JP3481279B2 - Moisture-curable composition with excellent storage stability - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-curable composition having excellent storage stability, and more particularly, to controlling the moisture content of fillers, plasticizers and the like added to the composition to an extremely low rate. The present invention relates to a moisture-curable composition having excellent storage stability, which can ensure good storage stability without strict water management.

[0002]

2. Description of the Related Art As a curable composition used for building sealants and the like, a polymer containing two or more isocyanate groups in one molecule and a compound containing a trialkylsilylthio group or a triphenylsilylthio group. The one-component moisture-curable composition containing the compound does not expand or foam during curing and has excellent curability as compared with the conventional one-component curable polyurethane composition. 14
It is proposed in Japanese Patent No. 5321. However, since the silylthio group reacts extremely easily with water, in order to maintain the storage stability of such a moisture-curable composition, the water content of these additives should be kept extremely low when blending fillers, plasticizers, etc. Strict water management is required. However, it is very difficult in practice to control the water content of these additives and the like, which is a serious problem in producing the moisture-curable composition.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and strictly controls the moisture content of fillers, plasticizers and the like added to the composition to an extremely low rate. It is an object of the present invention to provide a moisture-curable composition having excellent storage stability, which can ensure good storage stability without needing to perform proper water management.

[0004]

In order to achieve such an object, the moisture-curable composition of the present invention has a surface of a polyisocyanate compound, a compound having two or more silylthio groups in the molecule, and a fatty acid ester. Treated calcium carbonate and the following general formula (1)

[Chemical 3] (In the formula, R ¹ is a hydrogen atom , a fluorine atom or a carbon number 1
~ 20 monovalent organic groups, silicon-hydrogen bond , silicon-fluorine
It is bonded to a silicon atom through an elementary bond or a silicon-carbon bond. R ¹ is, for example, a methyl group , an ethyl group ,
Dodecyl group , aminoethyl group , vinyl group , methyl vinyl
Examples thereof include a group , an isobutyl group , a phenyl group , a benzyl group and a fluoro group. R ² is a monovalent organic group having 1 to 30 carbon atoms, such as a methyl group , a butyl group , and lauryl.
Group , stearyl group and the like . In the organic group,
Halogen atom, alkoxy group, nitrile group, acid amide
It may contain functional groups such as groups, ester groups, epoxy groups and the like.
Y is an oxygen atom or a nitrogen atom, n is 0, 1,
It is an integer selected from a few. ), Or the following general
Formula (2)

[Chemical 4] (Wherein, R ^3, R ⁴ and R ⁵ are, each independently represents an atom or atomic group in the same range as R ^1, R ⁶ is shows the atom or atomic group in the same range as R ^2, R ⁷ Has 1 carbon
~ 20 divalent organic groups are shown. R ⁷ is, for example, oxa
Examples thereof include a ryl group and a malonyl group. l and m are the number of repeating units, and n is 0 or a positive integer. ), A compound having at least one silyl ester group in the molecule is contained. Here, port
Two lysocyanate compounds and silylthio groups in the molecule
40 to 1 of calcium carbonate surface-treated with a fatty acid ester is added to 100 parts by weight of the mixture with the above compound.
It is preferably contained in a proportion of 20 parts by weight.

Further, with respect to 100 parts by weight of calcium carbonate surface-treated with a fatty acid ester, the general formula (1) :

[Chemical 5] (In the formula, R ¹ is a hydrogen atom , a fluorine atom or a carbon number 1
~ 20 monovalent organic groups, silicon-hydrogen bond , silicon-fluorine
It is bonded to a silicon atom through an elementary bond or a silicon-carbon bond. R ¹ is, for example, a methyl group , an ethyl group ,
Dodecyl group , aminoethyl group , vinyl group , methyl vinyl
Examples thereof include a group , an isobutyl group , a phenyl group , a benzyl group and a fluoro group. R ² is a monovalent organic group having 1 to 30 carbon atoms, such as a methyl group , a butyl group , and lauryl.
Group , stearyl group and the like . In the organic group,
Halogen atom, alkoxy group, nitrile group, acid amide
It may contain functional groups such as groups, ester groups, epoxy groups and the like.
Y is an oxygen atom or a nitrogen atom, n is 0, 1,
It is an integer selected from a few. ), Or the following general
Formula (2)

[Chemical 6] (In the formula, R ³ , R ⁴ And R ⁵ each independently represents an atom or atomic group in the same range as R ^1, R ⁶ is shows the atom or atomic group in the same range as R ^2, R ⁷ is C 1 -C
~ 20 divalent organic groups are shown. R ⁷ is, for example, oxa
Examples thereof include a ryl group and a malonyl group. l and m are the number of repeating units, and n is 0 or a positive integer. It is preferable that 0.1 to 10 parts by weight of the compound having at least one silyl ester group represented by the formula (1) is contained in the molecule.

The present invention will be described in detail below. The essential components of the present invention are the following four components.

(1) Polyisocyanate compound A polyisocyanate compound having the general formula RN
Is a compound having a structure represented by ═C═O. In the present invention, those having a molecular weight of 500 to 10,000 are preferable, and those having a molecular weight of 2,000 to 5,000 are more preferable from the viewpoint of curability and stable storage stability.

In the present invention, any polyisocyanate compound may be used, and specifically, m-phenylene diisocyanate, toluene-2,4-diisocyanate, hexamethylene-1,6-diamine. Isocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, naphthalene-1,5
-Diisocyanate, 1-methoxyphenyl-2,4-
Diisocyanates such as diisocyanate, diphenylmethane-4,4'-diisocyanate and 4,4'-biphenylene diisocyanate; 4,4 ', 4 "-triphenylmethane diisocyanate and toluene-
Triisocyanates such as 2,4,6-triisocyanate; 4,4'-dimethyldiphenylmethane-2,
Examples thereof include tetraisocyanate such as 2 ', 5,5'-tetraisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

(2) Compound having two or more silylthio groups in the molecule It imparts curability to the composition of the present invention, and any compound having two or more silylthio groups in the molecule is used in the present invention. The molecular weight is preferably 200 to 10,000, more preferably 300 to 3,000.
belongs to.

Specific examples of such a compound include:
Some examples are as follows. RR'R "SiS (CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ S ₂ ) _q -CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂
SSiRR'R "(wherein R 1, R ', and R" are alkyl groups having 1 to 6 carbon atoms, particularly a group selected from a methyl group, an ethyl group, a phenyl group, and a chloromethyl group; q is 0 to 25. of an integer) among other this _{compound, (CH 3) 3 SiS (} CH 2 CH 2 OCH 2 OCH 2 CH 2 S 2) r -CH 2 CH 2 OCH 2 OCH 2 CH 2
A compound of SSi (CH ₃ ) (where r is an integer of 1 to 10) is preferable.

Besides this, RR'R "SiS (CH ₂ CH ₂ O) s-CH ₂ CH ₂
SSiRR'R ", (wherein R, R ', R" are as described above; s is an integer of 0 to 50) RR'R "SiSCH ₂ COOCH ₂ C (CH ₂ OCOCH ₂ SSiRR'R") _2- (RR'R "SiSCH
₂ CH ₂ COOCH ₂ ) ₂ CC ₂ H ₅ (in the formula, R, R ′, and R ″ are as described above) and the like.

These compounds can be synthesized by reacting a known compound containing two or more thiol groups in the molecule with a commercially available silyl reagent to convert the thiol group into a trialkylsilylthio group. . This compound may be used alone or in combination of two or more.

[0013] and an isocyanate group in the polyisocyanate compound, the ratio of <br/> Ru silylthio group to play the hydrolyzed to thiol groups by moisture, the molar ratio of [silylthio groups] / [the isocyanate groups], 0 It is preferably adjusted in the range of 0.8 to 1.2.

(3) Calcium Carbonate Surface Treated with Fatty Acid Ester To impart thixotropy (thixotropy and slump resistance) to the composition of the present invention, it is added as a filler. The fatty acid ester as a surface treatment agent for calcium carbonate is preferably an ester of a higher fatty acid having 8 or more carbon atoms, for example,
Examples include stearyl stearate, lauryl stearate, stearyl palmitate, and lauryl palmitate.

In the present invention, the surface treatment of calcium carbonate with a fatty acid ester is for giving sufficient thixotropy. The method of surface treatment can be performed using a known method, and is not particularly limited. For example, a fatty acid ester is added to an aqueous slurry of calcium carbonate and kneaded to adsorb the fatty acid ester on the surface of calcium carbonate. A method can be mentioned.

[0016] In the present invention compositions, the content of the calcium carbonate is not particularly limited, polyisocyanurate Trainer
Compound having two or more silylthio groups in the molecule
Mixture with compound (in the examples, also with prepolymer
Say. ) It is preferable that the content is 40 to 120 parts by weight with respect to 100 parts by weight. This is because if it is less than 40 parts by weight, good thixotropy cannot be obtained, while if it exceeds 120 parts by weight, the viscosity becomes too high and the elongation of the cured product becomes poor. In the present invention, the water content of calcium carbonate surface-treated with a fatty acid ester added as a filler may be about 0.1%, and strict water management is not required. By including the following compound (4) as an essential component in the composition, as described below,
It is possible to obtain the composition of the present invention having storage stability as good as when the water content of calcium carbonate is about 1/10.

(4) The following general formula (1) or the following general formula
Compounds represented by (2) These compounds are represented by the following general formula (1)

[Chemical 7] (In the formula, R ¹ is a hydrogen atom , a fluorine atom or a carbon number 1
~ 20 monovalent organic groups, silicon-hydrogen bond , silicon-fluorine
It is bonded to a silicon atom through an elementary bond or a silicon-carbon bond. R ¹ is, for example, a methyl group , an ethyl group ,
Dodecyl group , aminoethyl group , vinyl group , methyl vinyl
Examples thereof include a group , an isobutyl group , a phenyl group , a benzyl group and a fluoro group. R ² is a monovalent organic group having 1 to 30 carbon atoms, such as a methyl group , a butyl group , and lauryl.
Group , stearyl group and the like . In the organic group,
Halogen atom, alkoxy group, nitrile group, acid amide
It may contain functional groups such as groups, ester groups, epoxy groups and the like.
Y is an oxygen atom or a nitrogen atom, n is 0, 1,
It is an integer selected from a few. ) Or the following general formula
(2)

[Chemical 8] (Wherein, R ^3, R ⁴ and R ⁵ are, each independently represents an atom or atomic group in the same range as R ^1, R ⁶ is shows the atom or atomic group in the same range as R ^2, R ⁷ Has 1 carbon
~ 20 divalent organic groups are shown. R ⁷ is, for example, oxa
Examples thereof include a ryl group and a malonyl group. l and m are the number of repeating units, and n is 0 or a positive integer. Table in)
At least one silyl ester group in the molecule
It is of compounds having.

This compound has a high hydrolysis reactivity, so that the hydrolysis reaction is preferentially carried out with respect to water in the composition system. That is, by adding this compound, the water content contained in calcium carbonate surface-treated with a fatty acid ester is
Prior to the reaction with the silylthio group in the compound (2), the hydrolysis reaction is first performed with the compound. Therefore, the water content of the calcium carbonate is 0.1
%, Most of it is used for the hydrolysis reaction rather than the reaction with the silylthio group, and as a result, the water content of calcium carbonate is about 1/10 of 0.01%. It is possible to obtain the composition of the present invention with equally good storage stability.

The compound of the general formula (1) is a corresponding halogenated silane compound SiR ¹ _n X _4-n (wherein X is a chlorine source).
And a halogen atom such as a bromine atom. ) And the corresponding carboxylic acid, carboxylic acid metal salt or carboxylic acid amide. The silicone oil represented by the general formula (2) is a known substance, some of which are commercially available. For example, trade name KF manufactured by Shin-Etsu Chemical Co., Ltd.
Sold as -910, X-22-800 or X-22-715.

In the composition of the present invention, one of the above (4)
The content of the compound represented by the general formula (1) or general formula (2) is not particularly limited, with respect to 100 parts by weight of calcium carbonate surface treated with a fatty acid ester, 0.1 to 10
It is preferably contained in a ratio of parts by weight . This is because if it is less than 0.1 parts by weight, there is no effect on the storage stability, and if it exceeds 10 parts by weight, the curing time is delayed.

The composition of the present invention is prepared by mixing the above-mentioned essential components by a predetermined amount and stirring and mixing. In particular, a silylthio group is incorporated into the molecule in a polyisocyanate compound.
The mixture which contains a compound having more than eight advance prepared, to this mixture, the calcium carbonate, and the
Cyril es represented by general formula (1) or general formula (2)
A compound having at least one or more ter groups in the molecule (hereinafter
Below, it may be referred to as a “silyl ester group-containing compound”.
It ) May be obtained by adding a predetermined amount of each of the above compounds and stirring and mixing.

In addition to the above-mentioned essential components, a filler, a plasticizer, a solvent, an adhesion-imparting agent, a stabilizer, a colorant and the like may be contained within a range not impairing the gist of the present invention. Fillers include, for example, normal calcium carbonate, talc, kaolin,
Zeolites, diatomaceous earth, vinyl chloride paste resins, glass balloons, vinylidene chloride resin balloons, etc. are available. Solvents include, for example, aromatic hydrocarbons such as toluene and xylene, hexane, heptane, aliphatic hydrocarbons such as octane, acetone, ketones such as methyl ethyl ketone, and ether esters such as cellosolve acetate.
(1) Polyisocyanate compound and (2) Siri
It is used in the range of 1 to 40% by weight based on the mixture with the compound having two or more ruthio groups in the molecule . Adhesion-imparting agents include silane coupling agents, stabilizers include hindered phenol compounds, and coloring agents include titanium white, carbon black, red iron oxide, and the like.

[0023]

In the moisture-curable composition of the present invention, a polyisocyanate compound, a compound having two or more silylthio groups in the molecule, calcium carbonate surface-treated with a fatty acid ester, and the above general formula (1) or general formula formula
Since the compound having at least one silyl ester group represented by (2) in the molecule is contained, the moisture contained in the calcium carbonate is prior to the reaction with the silylthio group. Since a hydrolysis reaction first occurs with the silyl ester group-containing compound, most of the above-mentioned hydrolysis rather than the reaction with the silylthio group even if the water content of the calcium carbonate is about 0.1%. It is used in the reaction, and as a result, it is possible to obtain the composition of the present invention having storage stability as good as that in the case where the water content of calcium carbonate is about 1/10, which is about 0.01%.

[0024]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

(Example 1-4) <Polyisocyanate compound and compound having two or more silylthio groups in the molecule (LP600)> A urethane prepolymer having a terminal NCO and a component obtained by modifying a polysulfide polymer terminal to a silylthio group. LP600 (manufactured by Toray Thiokol Co., Ltd.) was used. In this compound, hydrolysis by water regenerates a thiol group from a silylthio group, and this thiol group reacts with an isocyanate group to form a thiourethane bond, thereby cross-linking.

<Calcium Carbonate Surface-Treated with Fatty Acid Ester (Sealets 300)> Using "Sealets 300" (manufactured by Maruo Calcium Co., Ltd.) having a water content of 0.01% (Examples 1 and 2) and water Those having a rate of 0.1% (Examples 3 to 5) were selected. Sealets 300 has an average primary particle size of about 0.07 μm surface-treated with fatty acid ester and about 10% by weight of fatty acid ester.
It is calcium carbonate contained.

<Compound containing silyl ester group (KF91
0 or SIO-218)> fatty acid ester-modified silicone oil ( "KF91
0 "; manufactured by Shin-Etsu Chemical Co., Ltd. ( Examples 1 to 4 ) and a fatty acid ester-modified organopolysiloxane compound (" SIO
-218 "; manufactured by Yokohama Rubber Co., Ltd. ( Example 5 ) was used.

Table 1 shows the compounding ratio of each of these components. A mixture (“LP600”) of a polyisocyanate compound in the number of parts by weight shown in Table 1 and a compound having two or more silylthio groups in the molecule was placed in a container with a stirrer, and calcium carbonate surface-treated with a fatty acid ester was added thereto. The silyl ester group-containing compound was added, and the mixture was stirred at 55 ° C. for 60 minutes and mixed to obtain a moisture-curable composition of the present invention.

Comparative Example 1 A moisture-curable composition was obtained in the same manner as in Example 1 except that the silyl ester group-containing compound was not added.

Comparative Example 2 A moisture-curable composition was obtained in the same manner as in Example 3, except that the silyl ester group-containing compound was not added in Example 3.

Using the moisture-curable compositions of Examples and Comparative Examples thus obtained, the following tests were conducted and evaluated at the initial stage and after 24 hours.

<Viscosity> The viscosity was examined using a B-type viscometer (rotor No. 7, measured at 20 ° C.). “Initial” refers to the viscosity (poise) when the composition is cooled to room temperature after being manufactured, and is “70 ° C. × 24
“Time” means 2 hours after the composition is kept at 70 ° C. for 24 hours.
Viscosity (poise) when cooled to 0 ° C.

<T. F. T (tack free time (when cured
Between). )> A polyethylene sheet was lightly applied to the surface of the composition at intervals of 30 minutes, and the time was taken until the composition did not adhere to the polyethylene sheet . "Initial" means a T.V. when a polyethylene sheet is applied at 30-minute intervals after the composition is cooled to room temperature after production. F. T evaluation, "70 ° C x 24 hours"
Is the T.V. when the composition is held at 70 ° C. for 24 hours, cooled to 20 ° C., and then a polyethylene sheet is applied at 30-minute intervals. F. It is a T evaluation.

[0034] * 1) Prepolymer containing a polyisocyanate compound and a compound having two or more silylthio groups in the molecule (Toray Thiokol Co., Ltd.) * 2) Fatty acid ester surface-treated calcium carbonate * 3) Fatty acid ester modified silicone oil * 4) Fatty acid ester modified silicone compound (manufactured by Yokohama Rubber Co., Ltd.)

As is clear from Table 1, the moisture-curable composition of the present invention has a water content of 0.01% even when a silyl ester group-containing compound having a water content of 0.1% is used. It is clear that it has the same degree of curability as when used. Further, this curability does not change either immediately after the production of the composition or after 24 hours of production, and it is clear from the table that the composition of the present invention has excellent storage stability.

[0036]

As described in detail above, according to the present invention,
Excellent storage stability, which can ensure good storage stability without strict water management that keeps the water content of fillers and plasticizers added to the composition to an extremely low rate. There is an effect that a moisture-curable composition is provided.

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Claims (3)

(57) [Claims] 1. A polyisocyanate compound, a compound having two or more silylthio groups in the molecule, calcium carbonate surface-treated with a fatty acid ester, and the following general formula (1): (In the formula, R ¹ is a hydrogen atom, a fluorine atom or a carbon number 1
~ 20 monovalent organic groups, silicon-hydrogen bond , silicon-fluorine
It is bonded to a silicon atom through an elementary bond or a silicon-carbon bond. R ² is a monovalent organic group having 1 to 30 carbon atoms, Y is an oxygen atom or a nitrogen atom, and n is an integer selected from 0, 1, 2, and 3. ), Or
The following general formula (2) : (Wherein, R ^3, R ⁴ and R ⁵ are, each independently represents an atom or atomic group in the same range as R ^1, R ⁶ is shows the atom or atomic group in the same range as R ^2, R ⁷ Has 1 carbon
~ 20 divalent organic groups are shown. l and m are the number of repeating units, and n is 0 or a positive integer. ) A moisture-curable composition having excellent storage stability, containing a compound having at least one silyl ester group represented by the formula (1). 2. The polyisocyanate compound and the silicone
Mixture 1 with a compound having two or more ruthio groups in the molecule
The moisture-curable composition excellent in storage stability according to claim 1, comprising 80 to 200 parts by weight of calcium carbonate surface-treated with the fatty acid ester with respect to 00 parts by weight. 3. Based on 100 parts by weight of calcium carbonate surface-treated with the fatty acid ester, the compound of the general formula (1) or
The storage stability according to claim 1 or 2, which comprises 0.1 to 10 parts by weight of a compound having at least one silyl ester group represented by the general formula (2) in the molecule. Excellent moisture curable composition.