., Makromol. Chem. 193, 1481 (1992)) and compositions containing the same (JP-A-1-14698 and JP-A-2).
-53880, JP-A-4-325539)
It has been known. On the other hand, as a polymer having a 5-membered ring thiocarbonate (1,3-oxathiolane-2-thione) group, 5- (methacryloyl) methyl-1,
Although a homopolymer of 3-oxathiolane-2-thione is described (Japanese Patent Laid-Open No. 247027/1993), the detailed polymerization method, physical properties and usefulness of the polymer are not described. Further, nothing is known about a copolymer having a 5-membered ring thiocarbonate group or a composition containing the same.

JP-A-7-145164 describes a method of crosslinking a polymer having an active hydrogen-containing functional group with a bifunctional 5-membered ring thiocarbonate compound. However, due to the structural characteristics of the bifunctional compound, the solubility in a solvent, the compatibility with other resins, and the like cannot be said to be sufficient, which is not always practical.

[0005]

The object of the present invention is to provide a thiocarbonate group-containing copolymer, and a paint containing the same.
It is intended to provide a resin composition useful for applications such as adhesives, inks, sealing agents, and sealants.

[0006]

The present invention has the general formula (I)

[0007]

Embedded image

(Wherein R ¹ , R ² and R ³ are the same or different and each represents hydrogen or lower alkyl)
The present invention relates to a copolymer containing at least one membered ring thiocarbonate group (hereinafter referred to as the copolymer of the present invention).
Furthermore, the present invention relates to a resin composition comprising the above-mentioned copolymer of the present invention and a nucleophile (hereinafter referred to as the resin composition of the present invention).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention causes a ring-opening reaction by the addition of a nucleophile coexisting with a 5-membered ring thiocarbonate group to a thiocarbonyl group, and the resulting thiol group undergoes spontaneous oxidation. To further form intermolecular SS crosslinks. Utilizing such reactivity, the resin composition can be improved in hardness, strength, adhesion, water resistance, chemical resistance, oxidation resistance, etc., and has excellent performance in coatings and adhesives. It can be used as an ink, an ink, a building sealant, a semiconductor sealant, and the like.

The physical properties of the copolymer and the resin composition of the present invention can be adjusted by the structure and / or composition ratio of the copolymer. For example, the solubility in a solvent and the compatibility with other resins. Etc. can be improved.
Furthermore, the curing reaction time can be increased by selecting the type of the nucleophile used in the (crosslinking) reaction system with the 5-membered ring thiocarbonate group and / or by adding a protective compound that reduces the reactivity of the nucleophile. It is also possible to obtain a resin composition which can be controlled and can be used as a one-pack type coating material having excellent storage stability.

In the definition of R ^{1 to} R ^{3 in} the copolymer of the present invention, lower alkyl represents a straight or branched chain having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and the like. . The copolymer of the present invention contains a structural unit containing a 5-membered thiocarbonate group and structural units 1 to 10 different from the structural unit, and can change various physical properties and reactivity in various ways as compared with a homopolymer. It has the feature.

The copolymer of the present invention includes a vinyl polymer containing at least one 5-membered thiocarbonate group represented by the general formula (I), a polyester resin, an alkyd resin, a polyamide resin, a polyether resin, and a polyurethane. Examples of the copolymer include resins and epoxy resins. Further, the copolymer of the present invention may be the above-mentioned copolymer chemically bonded to each other. The copolymer of the present invention is a vinyl-based polymer containing at least one 5-membered thiocarbonate group represented by the general formula (I), a polyester resin, an alkyd resin, a polyamide resin, a polyether resin, a polyurethane resin, The homopolymers such as epoxy resin may be chemically bonded to each other, or these homopolymers may be chemically bonded to the above copolymer. Among these, vinyl-based polymers and polyester resin copolymers are preferable examples. As a more preferable example of the vinyl polymer, the general formula (II)

[0013]

Embedded image

(Wherein R ¹ , R ² and R ³ are as defined above, R ⁴ and R ⁵ are the same or different and represent hydrogen or methyl, and n represents an integer of 1 to 4) Copolymers containing the represented (meth) acrylic acid derivatives are mentioned. In the copolymer of the present invention, when a monomer having a 5-membered thiocarbonate group is subjected to vinyl copolymerization, the vinyl-based monomer is preferably (meth) acrylic acid,
Maleic acid, fumaric acid, itaconic acid, crotonic acid, monoethyl maleate, monomethyl itaconate, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Butyl acrylate, isobutyl (meth) acrylate,
T-Butyl (meth) acrylate, (meth) acrylic acid 2
-Ethylhexyl, lauryl (meth) acrylate, styrene, vinyltoluene, α-methylstyrene, dimethylstyrene, n-methylol (meth) acrylamide,
(Meth) acrylamide, (meth) acrylonitrile,
Vinyl acetate, vinyl propionate, vinyl versatate, diethyl maleate, dibutyl maleate, diethyl fumarate, dibutyl fumarate, diethyl itaconate,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, dimethylamino Ethyl (meth) acrylate,
Examples thereof include diethylaminoethyl (meth) acrylate (meth) acrylamide, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, allyl alcohol, allyl alcohol ester, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and butadiene. Further, vinyl-based and non-vinyl-based copolymers can also be used, and examples of such copolymers include vinyl-modified epoxy resin (Japanese Patent Laid-Open No. 54-30249) and vinyl-modified polyester resin (Japanese Patent Laid-Open No. 1-129072). ), Vinyl-modified alkyd resin, vinyl-modified urethane resin (Japanese Patent Laid-Open No. 1-301761), and the like.

Further, as a more preferable example of the polyester resin, the general formula (III)

[0016]

[Chemical 6]

(In the formula, R ⁶ has 1 to 4 hydrogen atoms as B.
represents phenylene optionally substituted by r or cyclohexylene, R ⁷ is methylene, C (CH ₃ ) ₂
Or a polyester copolymer in which a hydroxy compound having a thiocarbonate group represented by S and m represents an integer of 1 to 40) is bound by an ester bond. Since the above polyester resin has a tough bisphenol skeleton in the molecule, the physical properties after crosslinking with an amino compound or the like are strong. The above polyester resin is
It can be obtained by adding the compound represented by the general formula (III) to the known polyester resin production process using a compound having a hydroxyl group, a compound having a carboxyl group and / or a hydroxycarboxylic acid.

As the compound having a hydroxyl group, a compound having two or more hydroxyl groups per molecule, preferably ethylene glycol, 1,3-propylene glycol, 1,
4-butylene glycol, 1,5-pentanediol,
There are neopentyl glycol, trimethylolpropane, pentaerythritol, butylethyl-1,3-propanediol and the like, and as the compound having a carboxyl group, a compound having two or more carboxyl groups per molecule or a precursor thereof (for example, acid Anhydride), preferably succinic acid, glutaric acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, trimellitic anhydride, pyromellitic anhydride, adipic acid,
Examples of hydroxy acids such as maleic acid and fumaric acid include dimethylolpropionic acid, dimethylolbutyric acid, lactic acid, malic acid and citric acid.

Further, the copolymer of the present invention needs to contain at least one 5-membered thiocarbonate group, but the content of the structural unit containing the 5-membered thiocarbonate group (on a monomer basis) in the copolymer is , Preferably 0.2 to 90 mol%. The weight average molecular weight (Mw) of the copolymer of the present invention is 1,000 to 40.
It is 50,000, preferably 5,000 to 200,000. Among the copolymers of the present invention, those particularly useful as a main component of water-based paints, inks, adhesives, sealants for construction, sealants for semiconductors, etc. are those having at least one carboxyl group in the molecule. The acid value of the carboxyl group is preferably 10 to 100 mg KOH / g (converted to resin).

The nucleophile which is a constituent component of the resin composition of the present invention may be any one as long as it undergoes a nucleophilic addition reaction to a thiocarbonyl group of a 5-membered ring thiocarbonate group, for example, an amino group, Examples thereof include compounds having a hydroxy group, an imino group, a thiol group, a phenolic hydroxyl group and the like. Of these, compounds having an amino group are particularly preferable, more preferable are those having two or more primary or secondary amino groups in the molecule, and further preferable are three or more primary or secondary amino groups. It has a base. The compound having an amino group is a compound having an optionally protected primary or secondary amino group, for example, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine ethylenediamine, 1,2- Diaminopropane, 1,3
-Diaminopropane, 1,4-diaminobutane, 1,6
-Diaminohexane, 1,8-diaminooctane, 4-
Aminomethyl-1,8-diaminooctane, dimer acid amide, amine adduct of epoxy resin, monoethanolamine, diethanolamine, 2-amino-2-methylpropanol, 1,2-diaminocyclohexane,
N, N'-bis (2-aminoethyl) ethylenediamine, N, N'-bis (3-aminopropyl) ethylenediamine, N, N'-dimethyldiaminopropane (DMD
AP), ethylenediamine, diethylenetriamine, triethylenetetramine, trisaminoethylamine, diethanolamine, dimethylamine, diethylamine,
Aliphatic primary or secondary amines such as diisopropylamine and dicyandiamide, alicyclic secondary amines such as pyrrolidine, piperidine, piperazine, morpholine and thiomorpholine, basic amino acids such as lysine, ornithine and arginine, aniline and diphenylamine, etc. Aromatic amines, aralkylamines such as benzylamine, pyrrole,
In addition to low molecular weight compounds such as basic nitrogen-containing heterocyclic compounds such as imidazole and triazole, (meth) acrylic acid monohydrazide, 2-aminoethyl (meth) acrylate,
Necessary with copolymers of vinyl-based polymerizable monomers having an amino group in the molecule such as allylamine, N-methylallylamine, diallylamine and other vinyl-based monomers or N-vinylformamide, N-vinylacetamide, etc. Depending on the above, a hydrolyzate of a copolymer with another vinyl-based monomer, a polyamine adduct of a polyepoxy compound, or an amino-protected form of these amine compounds can be mentioned.

The general formula (IV)

[0022]

[Chemical 7]

A compound represented by the formula: wherein R ⁸ represents hydrogen or methyl or ethyl, and R ⁹ represents linear or branched alkylene (having 2 to 16 carbon atoms) or phenylene, or The amino protected form may be used as a nucleophile. The compound represented by the general formula (IV) can be synthesized by a known method [Angew. Chem. Int. Ed ., 29, 138 (1990)].

As the amino protecting group, various kinds can be widely used as long as they reduce the nucleophilicity of the amino group, but azomethine or azomethinium salt obtained by the reaction with a low molecular weight carbonyl compound is preferable. Also,
The hydroxy compound as the nucleophile is methanol,
Alcohols such as ethanol, isopropanol, butanol, octanol, ethylene glycol, polyethylene glycol, or water (including hydroxy ions)
Represents

For the purpose of increasing the nucleophilicity of these hydroxy compounds, a tertiary amine such as triethylamine or a basic compound such as sodium hydroxide may be added in an amount of 1 to 100 mol% based on the hydroxy compound. Further, in the present invention, a compound having a primary or secondary amino group protected by a low molecular carbonyl compound is used as a nucleophile for controlling the reaction rate of a 5-membered thiocarbonate group and an amino group. The compound may be synthesized according to a known method for synthesizing ketimine or enamine. Alternatively, a commercially available ketimine or enamine compound [eg Epicure H-2, manufactured by Yuka Shell Epoxy Co., Ltd.] may be used. Examples of the low-molecular-weight carbonyl compound that may be used as a protective agent to reduce the reactivity of the above amino group include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ketone compounds such as cyclohexanone, or acetaldehyde, propionaldehyde, isobutyl. aldehyde,
Aldehyde compounds such as octyl aldehyde and (meth) acrolein having a boiling point of 150 ° C. or lower are preferable.
The low molecular weight carbonyl compound is usually used in an amount of 0.5 to 5 equivalents, preferably 0.8 to 1.5 equivalents, based on the nucleophile, but a large excess may also be used as a solvent.

Next, the method for producing the copolymer of the present invention and the resin composition of the present invention will be described. The polymer having a 5-membered thiocarbonate group in the molecule can be obtained by polymerizing the corresponding monomer by a known method. The monomer having a 5-membered ring thiocarbonate group is, for example, a known method (JP-A-5-247027;
N. Kihara et al., J. Org. Chem., 60, 473 (1995))
According to the above, it can be obtained by reacting an oxirane compound and carbon disulfide in the presence of an alkali halide such as lithium bromide.

[0027]

Embedded image

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n have the same meanings as described above) The compound represented by the general formula (III) is a commercially available epoxy resin (for example, E-1001-1007, manufactured by Yuka Shell Co., Ltd.) is obtained by reacting carbon disulfide in the presence of an alkali halide such as lithium bromide in the same manner as described above. Further, the polymer having a 5-membered thiocarbonate group in the molecule is obtained by previously obtaining a polymer having a functional group (carboxyl, hydroxyl, amino, etc.) by a known method,
It can also be produced by subjecting a polyfunctional 5-membered ring thiocarbonate compound to a pendant type coupling reaction.

The polymerization reaction is, for example, in the case of radical polymerization,
It is carried out at 0 to 100 ° C. for 1 to 24 hours in the presence of a polymerization initiator of 0.5 to 5 mol% with respect to the monomer. A purification means such as a reprecipitation method is used to isolate the produced polymer. In order to obtain a vinyl-based aqueous emulsion polymer, a known method using a monomer in water with an emulsifier and a polymerization initiator (Japanese Patent Laid-Open No. 54-110248, Japanese Patent Publication No. 58-20).
991) and emulsion polymerization.

The copolymer and resin composition of the present invention can have improved storage stability by having a core-shell structure. The core-shell type emulsion polymer in water can be synthesized by a known method (JP-A-57-3850, JP-A-61-136501).
The copolymer and resin composition of the present invention can be emulsified in water by a known method.

The polymerization solvent, which varies depending on the polymerization mode, is benzene, toluene, xylene, hexane, cyclohexane, ethyl acetate, butyl acetate, 3-methyl-3-.
Methoxybutyl acetate, ethylene glycol monobutyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methanol, ethanol, propanol, isopropanol, butanol, N-methylpyrrolidone, tetrahydrofuran, acetonitrile, ethylene glycol monobutyl ether, ethylene glycol mono Butyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, methoxybutanol, methoxybutyl acetate, 3-methyl-3-methoxy-1-butanol, water, dimethyl sulfoxide,
Dimethylformamide, dimethylacetamide and the like are used.

Although the polymerization initiator varies depending on the polymerization mode, for example, in radical polymerization, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, 2,2′-azobisvaleronitrile, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxy- 2-Ethylhexanoate, cumene hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxide, methyl ethyl ketone peroxide, m-chloroperbenzoic acid, potassium persulfate, sodium persulfate, ammonium persulfate and the like are used. .

As the emulsifier for the aqueous emulsion polymerization, anionic emulsifiers such as alkylbenzene sulfonate, nonionic emulsifiers such as polyethylene glycol alkylphenyl ether, and reactivity such as Eleminol JS-2 [manufactured by Sanyo Kasei Co., Ltd.] Emulsifiers, polymeric emulsifiers in which hydrophilic groups such as salts of carboxyl groups and salts of sulfone groups are introduced into various polymers such as vinyl-based and polyester-based polymers are used. Further, various protective colloids for stabilizing emulsion such as polyvinyl alcohol and cellulose can be used together.

In order to obtain an aqueous emulsion-dispersed resin composition by a method other than the aqueous emulsion polymerization, there are a self-emulsification method in which a tertiary amine salt of a carboxyl group is introduced into the molecule of the copolymer, and an emulsification method using an external emulsifier. . Further, among the copolymers of the present invention, when it is desired to obtain a water-soluble copolymer having a carboxyl group, a copolymer having a carboxyl group [for example, (meth) acrylic acid copolymer] is used in a water-soluble solvent such as ethylene glycol monobutyl ether. , Ammonia, trimethylamine, triethylamine, dimethylethanolamine, morpholine, sodium hydroxide, potassium hydroxide and the like.

Further, as a method for producing the copolymer,
Examples thereof include copolymerization in which another monomer is added to a monomer having a 5-membered ring thiocarbonate group in the molecule, block copolymerization in which another monomer is reacted after synthesis of a homopolymer, and a method of covalently bonding the polymer to each other.
Further, the copolymer of the present invention, in addition to the above production method,
For the polymer having an oxirane structure, a known method [JP-A-5-247027; N. Kihara et al., J. Or.
g. Chem., 60, 473 (1995)], it can also be obtained by reacting carbon disulfide in the presence of an alkali halide such as lithium bromide.

Further, in order to chemically bond the vinyl polymer and the polyester resin, a method of previously synthesizing the vinyl polymer and the polyester resin and then bonding them by esterification (JP-A-1- No. 129072), a vinyl monomer can be grafted by radical polymerization after synthesizing a polyester having a radically polymerizable functional group (such as a vinyl group or a conjugated double bond) in advance.

The epoxy resin used as the copolymer component of the present invention is E-1001-1007.
(Manufactured by Yuka Shell Co., Ltd.) is preferable, and in order to make these modified epoxy resins, animal and vegetable oil fatty acids may be chemically bonded to these resins. Examples of these animal and vegetable oil fatty acids include tall oil fatty acid, flaxseed oil fatty acid, soybean oil fatty acid, dehydrated castor oil fatty acid, Chinese tung oil fatty acid and the like, and examples of organic acids include octyl acid, benzoic acid, t-butyl benzoic acid. Examples thereof include acids and nonanoic acids.

In the resin composition of the present invention, the equivalent ratio of the nucleophile as a constituent component to the 5-membered ring thiocarbonate group is: amino group / 5-membered ring thiocarbonate group = 0.3 to 2.0,
Preferably 0.8 to 1.2 gives good coating performance.
The resin composition of the present invention is characterized by comprising at least one of the copolymers of the present invention and a nucleophile, and can be obtained by uniformly dispersing and mixing the two. It may be a solution or suspension with a solvent added. As the solvent for this purpose, for example, the above-mentioned polymerization solvent alone or a mixture of 2 to 4 kinds thereof is used in an amount of 0.2 to 100 times (weight ratio) with respect to the copolymer of the present invention. The resin composition containing such a solvent,
It can be obtained by adding a nucleophile to the polymerization reaction solution itself, a concentrated product thereof, or a product prepared by adding a necessary solvent to them, but by adding the nucleophile and the solvent to the isolated copolymer and stirring the mixture. You can also get

The solution or suspension of the resin composition of the present invention can be used as a clear paint or a clear ink itself, but by adding a pigment or a dispersed pigment, it can be used as a colored paint or a colored ink. You can also do it. As a method for dispersing the pigment, a known paint shaker, ball mill or the like can be used. Further, the resin composition of the present invention, if necessary, various ultraviolet absorbers,
Antioxidants, hindered amine light stabilizers, pigment dispersants and the like can be added, and if necessary, various commonly used alkyd resins, acrylic resins, cellulose resins, petroleum resins, epoxy resins, It may contain a styrene acrylic emulsion polymer, a water-soluble alkyd resin, a water-soluble acrylic resin, a plasticizer, a film-forming aid, and the like.

When the resin composition of the present invention is used for coating, conventional brush coating, electrostatic coating, etc. can be adopted as a coating method, and a wide range of curing conditions from normal temperature drying to overheat drying can be selected. Is possible. Further, as the type of the object to be coated, it can be applied to metals, wood, plastics, inorganic materials, concrete, asphalt, etc., and is useful as an undercoat, a topcoat, a one-coat finishing agent for protecting the material, improving the aesthetic appearance and the like.

[0041]

EXAMPLES Hereinafter, the embodiments of the present invention will be described with reference to Examples, Reference Examples and Test Examples.

Examples 1 to 3 and Reference Example 1 5- (methacryloyloxy) methyl-1,3-oxathiolane-2-thione (MOT) and methyl methacrylate were mixed at a ratio of 10 mmol to prepare a monomer mixture. Dimethyl sulfoxide (DMSO) solution, and 3
A glassy polymerization tube containing a mol% (monomer ratio) of AIBN was replaced with nitrogen, degassed, sealed under reduced pressure, and then left at 60 ° C. for 8 hours. The reaction mixture was poured into a large amount of methanol, the deposited precipitate was separated by filtration, washed with methanol and dried under reduced pressure to obtain the target (co) polymer.

The amount of solvent used in the polymerization reaction, obtained (co)
Table 1 shows the polymer composition ratio, yield, number average molecular weight (Mn), and molecular weight distribution (Mw / Mn).

[0044]

[Table 1]

In addition, ¹ H of the raw material monomer (MOT), the homopolymer (Reference Example 1) and the copolymer (Example 2) were used.
-NMR is shown in Figure 1.

Example 4 5- (methacryloyloxy) methyl-1,3-oxathiolane-2-thione (0.20 g), methyl methacrylate (3.5 g), methacrylic acid (0.30 g), and AIBN (0 A solution of 0.080 g of xylene (4.0 g) was stirred at 100 ° C. for 6 hours under a nitrogen atmosphere. Example 1
After the same post-treatment as above, the number average molecular weight of 25,000 (G
Polystyrene conversion by PC), acid value 47.5 mg KO
An H / g copolymer was obtained.

Example 5 189 mg (1.0 mmol) of the copolymer obtained in Example 3
Unit) in DMSO (1.5 ml) solution, butylamine 0.099 ml (1.0 mmol) in DMSO
(0.5 ml) solution was added at room temperature and stirred to obtain a resin composition.

Example 6 189 mg (1.0 mmol) of the copolymer obtained in Example 3
Unit) in DMSO (1.5 ml), diisopropylamine 0.14 ml (1.0 mmol) in DMS.
An O (0.5 ml) solution was added at room temperature and stirred to obtain a resin composition.

Example 7 131 mg (1.0 mmol) of the copolymer obtained in Example 1
A solution of 0.099 ml (1.0 mmol) of butylamine in acetone (0.5 ml) was added to a solution of (unit) in acetone (4.5 ml) at room temperature and stirred to obtain a resin composition.

Example 8 131 mg (1.0 mmol) of the copolymer obtained in Example 1
To a tetrahydrofuran (4.5 ml) solution of (unit), a tetrahydrofuran (0.5 ml) solution of benzylamine 0.11 ml (1.0 mmol) was added at room temperature and stirred to obtain a resin composition.

Example 9 165.6 g of deionized water was charged into a flask equipped with a dropping device, a stirrer, a thermometer, a cooling pipe and a nitrogen gas introducing pipe, heated to 60 ° C., and stirred under a nitrogen atmosphere. ,
Methyl methacrylate 80 g, butyl acrylate 157.
4 g, MOT 8.2 g, methacrylic acid 3.6 g, ammonium persulfate 10.7% aqueous solution 17.9 g, Emulgen 930 [nonionic emulsifier, manufactured by Kao Corporation] 12
g, Emulgen 931 [nonionic emulsifier, Kao Corporation]
Manufactured by the company] 6 g and 144.0 g of deionized water were added dropwise for 3 hours. After the dropping was completed, this was aged for 1 hour at 60 ° C. to complete the polymerization reaction, and a resin solution (emulsion) was obtained. The resulting resin solution had a milky appearance with solids content of 37% and 450 cps at 25 ° C.

Next, titanium oxide (blended at a resin solid content / pigment weight ratio of 1.0) was added to the resin solution to form a paint. DM for 100g of this paint
A resin composition was obtained by mixing 1.2 g of DAP.

Example 10 250 g of deionized water and Emulgen 930 [nonionic emulsifier, manufactured by Kao Corporation] in a flask equipped with a dropping device, a stirrer, a thermometer, a cooling pipe and a nitrogen gas introducing pipe 15
g, Emulgen 931 [nonionic emulsifier, Kao Corporation]
15g, and heated to 85 ° C., under a nitrogen atmosphere, 18 g of methyl methacrylate, 20 g of butyl acrylate,
Acrylic acid 1g, MOT 3.0g, Emulgen 930
[Nonionic emulsifier, manufactured by Kao Corporation] 1.25 g, Emulgen 931 [nonionic emulsifier, manufactured by Kao Corporation]
1.25 g, 8.3 g of a 3% aqueous solution of ammonium persulfate
Was added.

Next, 180 g of deionized water, Emulgen 930 [nonionic emulsifier, manufactured by Kao Corporation] 12.5
g, Emulgen 931 [nonionic emulsifier, Kao Corporation]
Company] 12.5 g, methyl methyl methacrylate 162
g, butyl acrylate 162 g, acrylic acid 9 g, MO
T 25 g and 33 g of a 3% aqueous solution of ammonium persulfate were added over 3 hours, and the polymerization reaction was carried out while maintaining the same temperature for 2 hours.

Further, 45 g of styrene and 4 of butyl acrylate
5 g, 2.5 g of acrylic acid, 7 g of MOT, 40 g of a 3% aqueous solution of ammonium persulfate were added over 0.5 hours, and 2
Polymerization was completed in time and cooled to room temperature to obtain a resin solution. Next, this resin solution was made into a paint in the same manner as in Example 9, and 1.8 g of a ketimine compound [Epicure H-2, manufactured by Yuka Shell Epoxy Co., Ltd.] was added to obtain a resin composition.

Example 11 Methyl isobutyl ketone 15 was placed in a flask equipped with a dropping device, a stirring device, a thermometer, a cooling pipe and a nitrogen gas introducing pipe.
0 g was charged and the temperature was raised to 100 ° C. Then after nitrogen substitution,
A mixed solution of 15 g of MOT, 135 g of butyl methacrylate and 1.5 g of t-butylperoxy-2-ethylhexanoate as a polymerization catalyst was added over 3 hours. Furthermore,
This was aged at 100 ° C. for 3 hours to complete the polymerization reaction. As a result, the solid content is 50% by weight and the weight average molecular weight is 2
5,000 resin solutions were obtained. Then, this resin solution was made into a paint in the same manner as in Example 9, and 100 g of this paint was further added.
Then, 3.4 g of DMDAP was added to obtain a resin composition.

Example 12 In Example 11, 150 g of methyl isobutyl ketone
Instead of ethylene glycol monobutyl ether 15
Instead of 0 g and butyl methacrylate 135 g, 10 g of acrylic acid and 125 g of butyl methacrylate were used to obtain an aqueous acrylic resin having a solid content of 50%, an acid value of 52 mgKOH / g, and a weight average molecular weight of 25,000. Further, this was neutralized with 14.3 g of triethylamine to obtain a resin solution.

Next, this resin solution was dispersed with titanium oxide in a paint shaker so that the resin solid content / pigment ratio (weight ratio) was 1, and diluted with water to a solid content of 40% by weight to form a paint. went. Furthermore, 3.4 g of DMDAP was added to 100 g of this paint to obtain a resin composition.

Example 13 In Example 11, 6.1 g of a ketimine compound [Epicure H-2, manufactured by Yuka Shell Epoxy Co., Ltd.] was added in place of 3.4 g of DMDAP to obtain a resin composition.

Example 14 A flask similar to that in Example 11 was charged with phthalic anhydride 417.
3 g, fumaric acid 40.6 g, butylethylpropanediol 544.4 g, trimethylolpropane 55.6
g, 30 g of xylene, and heated at 210 ° C. for 8 hours to give a polyester resin (hydroxyl value 85 mgKOH / g, acid value 3.4 mgKOH / g, weight average molecular weight 5,600) 1
000 g were obtained. Then, after adding 1950 g of xylene, 100 g of MOT, 320 g of butyl methacrylate, 320 g of styrene, 230 g of 2-hydroxyethyl methacrylate and t-butylperoxy-2- as a polymerization catalyst.
A mixed solution of 30 g of ethyl hexanoate was added dropwise over 3 hours and further aged at 100 ° C. for 3 hours to complete the polymerization, to obtain a resin solution having a solid content of 50% by weight and a weight average molecular weight of 37,000.

Further, this was made into a paint by the same method as in Example 9, and DMDAP 1.
2 g was added to obtain a resin composition.

Example 15 A resin composition was obtained in the same manner as in Example 14 except that 0.8 g of dicyandiamide was used instead of 1.2 g of DMDAP.

Example 16 Using a flask similar to that of Example 11, a bisphenol A / epicle hydrin type epoxy compound (E-100
1, manufactured by Yuka Shell Co., Ltd.) 500 g of methyl isobutyl ketone and 500 g of xylene, and then MOT
50 g, butyl methacrylate 160 g, styrene 16
0 g, 2-hydroxyethyl methacrylate 115 g,
t-Butylperoxy-2-ethylhexanoate 15
g of the mixed solution was added dropwise over 3 hours, and further at 100 ° C. for 3 hours.
Aging is carried out for a period of time to complete the polymerization, and a weight average molecular weight of 11,
300 vinyl modified epoxy resin solutions were obtained.

Further, this resin solution was made into a paint in the same manner as in Example 9, and DMDAP 1.2 was added to 100 g of this paint.
g was added to obtain a resin composition.

Example 17 Using a flask similar to that of Example 11, a bisphenol A / epicle hydrin type epoxy compound (E-100
4, manufactured by Yuka Shell Co., Ltd.) 792.2 g, dehydrated castor oil fatty acid 221.8 g, N, N ^, -dimethylcyclohexylamine 0.5 g, and xylene 30 g are heated at 220 ° C. for 10 hours to give an acid value of 2.5 mg KOH / g. The epoxy ester of was obtained. Then MOT 100g, butyl acrylate 32
0 g, 320 g of styrene, 230 g of 2-hydroxyethyl methacrylate, 30 g of t-butylperoxy-2-ethylhexanoate were added over 3 hours, and further 1
Polymerization was completed by aging at 00 ° C. for 3 hours to obtain a vinyl-modified epoxy ester resin solution having a weight average molecular weight of 45,000.

Further, this resin solution was made into a paint in the same manner as in Example 9, and DMDAP 1.
2 g was added to obtain a resin composition.

Example 18 In a flask similar to that used in Example 11, 98.3 g of the compound obtained in Reference Example 2, 136.6 g of adipic acid, 276.8 g of phthalic anhydride, 524.
1 g, trimethylolpropane 12.5 g, xylene 3
Add 0 g and acid value 7.8 mg KO at 210 ° C for 8 hours.
H / g, a resin having a weight average molecular weight of 5,000 was obtained, and after cooling, 950 g of xylene was added so that the solid content was 50%,
A resin solution was obtained. This resin solution was made into a paint in the same manner as in Example 9, and DMDAP was added to 100 g of this paint.
1.2 g was added to obtain a resin composition.

Example 19 In a flask similar to that of Example 11, 98.3 g of the compound obtained in Reference Example 2, 96.0 g of adipic acid, and 2 phthalic anhydrides were used.
76.8 g, maleic acid 40.6 g, butyl ethyl propane diol 524.1 g, trimethylol propane 1
2.5 g and xylene 30 g were added, and polyester resin (hydroxyl value 25 mg KOH / g, acid value 1.4 mg KOH / g, weight average molecular weight 5,600) was added at 200 ° C. for 8 hours.
000 g were obtained. Then, after adding 1950 g of xylene, a mixed solution of 100 g of MOT, 320 g of butyl acrylate, 550 g of styrene, and 30 g of t-butylperoxy-2-ethylhexanoate was added dropwise at 100 ° C. over 3 hours, and further 100 ° C. Aged for 3 hours to complete polymerization, solid content 50% by weight, weight average molecular weight 37,000
Was obtained.

Further, this resin solution was made into a paint in the same manner as in Example 9, and DMDAP 1.2 was added to 100 g of this paint.
g was added to obtain a resin composition.

Reference Example 2 5 L of tetrahydrofuran, 500 g of bisphenol A / epichlorohydrin type epoxy resin (E-1001, manufactured by Yuka Shell Co., Ltd.) and 25 g of lithium bromide were dissolved in a 10 L flask equipped with the same apparatus as in Example 11. After 340 mL of carbon disulfide was added dropwise to the solution at 25 ° C., the internal temperature was changed to 4
It was heated to 5 ° C. and reacted for 8 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and 5 L of chloroform and 3 L of water were added to the obtained concentrated residue.
L was added and liquid separation was performed. 5 L of saturated saline was added to the extracted organic phase, and the layers were separated again. The obtained organic phase was dried with 300 g of magnesium sulfate, and then chloroform was distilled off to obtain 445 g of a crude product.

A purified product was obtained by purifying 400 g of the crude product by silica gel column chromatography [(Daisogel IR-60, developing solvent chloroform / acetone = 20/1 (volume ratio)]]. The analysis results of NMR and IR of the obtained purified product are shown below. ¹ H-NMR (CDCl ₃ , δ ppm, 400 MH
z): 1.63 (s, 18H), 2.52 (d, J = 5.1Hz, 2H), 3.73 (d
d, J = 7.1,12.0Hz, 2H), 3.78 (dd, J = 7.6,8.0Hz, 2H), 4.10
(dd, J = 5.6,12.0Hz, 4H), 4.13 (dd, J = 4.6,8.0Hz, 4H), 4.
25 (dd, J = 5.6,10.3Hz, 2H), 4.30 (dd, J = 5.6,10.3Hz, 2H),
4.35 (q, J = 5.4Hz, 2H), 5.42 (m, 2H), 6.81 (dd, J = 1.7,8.
8Hz, 6H), 6.83 (dd, J = 2.0,8.8Hz, 6H), 7.13 (dd, J = 1.5,
8.0Hz, 12H) IR (NaCl, cm ^-1 ): 508, 1184, 1241, 1606, 3037, 344
Two

Test Examples 1 to 4 The resin compositions of Examples 5 to 8 were applied to an iron phosphate-treated steel sheet with an applicator so that the dry film thickness was 30 microns, and the coating film was dried at room temperature for 1 week. It was made. These coating films were evaluated for coating performance by the method described below.
Table 2 shows the evaluation results of the coating film performance of Test Examples 1 to 4.

[0073]

[Table 2]

Evaluation method of coating film Pencil hardness: It was carried out according to the hand scraping method of JIS K5400 (General test method for paints). Impact resistance: According to JIS K5400 (General test method for coating materials), a Deupon type impact tester was used to measure the height of peeling of the coating film by applying a weight of 500 g. Water resistance: According to JIS K5400 (General test method for paints), the test piece was immersed in warm water at 40 ° C for 120 hours and the appearance was visually observed. Alkali resistance: In accordance with JIS K5400 (General paint test method)
The test piece was immersed in a saturated solution of calcium hydroxide at 25 ° C. for 72 hours to visually inspect its appearance.

[0075]

INDUSTRIAL APPLICABILITY The present invention provides a thiocarbonate group-containing copolymer, and a resin composition containing the same, which is useful in applications such as paints, adhesives, inks, sealants for construction, and sealants for semiconductors.

[Brief description of drawings]

FIG. 1 shows ¹ H—N of a raw material monomer (MOT), a homopolymer (Reference Example 1), and a copolymer (Example 2).
An MR spectrum is shown. (A) Monomer _{(MOT) (CDCl 3) (} b) homopolymer (DMS0-d ₆₎ Reference Example 1 (c) of Example 2 Copolymer (DMS0-d ₆₎ s and w are solvents each of water Indicates a signal.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/17 C08K 5/17 C08L 33/14 LHY C08L 33/14 LHY C09D 11/10 PTK C09D 11/10 PTK 133/14 PFY 133/14 PFY C09J 133/14 JDE C09J 133/14 JDE C09K 3/10 C09K 3/10 F

Claims (10)

[Claims] 1. A compound of the general formula (I) (In the formula, R ¹ , R ² and R ³ are the same or different and each represents hydrogen or lower alkyl) A copolymer containing at least one 5-membered ring thiocarbonate group. 2. The copolymer according to claim 1, wherein the copolymer is a vinyl polymer. 3. A compound of the general formula (II) (In the formula, R ¹ , R ² and R ³ are as defined above, and R ⁴
And R ⁵ are the same or different and each represent hydrogen or methyl, and n represents an integer of 1 to 4). 4. The copolymer according to claim 1, wherein the copolymer is a polyester resin. 5. A compound represented by the general formula (III): (In the formula, R ⁶ represents phenylene in which 1 to 4 hydrogen atoms may be substituted with Br, or cyclohexylene, R ⁷ represents methylene, C (CH ₃ ) ₂ or S, and m Is an integer of 1 to 40), and the hydroxy compound represented by the formula (1) is bound by an ester bond. 6. A resin composition comprising the copolymer according to claim 1 and a nucleophile. 7. The resin composition according to claim 6, wherein the nucleophile is a compound having an optionally protected amino group. 8. The resin composition according to claim 7, wherein the amino group of the nucleophile is protected by a low molecular weight carbonyl compound. 9. The resin composition according to claim 7, which contains a solvent. 10. A paint comprising the copolymer according to claim 1 and a nucleophile.