JP2002285018A - Moisture-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture-curable resin composition of which the surface tackiness disappears in a short time as compared with the existing moisture- curable resin composition. SOLUTION: This moisture-curable resin composition is composed of 100 pts.wt. of an organic polymer (a) containing a silyl group and having at its molecular terminal or on its side chain at least one functional group having a silicon atom bound to a hydrolyzable group per molecule and 0.1-20 pts.wt. of a tin compound (b) of a carboxylic acid which is expressed in general formula (1) below (wherein, R<1> , R<2> , R<3> are each a 1-10C hydrocarbon group that may be identical or different) where the α carbon atom of the carboxylic acid is a tertiary carbon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-curable resin composition, and more particularly to a sealing agent which is cured in a short time after mixing a main component and a curing catalyst component, and in which surface tack is eliminated in a short time. The present invention relates to a two-component moisture-curable resin composition suitable for use as an adhesive or the like.

[0002]

2. Description of the Related Art As a curable resin composition useful as an adhesive or a sealing agent, a crosslinkable hydrolyzable resin having a main chain of polyether, polyester, or a polymer of an ethylenically unsaturated compound or a diene compound, etc. It is known to use an organic polymer having a silicon-containing group as a main component.
These are cured by forming siloxane bonds. The curable resin composition using the organic polymer having a hydrolyzable silicon-containing group is excellent in curability, storage stability, weather resistance, and the like. Examples of the curing catalyst for the organic polymer having a hydrolyzable silicon-containing group include tin (II) carboxylate compounds such as tin 2-ethylhexanoate and tin n-octylate; and organic catalysts such as dibutyltin dilaurate and dibutyltin maleate. Other organometallic compounds such as tin (IV) compounds, iron naphthenate, and lead octylate are used. Among them, organotin (IV) compounds and tin (II) carboxylate compounds are widely used because of their excellent curing speed and cured properties.

[0003]

However, since both organotin compounds and organolead compounds have a large effect on the environment and the human body, great care must be taken when using them. Conventionally, tin carboxylate (I-tin) such as tin 2-ethylhexanoate and tin-n-octylate is mainly used as an organic tin compound.
I) has been used (Japanese Patent Publication No. 61-60867), but all are carboxylic acids in which the carbon atom at the α-position of the carboxylic acid is a primary carbon or a secondary carbon, such as moisture in the air. And there is a problem that surface tack is not eliminated for a long time. Therefore, development of a curing catalyst having a practical curing speed and eliminating surface tack in a short time has been desired.

[0004]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of diligent research, 2
The present inventors have found a moisture-curable resin composition having a rapid curing property comparable to tin-ethylhexanoate, tin-n-octylate, etc., and in which the surface tack is eliminated in a short time, and completed the present invention.

That is, the present invention provides the following moisture-curable resin composition. (1) a group having a silicon atom bonded to a hydrolyzable group,
100 parts by weight of a silyl group-containing organic polymer (a) having at least one per molecule at a molecular terminal or a side chain, and the following general formula (1):

[0006]

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(Wherein R ¹ , R ² and R ³ are each a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ , R ² and R ³ may be the same or different from each other) Good)
A moisture-curable resin composition, wherein the carbon atom at the α-position of the carboxylic acid comprises 0.1 to 20 parts by weight of a carboxylic acid tin compound (b) which is a tertiary carbon. (2) A two-pack moisture-curable resin comprising a main component (A) containing the silyl group-containing organic polymer (a) and a curing catalyst component (B) containing the tin compound (b). The moisture-curable resin composition according to item (1), which is a composition. (3) In the above item (1) or (2), the silyl group-containing organic polymer (a) has a main chain of a polyether, a polymer of an ethylenically unsaturated compound, or a polymer of a diene compound. The moisture-curable resin composition according to the above. (4) The tin compound (b) is stannas bispivalate or stannas bisneodecanoate (1) to (1).
(3) The moisture-curable resin composition according to any one of the above items.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Organic polymer (a) used in the present invention
Is a group having a silicon atom bonded to a hydrolyzable group (hereinafter sometimes referred to as a silicon group bonded to a hydrolyzable group)
At the end or side chain of the molecule, at least 1
Organic polymer having a main chain of the polymer,
Examples include alkylene oxide polymers, polyethers, and ether / ester block copolymers. Also,
Examples include a polymer of an ethylenically unsaturated compound and a diene compound. These main-chain polymers are preferably liquid at room temperature.

The alkylene oxide polymer or polyether includes [CH ₂ CH ₂ O] n [CH (CH ₃ ) CH ₂ O] n [CH (C ₂ H ₅ ) CH ₂ O] n [CH ₂ CH those having one or more ₂ CH ₂ CH ₂ O] repeat units, such as n are exemplified. Here, n is an integer of 2 or more. These alkylene oxide polymers or polyethers may be used alone or in combination of two or more.

The polymers of the ethylenically unsaturated compounds and diene compounds include ethylene, propylene, acrylates, methacrylates, vinyl acetate,
Homopolymers such as acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene and the like, or copolymers of two or more of these. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid Ester copolymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylate, polymethacrylic acid Esters and the like. These may be used alone or in combination of two or more.

The silicon group bonded to the hydrolyzable 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 crosslinking agent. Specific examples 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. Here, the number of these hydrolyzable groups bonded to one silicon atom is selected from the range of 1-3. Further, the number of hydrolyzable groups bonded to one silicon atom may be one or more. Further, a hydrolyzable group and a non-hydrolyzable group may be bonded to one silicon atom. As the silicon group bonded to the hydrolyzable group, an alkoxysilyl group (including a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group) is particularly preferable in terms of easy handling. The silicon group bonded to the hydrolyzable group may be present at the terminal of the polymer molecule or may be present in a side chain. The silicon group bonded to the hydrolyzable group has at least one silicon group per molecule of the polymer.
Any number is sufficient, but from the viewpoint of curing speed and cured physical properties, it is preferable that the number is 1.5 or more per molecule on average. A known method can be adopted as a method for bonding the silicon group bonded to the hydrolyzable group to the main chain polymer.

The molecular weight of the organic polymer (a) used in the present invention is not particularly limited, but an excessively high molecular weight polymer has a high viscosity, so that it becomes difficult to use the curable resin composition when used. The number average molecular weight is desirably 30,000 or less.
Such an organic polymer can be produced by a known method, but a commercial product such as Kaneka MS polymer manufactured by Kaneka Chemical Industry Co., Ltd. may be used.

The curing catalyst (b) used in the present invention includes:
One or more of tin compounds of a carboxylic acid represented by the general formula (1) in which the carbon atom at the α-position of the carboxylic acid is a tertiary carbon (hereinafter, sometimes referred to as tin carboxylate) may be used. used. In the general formula (1), examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ , R ² , and R ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, Examples thereof include linear or branched alkyl groups such as heptyl, octyl, 2-ethylhexyl, nonyl, and decyl.

Among the tin carboxylate represented by the general formula (1), the following general formula (2):

[0015]

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(Wherein R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms). here,
In the tin carboxylate represented by the general formula (2), a carboxylic acid in which the carbon atom at the α-position is a tertiary carbon and at least two hydrocarbon groups at the α-position are methyl groups is generally a neocarboxylic acid. It is called. Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
Examples thereof include linear or branched alkyl groups such as ec-butyl, pentyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl.

Specific examples of the tin carboxylate include stannas bisneodecanoate, stannas bispivalate, stannas bisneopentanoate, stannas bisneohexanoate, stannas bisneoheptanoate, and stannasubi. Suneooctanoate, Stanas bisneo undecanoate, Stanas bisneododedecanoate, Stanas bisneotridecanoate, Stanas bisneotetradecanoate, etc., can be used alone or in combination. Such a compound can be produced by a known method. Among these tin carboxylate salts, stannabis bispivalate and stanna bisbis neodecanoate [stanas bis (2,2-dimethyloctanoate)] are preferred from the viewpoint of ease of handling during use and stability of the compound. preferable.

In the moisture-curable resin composition of the present invention, the curing catalyst (b) comprises a silyl group-containing organic polymer (a).
0.1 to 20 parts by weight, especially 0.5 to 100 parts by weight
It is preferably used in a proportion of 10 to 10 parts by weight. If the amount of the curing catalyst (b) is less than the above range, the curing performance is poor,
The surface tack may not be improved. If the ratio exceeds the above range, physical properties and stability of the cured product may be reduced.

In the moisture-curable resin composition of the present invention, various known amino group-substituted alkoxysilane compounds or condensates thereof may be used in order to promote curing and improve adhesion to a substrate. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, δ-aminobutyl (methyl) diethoxysilane, N, N′-bis (Trimethoxysilylpropyl) ethylenediamine and partial hydrolysates thereof. Also, to improve the adhesion to the substrate,
Vinyl alkoxysilane compounds such as vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltriisopropoxysilane can be used.

The moisture-curable resin composition of the present invention further comprises a curable composition such as a filler, a coloring agent, a plasticizer, a curing accelerator, a curing retarder, an anti-sagging agent, an antioxidant, and a solvent. You may add the additive normally added.

For example, specific examples of the curing accelerator include butylamine, octylamine, laurylamine,
n-hexadecylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine,
Oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, polyoxyethylenediamine, polyoxypropylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N -Methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-
Diazabicyclo (5.4.0) undecene-7 (DB
And amine-based organic compounds such as U).

Examples of the filler include calcium carbonate, kaolin, talc, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, clay, calcined clay,
Glass, bentonite, organic bentonite, shirasu balloon, glass fiber, asbestos, glass filament, crushed quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, titanium dioxide, and the like.

Specific examples of the coloring agent include iron oxide, carbon black, phthalocyanine blue, and phthalocyanine green.

Specific examples of the plasticizer include phthalic esters such as dibutyl phthalate, dioctyl phthalate and butyl benzyl phthalate; dioctyl adipate, dioctyl succinate, diisodecyl succinate, diisodecyl sebacate, butyl oleate and the like. Aliphatic carboxylic esters, esters of polyol compounds such as pentaerythritol ester, trioctyl phosphate,
Phosphates such as tricresyl phosphate, epoxidized soybean oil, epoxy plasticizers such as benzyl epoxystearate, chlorinated paraffin, and the like are used.

As the anti-sagging agent, specifically, hydrogenated castor oil, silicic anhydride, organic bentonite, colloidal silica and the like are used.

As other additives, there may be used an adhesion imparting agent such as a phenol resin and an epoxy resin, an ultraviolet absorber, a radical chain inhibitor, a peroxide decomposer, and various antioxidants.

The moisture-curable resin composition of the present invention comprises a main component (A) containing the silyl group-containing organic polymer (a).
And a curing catalyst component (B) containing the tin compound (b)
It is preferably used as a two-pack type moisture-curable resin composition comprising: The main component (A) includes, in addition to the silyl group-containing organic polymer (a), the amino-substituted alkoxysilane compound, vinylalkoxysilane compound,
One or more of a filler, a colorant, a plasticizer, a curing accelerator, a curing retarder, an anti-sagging agent, an adhesion promoter, an ultraviolet absorber, a radical chain inhibitor, a peroxide decomposer, an antioxidant, and a solvent, or Two or more can be appropriately blended. The curing catalyst component (B) includes, in addition to the tin compound (b), an amino-substituted alkoxysilane compound, a vinylalkoxysilane compound, a filler, a colorant, a plasticizer, a curing accelerator, a curing retarder, One or more of an inhibitor, an adhesion-imparting agent, an ultraviolet absorber, a radical chain inhibitor, a peroxide decomposer, an antioxidant, a solvent and the like can be appropriately compounded.

[0028]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the scope of the present invention is not limited thereto.

Production Example 1 Neodecanoic acid (2,2-dimethyloctanoic acid) 344.5 was placed in a 1000 ml eggplant flask equipped with a nitrogen inlet tube.
g (2 mol) and 170 g of an aqueous sodium hydroxide solution (sodium hydroxide: 2 mol) were weighed and sufficiently mixed with a magnetic stirrer.
Mol), and the mixture was reacted at 60 ° C. for 20 minutes. The reaction mixture was extracted with toluene and concentrated under reduced pressure to obtain a pale yellow transparent liquid tin compound a.

The compound was analyzed by FT-IR, and the absorption of the carbonyl group of neodecanoic acid at 1738 cm ^-1 was 165.
It shifted to 0 cm ^-1, and the absorption of tin carbonyl was confirmed.
In addition, from the results of the following elemental analysis, it was confirmed that the product was Stanas bisneodecanoate.

[0031]

Production Example 2 204 g (2 mol) of pivalic acid and 170 g (2 mol of sodium hydroxide) of an aqueous solution of pivalic acid were weighed into a 1000 ml eggplant flask equipped with a nitrogen inlet tube, and thoroughly mixed with a magnetic stirrer. Thereafter, 225 g (1 mol) of stannous chloride was added and reacted at 60 ° C. for 20 minutes. The reaction mixture was extracted with toluene and concentrated under reduced pressure to obtain a pale yellow transparent liquid tin compound b.

This compound was analyzed by FT-IR to find that the absorption of the carbonyl group of pivalic acid at 1,738 cm ^-1 was 1,650.
cm ⁻¹ and absorption of tin carbonyl was confirmed. In addition, the result of the following elemental analysis confirmed that the product was stannas bispivalate.

[0034]

Examples 1 to 8 With respect to 100 parts by weight of a silyl group-containing organic polymer (MS Polymer S810 manufactured by Kanegafuchi Chemical Industry Co., Ltd.), various additives shown in Table 1 were added in the number of parts shown in Table 1 ( Parts by weight) and kneaded to prepare a main component. On the other hand, Production Examples 1 and 2
Table 1 shows the tin compound a or b and various additives obtained in
(A part by weight based on 100 parts by weight of a silyl group-containing organic polymer (MS Polymer S810 manufactured by Kaneka Chemical Industry Co., Ltd.)) was mixed and kneaded to prepare a curing catalyst component.

For the moisture-curable resin composition obtained by mixing the obtained main component and the curing catalyst component, the snap time (time until the latter half of the mixing of the two components to gel and no fluidity) and the tack free time (both components) (Time until surface tack disappears after mixing). The preparation of the main component and the curing catalyst component, and the mixing and curing of both components were performed in a constant temperature room at room temperature of 25 ° C. and humidity of 60%. Table 1 shows the results.

Comparative Examples 1 to 4 Various additives shown in Table 1 were added to 100 parts by weight of a silyl group-containing organic polymer (MS Polymer S810 manufactured by Kaneka Chemical Industry Co., Ltd.) in the number of parts shown in Table 1 ( Parts by weight) and kneaded to prepare a main component. On the other hand, tin 2-ethylhexanoate or tin n-octylate, which has been conventionally used, and various additives are shown in Table 1 in terms of the number of parts (silyl group-containing organic polymer (MS Polymer S manufactured by Kaneguchi Chemical Industry Co., Ltd.)
810) 100 parts by weight) were mixed and kneaded to prepare a curing catalyst component.

With respect to the moisture-curable resin composition obtained by mixing the obtained main component and the curing catalyst component, the snap time and tack-free time were measured in the same manner as in Examples 1 to 8. Table 1 shows the results.

The details of the materials shown in Table 1 are as follows. MS Polymer S810: Silyl group-terminated polyether Calcium carbonate: Filler Nocrack NS-6: Antioxidant (manufactured by Ouchi Shinko Chemical Co., Ltd.) Smoyl P-350: Liquid paraffin (Muramatsu Oil Co., Ltd.)
Tinuvin 327: UV absorber (LF-101 manufactured by Tokyo Fine Chemical Co., Ltd.) A-171: Vinyl alkoxysilane compound (manufactured by Nippon Unicar Co., Ltd.) A-1100: Amino group-substituted alkoxysilane compound (Nihon Unicar Co., Ltd.) Laurylamine: First-class reagent manufactured by Kanto Chemical Co., Ltd. Bis (2-ethylhexanoic acid) tin: manufactured by Nitto Kasei Co., Ltd. Bis (n-octylic acid) tin: manufactured by Nitto Kasei Co., Ltd.

[0040]

[Table 1]

[0041]

As is clear from Table 1, when the moisture-curable resin composition of the present invention is used, the surface tack-free time is reduced as compared with the conventional moisture-curable resin composition. Such a moisture-curable resin composition is useful as a sealing agent, a coating agent, and an elastic adhesive.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 201/10 C09J 201/10 C09K 3/10 C09K 3/10 GZ (72) Inventor Hitoshi Tabuchi Osaka Prefecture 3-17-17 Nishi-Awaji, Higashi-Yodogawa-ku, Osaka F-term in Nitto Kasei Co., Ltd. (reference) 4H017 AA04 AA31 AB15 AC05 4J002 CH051 CP121 CP181 EG046 FD146 GJ01 GJ02 4J040 CA041 CA081 CA091 CA141 DA021 DA101 DA121 DA141 DB031 DE021 DF1 DF1 EE011 GA29 GA31 HB25 HC03 HC23 HC26 HD42 JB04 KA14 KA16 LA01 LA06 PA34

Claims (4)

[Claims] 1. A silyl group-containing organic polymer (a) having at least one group having a silicon atom bonded to a hydrolyzable group at a molecular terminal or a side chain per molecule, and 100 parts by weight of the following general formula: (1): (Wherein R ¹ , R ² and R ³ each have 1 to 10 carbon atoms)
Wherein R ¹ , R ² and R ³ may be the same or different from each other), wherein the carbon atom at the α-position of the carboxylic acid is a tertiary carbon. A moisture-curable resin composition comprising an acid tin compound (b) in an amount of 0.1 to 20 parts by weight. 2. A two-pack type moisture curing comprising a main component (A) containing the silyl group-containing organic polymer (a) and a curing catalyst component (B) containing the tin compound (b). The moisture-curable resin composition according to claim 1, which is a mold resin composition. 3. The organic polymer (a) containing a silyl group,
The moisture-curable resin composition according to claim 1 or 2, wherein the main chain is a polyether, a polymer of an ethylenically unsaturated compound, or a polymer of a diene-based compound. 4. The moisture-curable resin composition according to claim 1, wherein the tin compound (b) is stannas bispivalate or stannas bisneodecanoate.