JP2001151785A - Coupling agent for calcium carbonate and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound useful as a coupling agent acting on a polymer having reactivity and on calcium carbonate and provide a resin composition containing the compound, a polymer having reactivity and calcium carbonate. SOLUTION: The objective compound is expressed by formula (1) or (2) (R1 is an alkylene, vinylene or phenylene; R2 is an alkyl having hydrolyzable silyl group; R3 is H, an alkyl, phenyl or an alkyl having hydrolyzable silyl group; R4 is an alkylene, vinylene or phenylene; and R5 is an alkyl having oxazolidine structure). The resin composition contains one of the above compounds, a polymer containing reactive group and calcium carbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound suitable as a coupling agent acting on both a polymer having a reaction activity and calcium carbonate, and a resin composition containing the compound, the polymer having a reaction activity and calcium carbonate. And about.

[0002]

2. Description of the Related Art In general, when a rubber product is manufactured, by adding a filler such as calcium carbonate, the strength and stability are increased, and the overall appearance and feel, such as anti-slip and matting, are improved, and the fluidity is further improved. It is possible to make it easy to process by improving the properties and dispersibility. It is also known that calcium carbonate is used as a bulking agent in that it is inexpensive, and it is also useful for saving production costs.

[0003] When calcium carbonate is added to a polymer having a reaction activity, calcium carbonate is generally subjected to a surface treatment in order to maintain storage stability. For example, Japanese Patent Application Laid-Open No. 2-38309 proposes that a precipitated calcium carbonate is subjected to a surface treatment with a fatty acid ester such as stearyl stearate. However, when calcium carbonate surface-treated with the above fatty acid ester is used, the fatty acid ester as a surface treatment agent elutes during storage and aggregates in the liquid resin composition,
There is a problem that the precipitates are deposited, and as a result, the appearance of the cured product surface is impaired.

Japanese Patent Application Laid-Open No. 09-263708 discloses a one-pack type moisture in which calcium carbonate treated with a surface treatment agent for calcium carbonate comprising a compound having an alkyl ester group of isocyanate is blended as a measure for solving such a problem. Curable resin compositions have been proposed.

However, since the surface-treated calcium carbonate as described above has a small surface polarity, it can enhance the dispersibility of the rubber or form a chemical bond with the rubber particles directly or via a vulcanizing agent with the filler particles. There is a need. As such a method, it is generally known to use various coupling agents. For example, JP-A-10-31
No. 6811 discloses a large number of surface treatment agents for calcium carbonate, and a silane coupling agent having a hydrolyzable silyl group is compounded in order to improve the adhesive strength of the curable composition. However, such a coupling agent does not have sufficient interaction with calcium carbonate, and a more effective coupling agent for a curable composition containing calcium carbonate has been desired.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a compound suitable as a coupling agent for calcium carbonate, which is added to a resin composition containing calcium carbonate to improve its strength and modulus, and a resin composition containing the compound. The purpose is to provide things.

[0007]

Means for Solving the Problems The present invention provides the following formula (1)
Is provided.

[0008]

Embedded image In the formula (1), R ¹ is a branched alkylene group having 1 to 18 carbon atoms, a vinylene group or a phenylene group, and R ² is a C ¹ to C 18 having a hydrolyzable silyl group.
R ³ is a hydrogen atom, having 1 to 18 carbon atoms.
Is a C1-C18 alkyl group having a branched alkyl group, phenyl group or hydrolyzable silyl group. The present invention also provides a compound represented by the above formula (1), which is suitable as a coupling agent for calcium carbonate.

Next, the present invention provides a compound represented by the following formula (2).

[0010]

Embedded image In the formula (2), R ⁴ is a branched alkylene group having 1 to 18 carbon atoms, a vinylene group, or a phenylene group, and R ⁵ has 1 to 1 carbon atoms having an oxazolidine structure.
8 alkyl groups. The present invention also provides a compound represented by the formula (2), which is suitable as a coupling agent for calcium carbonate.

The present invention further provides at least one compound selected from the group consisting of compounds represented by the above formula (1),
A resin composition comprising a hydrolyzable silyl group-containing polymer and calcium carbonate.

The present invention also provides a resin composition comprising at least one selected from the group consisting of compounds represented by the formula (2), an isocyanate group-containing polymer, and calcium carbonate. I do.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The compound represented by the formula (1) or (2) of the present invention is a compound suitable for being added to a curable resin composition containing calcium carbonate. Here, a resin composition containing at least one selected from the group consisting of the compounds represented by the formula (1), a hydrolyzable silyl group-containing polymer, and calcium carbonate is provided as a resin composition A. A resin composition comprising at least one selected from the group consisting of the compounds represented by the formula (2), an isocyanate group-containing polymer, and calcium carbonate, as a resin composition B, Each composition will be described in detail including the details of the compound having the above structure of the present invention.

[0014] 1. Resin Composition A The resin composition A of the present invention comprises at least one compound selected from the group consisting of compounds represented by the formula (1) (hereinafter, referred to as compound A), calcium carbonate, and a hydrolyzable silyl group-containing compound. And a polymer. (I) Compound A The compound A of the present invention is represented by the following formula (1).

[0015]

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Here, in the formula (1), R ¹ has 1 to 1 carbon atoms.
8 is an alkylene group, a vinylene group or a phenylene group which may be branched, R ² is an alkyl group having 1 to 18 carbon atoms having a hydrolyzable silyl group, R ³ is a hydrogen atom,
It is an alkyl group having 1 to 18 carbon atoms, which may have a branched alkyl group, a phenyl group or a hydrolyzable silyl group.

R ¹ is a branched alkylene group having 1 to 18 carbon atoms, a vinylene group or a phenylene group, preferably a 1 to 8 branched alkylene group, a vinylene group or a phenylene group. From the viewpoint of synthesis, an ethylene group or a phenylene group is more preferable.

R ² is an alkyl group having a hydrolyzable silyl group and having 1 to 18 carbon atoms.
To 6 alkyl groups. The hydrolyzable silyl group is a group that causes a condensation reaction by using a catalyst or the like, if necessary, in the presence of moisture or a cross-linking agent.Examples include a silyl halide group, an alkoxysilyl group, and an alkenyloxysilyl group. Group, acyloxysilyl group, aminosilyl group,
Examples include an aminooxysilyl group, an oximesilyl group, and an amidosilyl group.

Among these, an alkoxysilyl group having a mild hydrolyzability is preferable, and a trimethoxysilyl group or a triethoxysilyl group is more preferable. Therefore, as R ² , specifically,
A preferred example is a trimethoxysilylpropyl group or a triethoxysilylpropyl group.

R ³ is a hydrogen atom, a C1-C18 alkyl group which may be branched, a phenyl group or a C1-C18 alkyl group having a hydrolyzable silyl group. Examples of the alkyl group having 1 to 18 carbon atoms which may be branched include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The alkyl group having a hydrolyzable silyl group include the same as R ^2. Accordingly, R ³ is preferably a hydrogen atom, a phenyl group, a trimethoxysilylpropyl group or a triethoxysilylpropyl group.

The compound A of the present invention is a compound obtained by reacting an acid anhydride represented by the following formula (3) with a primary amine or a secondary amine represented by the following formula (4).

[0022]

Embedded image Here, R ¹ , R ² and R ³ in the formulas (3) and (4) have the same meaning as in the formula (1).

The acid anhydride represented by the above formula (3) is specifically exemplified by succinic acid, adipic anhydride azelaic anhydride, sebacic anhydride, methylene succinic anhydride, maleic anhydride, citraconic anhydride. And cyclic aliphatic acid anhydrides such as tetrahydrophthalic anhydride and hexahydrophthalic anhydride, and aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride. Among them, succinic anhydride and phthalic anhydride are particularly preferred in terms of easy handling.

The primary amine or secondary amine represented by the above formula (4) is preferably a compound having the following structure (A1110, A1100 and A1100 manufactured by Nippon Unicar Co., Ltd.).
1170).

[0025]

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The compound A of the present invention comprises the above acid anhydride and
Secondary or secondary amine, preferably at room temperature to 6
It is obtained by reacting for 2 to 3 hours while stirring in a temperature range of 0 ° C.

The compound A of the present invention is preferably
Compounds 1 to 5 having the following structures.

[0028]

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(Ii) Hydrolyzable Silyl Group-Containing Polymer The hydrolyzable silyl group-containing polymer used in the present invention is a polymer having at least one hydrolyzable silyl group in the molecule, and May be present at the terminal in the molecule or at the side chain.

Specifically, a hydrolyzable silyl group-containing polyether, a hydrolyzable silyl group-containing polyester, a hydrolyzable silyl group-containing vinyl polymer, a hydrolyzable silyl group-containing polyester-modified vinyl polymer, Examples of the polymer include a hydrolyzable silyl group-containing organic polymer such as a degradable silyl group-containing diallyl phthalate-based polymer and a hydrolyzable silyl group-containing diaryl phthalate-based polymer.

In the case of the hydrolyzable silyl group-containing polyether, the main chain polyether is produced by a method of cationic polymerization or anionic polymerization using ethylene oxide, propylene oxide, butene oxide, tetrahydrofuran or the like as a raw material. Things.

When the main chain is a polyester, a carboxylic acid such as maleic acid, succinic acid, glutaric acid, adipic acid or phthalic acid, an anhydride thereof, an ester thereof or a halide thereof is mixed with a stoichiometric excess of ethylene. Glycol,
Polyester polyols prepared by reacting a polyol such as propylene glycol or glycerin, or lactone polyols obtained by ring-opening polymerization of lactones are used as useful polyester main chains.

The vinyl monomer used for producing the hydrolyzable silyl group-containing vinyl resin is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, polycarboxylic acid (maleic acid,
Esters of unsaturated carboxylic acids such as diesters or half esters of C1-C20 linear or branched alcohols such as fumaric acid and itaconic acid: styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4- Aromatic hydrogen chloride-based vinyl compounds such as hydroxystyrene and vinyltoluene: vinyl esters and allyl ester compounds such as vinyl acetate, vinyl propionate and diallyl phthalate: nitrile group-containing vinyl compounds such as (meth) acrylonitrile: glycidyl (meth) Epoxy group-containing vinyl compounds such as acrylate: amino group-containing vinyl compounds such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, vinylpyridine, and aminoethyl vinyl ether: (meth Acrylamide, itaconic acid diamide, alpha Echiru (meth) acrylamide, crotonic amide, diamide of maleic acid, fumaric acid diamide, N- vinylpyrrolidone, N- butoxymethyl (meth) acrylamide, N. Amide group-containing vinyl compounds such as N-dimethylacrylamide, N-methylacrylamide, and acryloylmorpholine: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) Acrylamide, Aronix 5700
(Manufactured by Toa Gosei Co., Ltd.), Placcol FA-1, Placcol FA-4, Pl
accol FN-1, Placcol FN-4, (Daicel Chemical Co., Ltd.)
Hydroxyl-containing vinyl compounds such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, etc., and their salts (alkali metal salts, ammonium salts, amine salts, etc.): unsaturated such as maleic anhydride Carboxylic acid anhydrides: Other vinyl compounds such as vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, maleimide, N-vinylimidazole, and vinyl sulfonic acid.
Alternatively, condensable cold-curable silicone rubbers having these hydrolyzable silyl groups as reactive groups, silicone varnishes, and organopolysiloxanes used as silicone varnishes for paints, and the like.

Examples of the hydrolyzable silyl group include a halogenated silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group and an amidosilyl group. In particular, an alkoxysilyl group having a mild hydrolyzability is preferable from the viewpoint of curability.

As the polymer having a hydrolyzable silyl group used in the present invention, any one of the above-mentioned polymers may be used alone.
More than one species may be used in combination, and specifically, MS polymer or Cyril manufactured by Kaneka Chemical Industry Co., Ltd., Exester manufactured by Asahi Glass Co., Ltd., or the like can be used.

(Iii) Calcium carbonate The resin composition A of the present invention contains calcium carbonate.
Calcium carbonate is not particularly limited, and conventionally known ones can be used.In particular, when surface-treated calcium carbonate is contained, the viscosity can be adjusted, and good initial thixotropy and storage stability can be obtained. It is preferable in that it can be performed.

As such calcium carbonate, conventionally known surface-treated calcium carbonate surface-treated with fatty acid, resin acid or fatty acid ester can be used. Further, calcium carbonate surface-treated with the compound A of the present invention may be used. Specifically, calcium carbonate surface-treated with fatty acids includes Calfine 20
0 (manufactured by Maruo Calcium Co., Ltd.), White Inn 305 (manufactured by heavy calcium carbonate, manufactured by Shiroishi Calcium Co., Ltd.), and Sealetz 200 (manufactured by Maruo Calcium Co., Ltd.) are preferably used as the calcium carbonate surface-treated with a fatty acid ester.

The resin composition A of the present invention may further comprise a plasticizer, a solvent, an antioxidant, an antioxidant, an antioxidant, a pigment, a dye, an antistatic agent, in addition to the above essential components, as long as the object of the present invention is not impaired. , A flame retardant, an adhesion-imparting agent, a dispersant and the like.

As the plasticizer, dioctyl phthalate (DOP), dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), dioctyl adipate,
Indecyl succinate, diethylene glycol benzoate, pentaerythritol ester, butyl oleate, methyl acetyl ricinoleate, tricresyl phosphate, trioctyl phosphate, propylene glycol adipate polyester, butylene glycol adipate polyester, and the like are used. These plasticizers may be used alone or in combination of two or more.

Examples of the solvent include ethyl acetate, butyl acetate, cellosolve acetate, mineral spirit,
Examples include toluene, xylene, dimethylacetamide, methyl ethyl ketone, acetone, n-hexane, methylene chloride, tetrahydrofuran, ethyl ether, dioxane and the like. One of these solvents may be used alone, or two or more thereof may be used in combination.

As antioxidants, butylhydroxytoluene (BHT), butylhydroxyanisole (BH)
A), triphenyl phosphite and the like. Examples of the antioxidant include hindered phenol compounds, benzotriazole compounds, hindered amine compounds, and the like.
The pigment may be an inorganic pigment or an organic pigment. As inorganic pigments, titanium dioxide, zinc oxide, ultramarine, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum,
Hydrochloride, sulfate and the like.

The compounding ratio of each component in the resin composition A of the present invention is such that calcium carbonate is 20 to 300 parts by weight, and compound A is 100 parts by weight of the resin component in the resin composition A.
Is suitably in the range of 0.1 to 10 parts by weight. When the calcium carbonate is within this range, the fluidity and dispersibility of the resin composition A are improved, and processing becomes easier. Further, Compound A varies depending on the amount of calcium carbonate to be blended, but within the range of 0.1 to 10 parts by weight, the dispersibility of calcium carbonate in the hydrolyzable silyl group-containing polymer is sufficiently increased, Excellent tensile properties, low residual strain and high elasticity can be imparted to the vulcanized rubber.

The method for producing the resin composition A of the present invention is not particularly limited. For example, the above-mentioned essential components and optional components are appropriately added to a reaction vessel, and the mixture is sufficiently mixed under reduced pressure using a stirrer such as a mixing mixer. And obtained by kneading.

In the resin composition A of the present invention thus obtained, the hydrolyzable silyl group of the compound A is the same as the hydrolyzable silyl group of the polymer containing a hydrolyzable group contained in the resin composition A. , And the carboxyl group of the compound A can interact with the calcium carbonate contained in the resin composition A.
Therefore, in such a resin composition A, the compound A of the present invention functions as a coupling agent, and the resin composition A
Can be improved in strength and modulus.

The resin composition A of the present invention can be used for various adhesives, pressure-sensitive adhesives, paints, sealing materials and the like. Compound A of the present invention can also be used as a surface treatment agent for calcium carbonate.

2. Resin Composition B The resin composition B of the present invention comprises at least one compound selected from the group consisting of compounds represented by the formula (2) (hereinafter, referred to as compound B), an isocyanate group-containing polymer, and calcium carbonate. Including.

(I) Compound B The compound B of the present invention is represented by the following formula (2).

[0048]

Embedded image Here, R ⁴ is an alkylene group having 1 to 18 carbon atoms which may be branched, a vinylene group or a phenylene group, and R ⁵ is an alkyl group having 1 to 18 carbon atoms having an oxazolidine structure.

R ⁴ is a branched alkylene group having 1 to 18 carbon atoms, a vinylene group or a phenylene group, preferably a branched alkylene group having 1 to 8 carbon atoms, a vinylene group or a phenylene group. From the viewpoint that the synthesis is easy, an ethylene group and a phenylene group are more preferable.

R ⁵ is a hydrocarbon group having an oxazolidine structure, for example, a compound represented by the following formula (5) or (6).

[0051]

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In the above formula, R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are a hydrogen atom or a C 1 to C 18 Represents any one of the above alkyl groups. Specifically, examples of R ⁶ include an alkyl group such as a methyl group, an ethyl group, and a dimethyl group, and an alkoxy group such as a methoxy group and an ethoxy group.

R ⁷ and R ⁸ may be the same or different from each other, and include an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-pentyl group (that is, a 1-methylbutyl group). Is mentioned. In particular, R ⁷ ,
It is preferable that one of R ⁸ is a hydrogen atom and the other is an isopropyl group or a 2-pentyl group.

Specific examples of the oxazolidine having an aliphatic group include 2-isopropyl-3-ethyloxazolidine (a) and 2- (1-methylbutyl) represented by the following formula:
-3-ethyloxazolidine (b). Specific examples of the oxazolidine having an aromatic group include 2-phenyl-3-ethyloxazolidine (c) and 2- (p-methoxyphenyl) -3-ethyloxazolidine (d) represented by the following formula. Among these, 2-phenyl-3-ethyloxazolidine (c) is particularly preferable in terms of curability and storage stability.

[0055]

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The compound B of the present invention is obtained by reacting the acid anhydride used in the above compound A with the corresponding hydroxyalkyl oxazolidine compound. Specific examples of the acid anhydride used for the compound B of the present invention include the same ones as those exemplified for the compound A, and preferably succinic anhydride and phthalic anhydride.

As the hydroxyalkyl oxazolidine compound, specifically, 2-isopropyl-3- (2-hydroxyethyl) oxazolidine (a '), 2- (1-methylbutyl) -3 represented by the following formula: − (2-
(Hydroxyethyl) oxazolidine (b '), 2-phenyl-3- (2-hydroxyethyl) oxazolidine (c'), 2- (p-methoxyphenyl) -3- (2-
(Hydroxyethyl) oxazolidine (d ').

[0058]

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The compound B of the present invention is prepared by dissolving the above acid anhydride and the compound represented by the formula (5) or (6) at a temperature at which the acid anhydride dissolves in the hydroxyalkyl oxazolidine compound, preferably at 80 to 140 ° C. And the reaction is carried out for 1 to 3 hours while stirring in the temperature range described above.

The compound B of the present invention obtained as described above is preferably a compound having the following structure.

[0061]

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(Ii) Isocyanate Group-Containing Polymer The resin composition B of the present invention contains an isocyanate group-containing polymer. Examples of the isocyanate group-containing polymer include urethane prepolymers obtained by reacting a polyol compound with an excess of a polyisocyanate compound (that is, an excess of NCO groups relative to OH groups).
Generally, 0.5 to 5% by weight of isocyanate groups are contained at the molecular terminals.

Examples of the polyisocyanate compound for producing such a urethane prepolymer include:
Aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, and polymethylene polyphenylene polyisocyanate; Aliphatic polyisocyanates such as methylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate; aryl aliphatic polyisocyanates such as xylylene diisocyanate; . These may be used alone or in combination of two or more.

As the polyol compound for forming the urethane prepolymer, a polyether polyol, a polyester polyol, another polyol, or a mixed polyol obtained by mixing these polyols can be used. As the polyether polyol, ethylene oxide,
Products obtained by addition polymerization of one or more compounds having two or more active hydrogens to one or more alkylene oxides such as propylene oxide, butylene oxide, styrene oxide, and tetrahydrofuran. it can. Examples of the compound having two or more active hydrogens include polyhydric alcohols, amines, and alkanolamines.

As the polyhydric alcohol, ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, 1,4-butanediol, 4,4′-dihydroxyphenylpropane,
Examples of amines such as 4'-dihydroxyphenylmethane and pentaerythritol include ethylenediamine and propanolamine, and examples of alkanolamines include ethanolamine and propanolamine.

As the polyester polyol,
One or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, or other low molecular weight polyols, and glutaric acid, adipic acid , Pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, or a condensation polymer with one or more low molecular carboxylic acids or oligomeric acids, and propionlactone, valerolactone, etc. Ring-opening polymers and the like.

Other polyols include polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, acrylic polyols and the like, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol and the like. Of low molecular weight polyols.

In obtaining such a urethane prepolymer having an isocyanate group at the molecular end formed by using a polyol compound and an excess of a polyisocyanate compound, the mixing ratio of the polyol compound and the polyisocyanate compound may be as follows. 1 equivalent of compound (OH equivalent)
Per equivalent of polyisocyanate compound 1.2 to 5 equivalents (N
CO equivalent), and more preferably 1.5 to 3 equivalents.

The urethane prepolymer is produced by mixing the two compounds at a predetermined ratio in the same manner as in a usual urethane prepolymer, and heating and stirring at 30 to 120 ° C., preferably 50 to 100 ° C. Done by

(Iii) Calcium carbonate Calcium carbonate contained in the resin composition B of the present invention is:
The same thing as the thing used for the above-mentioned resin composition A is used. Particularly, calcium carbonate surface-treated with fatty acids includes Calfine 200 (manufactured by Maruo Calcium Co., Ltd.), White Inn 305 (heavy calcium carbonate, manufactured by Shiroishi Calcium Co., Ltd.), and calcium carbonate surface-treated with fatty acid esters, Sealets 200 (manufactured by Maruo Calcium Co., Ltd.) or the like is suitably used, and by adding these, the viscosity can be adjusted and good initial thixotropy and storage stability can be obtained.

The resin composition B of the present invention can contain optional components in addition to the above essential components as long as the object of the present invention is not impaired. The optional components are exemplified by the resin composition A described above. The same ones are used.

The compounding ratio of each component in the resin composition B of the present invention is such that calcium carbonate is 20 to 300 parts by weight, and compound B is 100 parts by weight of the resin component in the resin composition B.
Is suitably in the range of 0.1 to 10 parts by weight. When the calcium carbonate is in this range, the fluidity and dispersibility of the resin composition B are improved, and processing becomes easier. Further, the compound B varies depending on the amount of calcium carbonate to be blended, but within the range of 0.1 to 10 parts by weight, the dispersibility of the calcium carbonate in the isocyanate group-containing polymer is sufficiently increased, and the excellent tensile strength is obtained. Properties, low residual strain, high elasticity, etc. can be imparted to the vulcanized rubber.

The resin composition B of the present invention is prepared in the same manner as the resin composition A described above. In the obtained resin composition B, the compound B of the present invention reacts with the isocyanate group of the isocyanate group-containing polymer in the resin composition B by a functional group formed by undergoing hydrolysis as shown in the following formula. can do.

[0074]

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On the other hand, the carboxyl group in compound B can interact with calcium carbonate, and as a result, the adhesive strength and modulus of the cured product of resin composition B can be improved.

The resin composition B of the present invention can be used for various adhesives, pressure-sensitive adhesives, paints, sealing materials and the like. The compound B of the present invention can also be used as a surface treatment agent for calcium carbonate. it can.

[0077]

The present invention will be specifically described below with reference to examples. 1. Resin composition A <Synthesis of compounds 1 to 5> Compounds 1 to 5 having the following structure
Was synthesized as follows.

[0078]

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In the composition shown in Table 1 below, succinic anhydride or phthalic anhydride was replaced with an aminosilane (A11
10, A1100 or A1170; manufactured by Nippon Unicar Co., Ltd.) for 2 hours with stirring in a temperature range of room temperature to 60 ° C. to obtain a target compound.

[0080]

[Table 1]

[0081]

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(Example 1) <Preparation method of resin composition A> Modified silicone sealant containing a hydrolyzable silyl group-containing polymer and calcium carbonate (Super One LM; manufactured by Yokohama Rubber Co., Ltd.) 100
0.5 parts by weight of the obtained compound 1 was added to the parts by weight, and the mixture was stirred and kneaded using a mixing mixer to obtain a resin composition A.
I got

<Evaluation of Physical Properties> Resin composition A obtained above
The two aluminum plates are bonded to an H-form in accordance with the method described in JIS A5757, and the tensile strength (T _B ), elongation (E _B ), 50% tensile stress (M ₅₀ ) after 7 days at 20 ° C. 1
The measurement of the 50% tensile stress (M ₁₅₀ ) was performed according to the method described in JIS A5557. Table 2 shows the results.

Example 2 A resin composition A was prepared in the same manner as in Example 1 except that Compound 2 was used instead of Compound 1, and the physical properties were evaluated. Table 2 shows the results.

Example 3 A resin composition A was prepared in the same manner as in Example 1 except that Compound 3 was used instead of Compound 1, and physical properties were evaluated. Table 2 shows the results.

Example 4 A resin composition A was prepared in the same manner as in Example 1 except that Compound 4 was used instead of Compound 1, and the physical properties were evaluated. Table 2 shows the results.

Example 5 A resin composition A was prepared in the same manner as in Example 1 except that Compound 5 was used instead of Compound 1, and the physical properties were evaluated. Table 2 shows the results.

(Comparative Example 1) Table 2 shows the evaluation of physical properties when only the modified silicone sealant (same as in Examples 1 to 5) was used.

[0089]

[Table 2]

From Table 2, it can be seen that in the resin composition A, the change in strength due to the addition of the above compounds 1 to 5 is greatly improved in Examples 2 and 3, and particularly in Example 3. Then there are some that have declined slightly. However, it can be seen that the tensile stress increases by 30% or more, and improves by 44% at the maximum.

[0091] 2. Resin Composition B Next, a resin composition B was prepared as follows, and physical properties were compared. <Synthesis of Compounds 6 and 7> Compounds 6 and 7 having the following structures were synthesized as follows.

[0092]

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In the formulation shown in Table 3 below, succinic anhydride or phthalic anhydride was combined with (2-phenyl-3- (2-hydroxyethyl) oxazolidine (in the table, referred to as an oxazolidine compound)) at 80-120 ° C. The reaction was carried out for 2 hours while stirring in the temperature range to obtain the target compound.

[0094]

[Table 3]

Examples 6 and 7 <Method for Preparing Resin Composition B> Polyurethane Sealant Containing Urethane Prepolymer Containing Isocyanate Group at Terminal and Calcium Carbonate (Seal 21; manufactured by Yokohama Rubber Co., Ltd.) 100 The resulting compound 6 was added in an amount of 0.5 part by weight or 1.0 part by weight with respect to part by weight, and stirred and kneaded using a mixing mixer to obtain a resin composition B.

<Evaluation of physical properties> Resin composition B obtained above
The two aluminum plates are bonded to an H-form in accordance with the method described in JIS A5757, and the tensile strength (T _B ), elongation (E _B ), 50% tensile stress (M ₅₀ ) after 7 days at 20 ° C. 1
The measurement of the 50% tensile stress (M ₁₅₀ ) was performed according to the method described in JIS A5557. Table 4 shows the results.

Examples 8 and 9 Resin composition A was prepared in the same manner as in Examples 6 and 7, except that Compound 7 was used in place of Compound 6, and the physical properties were evaluated. Table 4 shows the results.

Comparative Example 2 A resin composition was prepared in the same manner as in Examples 6 to 9 except that the compound 6 or 7 was not blended, and the physical properties were evaluated. Table 4 shows the results.

[0099]

[Table 4]

Table 4 shows that the addition of compound 6 or 7 to resin composition B significantly increased the strength in any of the examples. Also, the tensile stress has increased almost twice at the maximum, and the elongation also increases.

[0101]

As described above, the compound A of the present invention is contained in the resin composition containing the reactive polymer and calcium carbonate.
Or by adding B, the compound interacts with both the reactive polymer and calcium carbonate to enhance the dispersibility of calcium carbonate, and as a result,
The strength and modulus of the resin composition can be improved. Such a resin composition can be applied to various adhesives, pressure-sensitive adhesives, paints, sealing agents, and the like. Further, the compound of the present invention can also be used as a surface treatment agent for calcium carbonate.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroyuki Hosoda 2-1 Oiwake, Hiratsuka-shi, Kanagawa F-term in Yokohama Rubber Co., Ltd. Hiratsuka Works 4C056 AA01 AB01 AC02 AD01 AE01 BA08 BC04 4H049 VN01 VP01 VQ37 VR21 VR43 VU22 VW02 4J002 BC031 BC111 BC121 BD001 BD031 BE001 BF051 BG021 BG071 BG081 BG091 BG121 BH001 BQ001 CF271 CH051 CK021 DE237 EU226 EX076 FD020 FD070 FD090

Claims (4)

[Claims] 1. A compound represented by the following formula (1). Embedded image (In the formula (1), R ¹ is a branched alkylene group having 1 to 18 carbon atoms, a vinylene group or a phenylene group, and R ² is a C 1 to C 1 having a hydrolyzable silyl group.
8 is an alkyl group, R ³ is a hydrogen atom, and has 1 to 1 carbon atoms.
It is an alkyl group having 1 to 18 carbon atoms having 8 branched alkyl groups, phenyl groups or hydrolyzable silyl groups. ) 2. A compound represented by the following formula (2). Embedded image (In the formula (2), R ⁴ is a branched alkylene group having 1 to 18 carbon atoms, a vinylene group or a phenylene group, and R ⁵ has 1 to 1 carbon atoms having an oxazolidine structure.
8 alkyl groups. ) 3. A resin composition comprising at least one compound selected from the group consisting of the compounds represented by the formula (1), a hydrolyzable silyl group-containing polymer, and calcium carbonate. 4. A resin composition comprising at least one selected from the group consisting of compounds represented by the formula (2), an isocyanate group-containing polymer, and calcium carbonate.