JPH0662803B2 - Curable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable composition having improved tensile properties after curing, surface properties, and dispersibility upon compounding.

(Prior Art and Problems) The present inventors have already found that a polymer having a reactive silicon functional group is useful as a sealing material, and have proposed a production method / composition thereof. A curable composition containing a polymer having a reactive silicon functional group is inexpensive and has excellent performance, but depending on the compounding composition, the tensile properties and surface properties after curing are insufficient. In addition, coal char coagulation occurs at the time of blending, and it is necessary to use a roll or the like to disperse the charcoal.

(Means for Solving the Problems) The inventors of the present invention have conducted extensive studies to improve the problem, and as a result, limit the calcium carbonate used as a compounding agent to impair other excellent performances. Therefore, they have found that the conventional drawbacks can be solved, and arrived at the present invention.

That is, the present invention relates to an organic polymer containing at least one reactive silicon functional group in one molecule and 0.05 to 1.0 μm.
The present invention relates to a curable composition characterized by containing as an active ingredient the uniform cubic calcium carbonate of.

Organic polymers having at least one reactive silicon functional group in the molecule, which are used in the present invention, are disclosed in JP-B-45.
-36319, 46-12154, 49-32673, JP-A-50-15659
9, 51-73561, 54-6096, 55-82123, 55-123
620, 55-125121, 55-131022, 55-135135, 5
It can be obtained by the method proposed in 5-137129 or the like, but preferably the main chain is essentially a polyether, polyester or ether-ester block copolymer and has a molecular weight of 300 to 30,000. Even more preferred are alkylene oxide polymers having a molecular weight of 500 to 15,000 and having reactive silicon functional groups attached to the ends of the molecule.

The reactive silicon functional group mentioned here causes a condensation reaction by using a catalyst or the like as necessary in the presence of moisture or a cross-linking agent such as a hydrolyzable group or a silanol group bonded to a silicon atom. It is a base.

Polyethers having at least one reactive silicon functional group in at least one molecule used in the present invention are, for example, compounds of the general formula And a silicon hydride compound represented by the general formula Wherein, Z is ^{-R 1 2 -, R 1 2} OR 1 2 -, (R ^{1 2} is the same or a divalent hydrocarbon group having a carbon number of 1 to 20 in heterologous) polyethers with platinum stroll having olefin groups represented by], chloroplatinic acid, platinum alcohol compounds, platinum olefinic complexone try , Platinum aldehyde complex, platinum ketone complex and the like can be produced by addition reaction using a platinum compound as a catalyst. In the ^{formula, R 1 0} to 20 carbon atoms
Same or different monovalent hydrocarbon groups, for example, alkyl groups such as methyl and ethyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl group; aralkyl groups such as benzyl group; ^{1 3)} ₃ SiO- encompasses triorganosiloxy groups cormorant represented by (R ^{1 3} represents a monovalent hydrocarbon group having 1 to 20 the same or different carbon atoms). In the formula, X represents a silanol group or a different or the same kind of hydrolyzable group, and is a halogen atom, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenyl group. Examples include oxy groups. Specific examples of the silicon hydride compound represented by the formula include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and trimethylsiloxydichlorosilane;
Trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1,3,3,5,5,
Alkoxysilanes such as 7,7-heptamethyl-1,1-dimethoxytetrasiloxane; Acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane; Bis (dimethylketoximate)
Methylsilane, bis (cyclohexyl ketoximate)
Ketoxymate silanes such as methylsilane and bis (diethylketoximate) trimethylsiloxysilane; dimethylsilane, trimethylsiloxymethylsilane, 1,1
Examples thereof include hydrosilanes such as dimethyl-2,2-dimethyldisiloxane; alkenyloxysilanes such as methyltri (isopropenyloxy) silane, but are not limited thereto.

In the above-mentioned production method, after reacting the silicon hydride compound of the formula with a polyether having the olefin group of the formula, a part or all of the X groups are further converted into another hydrolyzable group or a hydroxyl group. You can For example, when the X group is a halogen atom or a hydrogen atom, it is preferably converted into an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group, a hydroxyl group or the like for use. In the formula, R ^{1 1} is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom. Z is a divalent organic group having 1 to 20 carbon atoms which is the same or different and is preferably a hydrocarbon group or a hydrocarbon group containing an ether bond, an ester bond, a urethane bond or a carbonate bond, particularly a methylene group. . A specific method for producing a polyether having an olefin group represented by the formula is, for example, the method presented in JP-A-54-6097, or allylglycidyl when an epoxy compound such as ethylene oxide or propylene oxide is polymerized. An example is a method of introducing an olefin group into the side chain by adding an olefin group-containing epoxy compound such as ether and copolymerizing the compound.

The backbone of the polyether used in the present invention is essentially of the formula-
R ¹ —O— (wherein R ¹ is a divalent organic group, most of which is most effective when it is a hydrocarbon group having 1 to 8 carbon atoms). Those having a repeating unit are preferred. R ¹ is specifically -CH
_2- , —CH ₂ CH ₂ CH ₂ CH ₂ — and the like. It may be composed of only one kind of repeating unit, or a polyether composed of two or more kinds of repeating units is effectively used. Especially among them Is preferred. The polyether having a molecular weight of 300 to 30,000 can be effectively used, but a polyether having a molecular weight of 500 to 15,000 is preferable. Such polyethers can be produced by the methods disclosed in JP-A-53-129247 and JP-A-54-6097.

It is also possible to use two or more of the above organic polymers in combination.

Further, an organic polymer obtained by polymerizing a polymerizable monomer in the presence of the organic polymer can also be used. For the production method of the organic polymer, see JP-A-59-78.
223, JP-A-60-228516, and JP-A-60-228517, specifically, in the presence of an organic polymer having at least one reactive silicon functional group in the molecule. ,
General formula Vinyl-based monomer represented by 1 selected from the group consisting of vinyl monomers represented by
It can be obtained by polymerizing one kind or two or more kinds of polymerizable monomers.

Specific examples of the vinyl-based monomer represented by the general formula include ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, pyridine, styrene and chloro. Styrene, 2-methylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-acrylic acid
Ethylhexyl, 2-hydroxyethyl acrylate, benzyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, glycidyl methacrylate, acrylamide, Methacrylamide, n-methyl acrylamide and the like can be exemplified.

Specifically as the vinyl-based monomer represented by the general formula, Can be exemplified, but especially Is preferred.

The vinyl-based monomer may be used alone or in combination of two or more. These polymerizable monomers are polyether 100 containing reactive silicon functional groups.
It can be used in an amount of 0.1 to 1000 parts by weight, preferably 1 to 200 parts by weight, based on parts by weight.

The polymerization can be carried out by a usual method, and specifically, a method using a radical initiator, a method using ultraviolet rays, X-rays, γ-rays, irradiation or the like can be adopted. Specific examples of the radical initiator include benzoyl peroxide, bezoyl hydroperoxide, di-t-butyl peroxide and di-t-.
Peroxides such as butylhaldroperoxide, acetyl peroxide, lauroyl peroxide, hydrogen peroxide, etc .; azo compounds such as azo-bis-isobutyronitrile; persulfates, di-isopropylperoxy-dicarbonate Peroxidic compounds and the like. The solvent can be used if necessary. When used, a solvent inert to both the organic polymer having a reactive silicon functional group and the vinyl monomer is preferable, and specific examples thereof include ethers, hydrocarbons, acetic acid esters and the like. To be The polymerization temperature is not particularly limited, and in the case of the polymerization method and the method using a radical initiator, the optimum temperature can be set depending on the type of the initiator used, but it is usually preferably 50 to 150 ° C. If necessary, the polymerization degree of the vinyl-based monomer can be adjusted by using a chain transfer agent such as mercaptans and halogen-containing compounds. The vinyl-based monomer may be charged all at once, or may be charged separately or continuously for the purpose of adjusting the amount of heat generation.

Further, an organic polymer having a polymer of a specific vinyl monomer as a main chain and having a reactive silico functional group at the terminal can also be used. The method for producing the organic polymer is described in JP-A-59-1680.
Specifically disclosed in 14, specifically, a compound represented by the general formula as a radical polymerization initiator, an organic silicon compound selected from the group consisting of compounds represented by the general formula and a chain transfer agent, It is obtained by polymerizing an acrylic acid ester or a methacrylic acid ester represented by the following general formula and an unsaturated organosilicon compound monomer.

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms) As the component (C) used in the present invention, acrylic acid alkyl esters or methacrylic acid alkyl esters One of them may be used, or two or more thereof may be mixed and used. The alkyl group may be a branched alkyl group or an unbranched alkyl group. Specific examples of the alkyl group include methyl, ethyl, n-butyl, isobutyl, 1-ethylpropyl, 1-methylbenzyl, 2-methylpentyl, 3-
Methylbenzil, 1-ethylbutyl, 2-ethylbutyl, isooctyl, 3,5,5-trimethylhexyl, 2-
Examples thereof include alkyl groups such as ethylhexyl, decyl and dodecyl.

In the present invention, the component (C) may be partially replaced with another copolymerizable unsaturated monomer. Examples of the unsaturated monomer that can be substituted include styrenes such as styrene, α-methylstyrene, vinyltoluene and 2-chlorostyrene, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and 2-ethylhexyl vinyl ether, acrylic acid and methacrylic acid. Carboxyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, N-methylaminoethyl acrylate, acrylamide, N-methylol acrylamide, etc.
Acrylic acid compounds or methacrylic acid compounds containing functional groups such as hydroxyl group, epoxy group, amino group, amide group, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol methacrylate, trimethylolpropane Unsaturated monomers containing two or more functional groups capable of copolymerization in one molecule such as triacrylate, trimethylolpropane trimethacrylate, oligoester acrylate, methylenebisacrylamide, diallyl phthalate, maleic anhydride, and silicic acid. Cinnamic acid vinyl ester, vinyl pyridine,
Examples thereof include vinyl monomers having 2 to 30 carbon atoms such as acrylonitrile, methacrylonitrile, ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl acetate, butadiene and chloroprene, but are not limited thereto.

The amount of the other copolymerizable unsaturated monomer substituting the component (C) for 1 minute is about 50% (% by weight, the same applies hereinafter) or less.

The unsaturated organosilicon compound monomer of the component (D) used in the present invention is used for copolymerizing with the component (C) to introduce a silicon functional group into the main chain of the polymer. The silicon functional group in the component (E) or the component (F) is introduced at the terminal of the polymer, but the silicon functional group is not completely introduced at all the terminals. A small amount of the component monomers is used in combination. The component (D) may be one having at least one carbon-carbon double bond and at least one silicon atom bonded to a hydrolyzable group, and is typically a general formula. ^(Wherein, similarly to ^{R 6, R 8, X,} a is ^{the, R 1 2} is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably methylene, ethylene, propylene, butylene, hexylene, phenylene, Groups such as cyclohexylene, b is 0 or 1
Is shown). Specific examples of the monovalent hydrocarbon group represented by R ⁸ include groups such as methyl, ethyl, propyl, butyl and phenyl. Specific examples of the hydrolyzable group represented by X include halogen groups derived from fluorine, chlorine, bromine and iodine,
General formula: -OZ (In the formula, Z is an alkenyl group having 1 to 18 carbon atoms, a saturated or unsaturated hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon ether group, an acyl group or an N, N-amino group. Represents a group), an amino group, a general formula:-
ON = CR ^{1 0} ₂ (wherein, R ^{1 0} represents a monovalent hydrocarbon group having 1 to 20 carbon atoms), a ketoxime group represented by the general formula: -ON = CR ^{1 2} (wherein R 1 ^{1 2} 1-20 carbon atoms
Represents a divalent hydrocarbon group of), a ketoxime group represented by the general formula: ^{(Wherein, R 1 0} is as defined ^{above, R 1 4} 1 to 18 carbon atoms
The amide group and the like represented by Of the above X, an alkoxy group such as a methoxy group or an ethoxy group is particularly preferable from the viewpoint of easy handling.

Specific examples of the component (D) represented by the general formula include:
Vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltyldimethoxysilane, γ- Methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ
Examples include, but are not limited to, acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldiethoxysilane, and the like.

The amount of the component (D) used in the present invention is 100 parts of the component (C).
Usually 0.01 to 20 parts per part, but especially (C) component 1
The amount used is preferably 0.05 mol or less based on mol. Of course, the component (D) may not be used depending on the purpose.
When the amount of the component (D) used exceeds 20 parts, there is a drawback that the improvement in elongation due to the silicon functional group present at the terminal of the polymer molecule is small.

The component (E) used in the present invention is used as a chain transfer agent for introducing a silicon functional group at the molecular end of the polymer,
Conventional chain transfer agents containing silicon functional groups can be used. As typical commercially available chain transfer agents, compounds represented by the general formula or are mentioned. R ⁹ in this general formula or is preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, and specific examples thereof include groups such as methylene, ethylene, propylene, butylene, hexylene, phenylene and cyclohexylene. can give. R ⁸ , a
Is the same as the above, and X is the same as the above, but an alkoxy group such as a methoxy group and an ethoxy group is particularly preferable from the viewpoint of easy handling. Specific examples of the compound represented by the general formula or However, the present invention is not limited to these.

The amount of the component (E) used in the present invention is usually 0.01 to 20 parts per 100 parts of the component (C).
It is preferably 0.05 mol or less based on mol. If the amount of the component (E) used exceeds 20 parts, the molecular weight becomes too small. Depending on the purpose, the polymerization may be carried out without using the component (E), the molecular weight may be adjusted by using an ordinary chain transfer agent containing no silicon functional group without using the component (E), or The chain transfer agent and the component (E) may be used together to adjust the molecular weight.

The component (F) used in the present invention is a silicon group-containing radical polymerization initiator for introducing a silicon functional group at the molecular end of the polymer, and an azo-based or peroxide-based compound can be used. Of those compounds, the general formula (Wherein, R ^{8, X,} a are as defined above, R ^{1 5} is a divalent hydrocarbon group having 2 to 18 carbon atoms) compounds of azo represented by is preferable, particularly X is a methoxy group , Preferred for alkoxy groups such as ethoxy groups. Specific examples of such azo compounds include: Azobis-2- (6-methyldimethoxysilyl-2-cyanohexane) Examples thereof include, but are not limited to, azobis-2- (6-trimethoxysilyl-2-cyanohexane) and azobis-2- (6-methyldiacetoxysilyl-2-cyanohexane). In addition, specific examples of the peroxide compound include: And the like, but are not limited thereto.

The silicon functional group-containing radical polymerization initiator which is the component (F) may be used in an amount of 0.01 to 20 parts per 100 parts of the component (C), but only the component (F) is used as a radical polymerization initiator. The component (F) is not limited, and an azo-based or peroxide-based normal radical polymerization initiator containing no silicon functional group may be used in combination.

It is preferable that one molecule of the organic polymer of the present invention contains an average of 1.2 to 3.5 silicon functional groups. The average molecular weight used is from 100 to 100,000, and preferably one having an average molecular weight of from 3000 to 50,000.

Examples of main polymerization reaction of the monomer component used in the present invention are as follows.

(I) I · + nM → IMn · (ii) 2I-Mn · → I-M 2 n-I (iii) 2I-Mn → IMn -. 1 -M '+ IMn - 1 -M "(iv ) I-Mn. + Y-SH-> I-Mn-H + Y-S. (V) Y-S. + NM-> Y-S-Mn. (In the formula, I. is a polymerization initiator radical, M is a monomer, I-
Mn · is a polymerization developer radical in which n monomers are polymerized, M ′ and M ″ are molecular terminals generated from I-Mn _{- 1-} M ·, and Y is a general formula. (In the formula, R ⁸ , R ⁹ , X and a are the same as the above), Y-
S. is a radical generated from Y-SH, Y-S-Mn. Is Y-
S · represents a radical obtained by polymerizing n monomers. ) As shown in (i), the monomer M is polymerized by I · generated from the polymerization initiator to form I-Mn ·. Generated I-Mn
- or it generates _I-M 2 _n-I as shown in (ii),
As shown in (iii), a disproportionation reaction occurs and I-Mn _{- 1-}
M'and I-Mn _{- 1-} M "are produced. As shown in (iv), I-Mn-reacts with a chain transfer agent represented by Y-SH to produce I-Mn-H. The produced Y-S * reacts with the monomer M to become Y-Mn * in the same manner as I * shown in (i), and the Y-S-Mn * produced in (v) is I * shown in (ii).
-A recombination reaction similar to -Mn- or a disproportionation reaction as shown in (iii) is performed. As can be seen from the polymer reaction of (i) to (v) above, the use of a polymerization initiator radical I · having a silicon functional group in the radical I can increase the content of the silicon functional group at the terminal of the polymer molecule. As can be seen from the elementary reactions (iv) to (v), if a silicon functional group-containing chain transfer agent is used as the chain transfer agent, the reaction (i) takes precedence over the reaction (i).
Since the reaction of v) can occur, the content of silicon functional groups at the polymer molecule ends can be further increased. In particular, When such a chain transfer agent is used, a silicon functional group can be introduced into both ends of the polymer obtained by the reaction (iv), so that the silicon functional group content at the polymer molecular terminal can be further increased. When acrylic acid esters are used as M, the disproportionation reaction of (iii) tends to occur preferentially over the recombination reaction of (ii), so that it contains a silicon functional group such as M ′ or M ″. Unterminated terminals are considerably formed depending on the polymerization conditions, and in such a case, a curable composition having practically no problem can be obtained by copolymerizing the component (D) with a small amount of M.

In the case of polymerization, all the monomers of the component (C) and, if necessary, the component (D) may be charged all at once from the beginning of the polymerization. At first, only a part of the monomer is charged and the remaining monomer is charged. The monomer may be gradually charged by a dropping method as the polymerization reaction proceeds. The polymerization initiator as the component (F) and the chain transfer agent as the component (E) may be charged in the same manner as in the above-mentioned monomer. For example, only a part is initially charged, and the rest is dissolved in the monomer and charged. You may take a method. The polymerization is preferably performed by a bulk polymerization method which is performed without using a solvent, but a solution polymerization method using a solvent may be used. When a solvent is used, a solvent such as heptane, toluene or isopropanol may be used in an amount of 30 parts or less based on 100 parts of the total amount of the monomer, the polymerization initiator and the chain transfer agent. When the hydrolyzable group contained in the component (D), the component (E) and / or the component (F) is an alkoxy group, the composition is prepared by a usual emulsion polymerization method or suspension polymerization method. You can also do it.

In the present invention, among the above polymers, (a) at least one reactive silicon functional group is contained in one molecule, and the main chain is essentially of the formula —R ¹ —O— (wherein R ¹
Is a polyether containing a repeating unit represented by a divalent carbon-hydrogen group having 1 to 8 carbon atoms), and (b) in the presence of an organic polymer having at least one reactive silicon functional group in the molecule. (A) General formula (In the formula, R ² is a hydrogen atom, a halogen atom or a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ³ is the same group as R ² , a substituted or unsubstituted Monovalent aromatic hydrocarbon group, alkenyl group, carboxyl group, acyloxy group, alkoxycarbonyl group, nitrile group,
A vinyl-based monomer represented by the formula (1), which is a pyridyl group, an amide group, or a glycidoxy group, and (B) a general formula (In the formula, R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms selected from an alkyl group, an aryl group and an aralkyl group;
⁵ is an organic residue having a polymerizable double bond, X is a hydrolyzable group, a is an integer of 0, 1, 2) and is selected from the group consisting of vinyl monomers 1
Or a polymer obtained by polymerizing two or more kinds of polymerizable monomers, or (C) (C) the general formula (In the formula, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms.) 100 weight% of a monomer containing acrylic acid ester or methacrylic acid ester as a main component Parts, (D) 0 to 20 parts by weight of unsaturated organosilicon compound monomer, (E) general formula (In the formula, R ⁸ is a monovalent hydrocarbon group having 1 to 6 carbon atoms,
R ⁹ is a divalent organic group, X is a hydrolyzable group, a is 0, 1 or 2, and a compound represented by the general formula (In the formula, R ⁸ , R ⁹ , X, and a are the same as the above) 0 to 20 parts by weight of an organosilicon compound selected from the group consisting of the compounds: (In the formula, R ⁸ , R ⁹ , X, and a are the same as the above). A mixture of 0.01 to 20 parts by weight of a radical polymerization initiator having a group represented by )
Is used as a chain transfer agent, and a polymer obtained by polymerizing the unsaturated monomers (C) and (D) and having an organosilicon group at its terminal is used.

The organic polymer used in the present invention may be used alone or in combination of two or more kinds.

The uniform cubic calcium carbonate of 0.05 to 1.0 μm used in the present invention is, for example, JP-B-53-43694 and JP-B-54.
-28397, namely, carbon dioxide gas of a suspension of calcium hydroxide in which fine cubic calcium carbonate is added and mixed as a nucleating agent or a mixed water suspension in which an alkali metal carbonate is added thereto It is manufactured by successively growing crystals on the nucleating agent by spraying in an air stream. The calcium carbonate has few agglomerated particles and good dispersibility as it is, but it is desirable that the calcium carbonate is surface-treated with an organic substance or an inorganic substance in order to obtain better performance. Examples of the surface treatment agent include higher fatty acid-based organic substances,
Examples thereof include resin acid organic substances, aromatic carboxylic acid esters, and surfactants. In the present invention, it is preferable to use a higher fatty acid organic compound.

These uniform cubic calcium carbonates are polymers with at least one reactive silicon functional group per molecule.
It is necessary to use 10 to 300 parts by weight, more preferably 30 to 200 parts by weight, based on 0 parts by weight. If it is used in an amount of less than 10 parts, the effect of improving the tensile properties and surface properties of the resulting composition after curing are insufficient. When it exceeds 300 parts by weight, the physical properties such as tensile properties are remarkably deteriorated.

When curing the composition of the present invention, a curing catalyst may or may not be used, but when it is used, for example, a metal carboxylate such as dibutyltin dilaurate, dibutyltin phthalate, tin octylate, titanium naphthenate, etc. Titanic acid esters such as tetrabutyl titanate, tetralysopropyl titanate and triethanolamine titanate; amines and ammonium salts. These are used alone or in combination.

The composition of the present invention may further contain various fillers, plasticizers, additives and the like. As the filler, for example, kaolin, talc, silica, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, carbon black, etc. are used in addition to the calcium carbonate. As the plasticizer, dioctyl phthalate, butylbenzyl phthalate, chlorinated paraffin, epoxidized soybean oil and the like are used. As the additive, hydrogenated castor oil, an anti-sagging agent such as organic bentonite, a coloring agent, an anti-aging agent and the like are used.

(Effects of the Invention) The composition thus obtained can be usefully used as an adhesive, an adhesive, a paint, a molding material and a cast rubber material, a foam material, etc., in addition to the sealing material composition. it can. For example, when applied to a sealing material composition, if the above-mentioned curing catalyst and compound are kneaded in the absence of water, it will be stable for a long period of time if stored in a sealed state, and exposed to moisture in the air to accelerate. A one-pack type sealant composition which is cured to form a good rubber elastic body is obtained.

(Example) Hereinafter, the present invention will be described with reference to examples.

Examples 1 and 2 Comparative Examples 1 and 2 Average molecular weight 8,000, as end groups Polypropylene oxide having 80% of all terminal groups, calcium carbonate, dioctyl epoxyhexahydrophthalate, dioctyl phthalate, hydrogenated castor oil, oligoester acrylate, 2,2'-methylene-bis-
(4-methyl-6-ter-butylphenol), 2
(2'-Hydroxy-3 ', 5'-di-ter-butylphenyl) -5-chlorobenzotriazole was kneaded by passing it through three paint rolls a predetermined number of times with the composition shown in the table, and kneading the mixture. After that, tin laurylamine octylate, dioctyl phthalate, and calcium carbonate were added as a curing agent, and after kneading well, an H-type test piece was prepared according to JIS-A5758, and the tensile properties were measured.

In Table _{1, M 5 0, M 1 5} 0, T B, E B is the tensile properties, 50% modulus, respectively, 150% modulus, breaking strength at, showing the elongation at break.

Among the calcium carbonates shown in Table 1, Vigot-10 is a calcium carbonate manufactured by Shiraishi Industry Co., Ltd. which satisfies the conditions of the present invention and has the following powder properties.

Average particle size 0.10μm Whiteness 95.0% Apparent specific gravity 0.25g / ml BET specific surface area 14.4m ² / g pH 9.7 Oil absorption (boiled linseed oil) 30.0ml / 100g Whiten SB is manufactured by Shiraishi Industry Co., Ltd. Spindle-shaped calcium carbonate, CCR is an ultrafine calcium carbonate manufactured by Shiroishi Industry Co., Ltd., which does not satisfy the conditions of the present invention. As is clear from Table 1, when Vigot-10, which is a uniform cubic calcium carbonate, is used, the dispersibility is good and stable physical properties can be obtained with one roll pass, and elongation and strength at break are remarkably improved. It can be seen that a cure is obtained.

Reference Example 1 80% of all ends are 100 g of a reactive silicon-terminated propylene oxide polymer having an average molecular weight of 8200, which is a group, is placed in a reaction vessel, devolatilized under reduced pressure, purged with nitrogen, and then heated to 90 ° C. with stirring. Separately prepared n-butyl acrylate 92.2
g, γ-methacryloxypropyldimethoxysilane 2.8
A mixed solution of 5.0 g of 2,3'-azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added dropwise under a nitrogen atmosphere over 2 hours. 15 minutes and 30 minutes after the end of dropping, respectively, AIBN
Add 0.25 g each by dissolving in 4 times the weight of acetone. After the addition is completed, stirring is continued for 30 minutes to complete the polymerization reaction.

The obtained polymer was a viscous liquid with a slight yellow color and slightly turbidity. The amount of residual monomer by gas chromatography analysis (hereinafter abbreviated as GC analysis) was 0.5%, and the viscosity was 380 poise (23 ° C). Atsuta

Reference Example 2 80% of all ends are 100 g of a reactive silicon-terminated propylene oxide polymer having an average molecular weight of 8200 in a group is placed in a reaction vessel and devolatilized under reduced pressure.
After purging with nitrogen, warm to 90 ° C and stir. Separately prepared n-butyl acrylate 94.5
g, γ-mercaptopropyltrimethoxysilane 1.0 g, A
A mixed solution of 0.5 g of IBN is added dropwise under a nitrogen atmosphere for 2 hours. 15 minutes and 30 minutes after the end of dropping, AI
Dissolve 0.025 g of BN in 4 times the weight of acetone and add. After the addition is completed, stirring is continued for 30 minutes to complete the polymerization reaction.

The obtained polymer was a pale yellow, transparent viscous liquid, and the amount of residual monomer by GC analysis was 0.4% and the viscosity was 1920 poise.

Reference Example 3 The monomer mixture solution to be dropped is n-butyl acrylate 9
6.9g, γ-methacryloxypropyldimethoxysilane
0.3 g, γ-mercaptopropyldimethoxysilane 1.6 g,
Polymerization was performed under the same conditions as in Reference Example 2 except that the solution consisted of 0.5 g of AIBN.

The obtained polymer was a pale yellow, transparent viscous liquid, and the amount of residual monomer by GC analysis was 0.7%, and the viscosity was 490 poise (23 ° C).
It was.

Comparative Examples 3-5, Examples 3-5 100 parts by weight of the polymers obtained in Reference Examples 1-3, calcium carbonate, titanium oxide, dioctyl phthalate hydrogenated castor oil, styrenated phenol, benzotriazole-based UV absorber Was thoroughly mixed with three paint rolls three times in the composition shown in Table 2 and then separately prepared as a curing desolvent composed of tin octylate and laurylamine (the composition is shown in Table 2). ) And knead thoroughly.

An H-type test piece was prepared according to JIS-A5758 and the tensile properties were measured.

As is clear from Table 2, when Vigot-10, which is a uniform cubic calcium carbonate, is used, a remarkable effect of improving elongation at break and strength can be obtained.

Examples 6 to 8 and Comparative Examples 6 to 8 The components shown in Table 3 were mixed, stirred and uniformly dissolved. 25 g of the mixture was placed in a 200 ml four-necked flask which was replaced with dry nitrogen gas equipped with a stirrer and a cooling tube, and heated to 80 ° C. in an oil bath while passing nitrogen gas. Polymerization started after a few minutes and heat was generated, but after the heat generation became mild, the remaining mixture was gradually added dropwise using a dropping funnel to carry out polymerization. It took 3 hours to complete the dropping. The reaction was terminated when no exotherm was observed.

To 100 g of the composition, 10 g of dioctyl phthalate, 20 g of rutin-type titanium oxide and 80 g of calcium carbonate described in Table 3 were added and mixed with three paint rolls to prepare a paste. Dibutyltin dilaurate (2 g) and laurylamine (1 g) were added to the above paste, mixed well, poured into a mold with a depth of 3 mm, and cured in a dryer at 23 ° C x 55% RH x 7 days and further at 50 ° C x 7 days to cure. I got a product sheet.

JIS-3 K6301 standard No. 3 damper was punched from the obtained sheet, and a tensile test was carried out with an autograph at a tensile speed of 500 mm / min to measure the elongation rupture strength. The results are shown in Table 3.

In Table 3, MAPTMS is γ-methacryloxypropyltrimethoxysilane, MPTMS is γ-mercaptopropyltrimethoxysilane, Cat (1) is azobis-2- (6-trimethoxysilyl-2-cyanohexane), and VTES is Vinyltriethoxysilane, MPTES is γ-mercaptopropyltriethoxysilane, Cat (2) is azobis-2-
(6-methyldiethoxysilyl-2-cyanohexane), DSPTMS is _{(CH 3 O) 3 SiCH 2} CH 2 CH 2 -S-S-
CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ and Cat (3) are azobis-2
-(6-methyldiacetoxysilyl-2-cyanohexane).

As is clear from Table 3, the use of uniform cubic calcium carbonate, Vigot-10, gives a marked hardening in strength and elongation at break.

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Fumio Kawakubo 6-68-404 Nishiokuchiai, Suma-ku, Kobe City, Hyogo Prefecture (72) Inventor Katsuhiko Isayama 4-8-7 Chikushigaoka, Kita-ku, Kobe City, Hyogo Prefecture ( 56) References JP-A-52-73998 (JP, A) JP-A-59-78223 (JP, A) JP-A-56-104713 (JP, A) JP-B-54-28397 (JP, B2)

Claims (3)

[Claims] (A) At least one reactive silicon functional group is contained in one molecule, and the main chain is essentially of the formula -R ¹ -O-.
(In the formula, R ¹ is a divalent carbon-hydrogen group having 1 to 8 carbon atoms) A polyether containing a repeating unit, (b) having at least one reactive silicon functional group in the molecule In the presence of the organic polymer, (A) the general formula (In the formula, R ² is a hydrogen atom, a halogen atom or a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ³ is the same group as R ² , a substituted or unsubstituted Monovalent aromatic hydrocarbon group, alkenyl group, carboxyl group, acyloxy group, alkoxycarbonyl group, nitrile group,
A pyridyl group, an amide group, a glycidoxy group), and (B) a general formula (In the formula, R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms selected from an alkyl group, an aryl group and an aralkyl group;
⁵ is an organic residue having a polymerizable double bond, X is a hydrolyzable group, a is an integer of 0, 1, 2) and is selected from the group consisting of vinyl monomers 1
Polymer obtained by polymerizing one or more kinds of polymerizable monomers, and (c) (C) general formula (In the formula, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms.) 100 weight% of a monomer containing acrylic acid ester or methacrylic acid ester as a main component Parts, (D) 0 to 20 parts by weight of unsaturated organosilicon compound monomer, (E) general formula (In the formula, R ⁸ is a monovalent hydrocarbon group having 1 to 6 carbon atoms,
R ⁹ is a divalent organic group, X is a hydrolyzable group, a is 0, 1 or 2, and a compound represented by the general formula (In the formula, R ⁸ , R ⁹ , X, and a are the same as the above) 0 to 20 parts by weight of an organosilicon compound selected from the group consisting of the compounds: (In the formula, R ⁸ , R ⁹ , X, and a are the same as the above). A mixture of 0.01 to 20 parts by weight of a radical polymerization initiator having a group represented by )
As a chain transfer agent, at least one reactive silicon selected from the group consisting of a polymer having an organosilicon group at the terminal, which is obtained by polymerizing the unsaturated monomers (C) and (D). To 100 parts by weight of an organic polymer having a functional group, fine cubic calcium carbonate as a nucleating agent was added and mixed, or a suspension of calcium hydroxide or a mixed water suspension obtained by adding an alkali metal carbonate to the carbon dioxide gas was added. A uniform cubic calcium carbonate of 0.05 to 1.0 μm prepared by sequentially growing crystals on the nucleating agent by spraying in an air stream was used.
A curable composition comprising as an active ingredient a compounded amount of up to 300 parts by weight. 2. The organic polymer has a reactive silicon functional group at the end of the molecule and has a molecular weight of 500 to 15,000 (a).
The curable composition according to claim 1, which is a polymer of 3. The curable composition according to claim 1, wherein the organic polymer is a polymer of (C) in which the hydrolyzable group X is an alkoxy group.