JPH09302213A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition excellent in residual tack and tight adhesion to a coating material by blending a specified oxyalkylene polymer and a specified silicon compound. SOLUTION: This composition is obtained by blending an oxyalkylene polymer (A) which contains at least one reactive silicon group in the molecule and whose backbone preferably comprises a polymer composed mainly of propylene oxide and a silicon compound (B) which has at least one amino group and at least one trialkylsiloxy group in the molecule and which is represented by formula I (wherein R<8> is a 1-20C alkyl, etc.; R<9> to R<11> are each a 1-6C alkyl, etc.; Yd is aminated alkyl; X is hydroxyl, etc.; and (d) and (e) are each 1 or 2). A reactive silicon group can be introduced into the polymer A by any known method. For example, an oxyalkylene polymer (e.g. one having a number-average molecular weight of at least 6,000 and an Mw/Mn of at least 1.6) having functional groups, such as hydroxyl, epoxy and isocyanato groups, in the molecule is reacted with a compound having both a functional group reactive with these functional groups and a reactive silicon group.

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 which has excellent residual tack on the surface of a cured product and is excellent in coating adhesion when a coating is applied.

[0002]

2. Description of the Related Art Reactive silicon groups include, for example, -Si (O
A group represented by CH ₃ ) ₃ is hydrolyzed by water in the air or the like, and is silanol-condensed with another reactive silicon group through —Si (OH) ₃ to form a siloxane bond (Si—O—S).
It is a group that gives rise to i). Therefore, a polymer having a reactive silicon group cross-links and cures even at room temperature in the presence of moisture. Among such polymers, oxyalkylene polymers such as polyoxypropylene having a main chain skeleton have the property of being liquid at room temperature and becoming a rubber elastic body upon curing, and are widely used in building sealants and industrial sealants. ing. However, after filling and filling this in joints (gap between building materials such as wall materials), etc., residual tack (stickiness) remains on the surface of the cured product even after curing, causing surface contamination due to dust adhesion and aesthetically problematic. there were. Further, although the coating material may be applied to the surface of the cured product, the adhesion between the coating material and the sealant surface is not always sufficient, and there is a problem that it cannot be said to be sufficient especially when a solvent-based coating material is used.

[0003]

The object of the present invention is to provide a reactive silicon group which has a small residual tack on the surface of the cured product even after curing and has a large adhesive force between the coating and the sealant surface when the coating is applied. Another object of the present invention is to provide a curable composition containing the oxyalkylene polymer.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that a silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule as a surface modifier. It was found that the above problems can be solved by using, and the present invention has been completed.

That is, the present invention provides (a) an oxyalkylene polymer containing at least one reactive silicon group in the molecule and (b) at least one amino group and at least one trialkylsiloxy in the molecule. The present invention relates to a curable composition containing a silicon compound having a group.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The main chain skeleton of an oxyalkylene polymer containing (a) at least one reactive silicon group in one molecule contained in the present invention is essentially represented by the general formula (1).
Has a repeating unit represented by -R ¹ -O- (1) (In the formula, R ¹ is a divalent organic radical) R ¹ in the general formula (1) is 1 to 14 carbon atoms, more 2 to 4, linear or Branched alkylene groups are preferred. Specific examples of the repeating unit represented by the general formula _{(1), -CH 2 O -} , - CH 2 CH 2 O -, - CH 2 C
_{H (CH 3) O -,} - CH 2 CH (C 2 H 5) O -, - CH
_{2 C (CH 3) 2 O} -, - CH 2 CH 2 CH 2 CH 2 O- and the like. The main chain skeleton of the oxyalkylene polymer is 1
It may be composed of only types of repeating units, or may be composed of two or more types of repeating units. In particular, it is preferably composed of a polymer containing propylene oxide as a main component.

The reactive silicon group contained in the component (a) is a group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond. Representative examples of the general formula _{^{(2) - (SiR 2 2}} -a X a O) p -SiR 3 3-b X b (2) ( wherein, R ² and R ³ are both 1 carbon atoms 20 alkyl group, C6-20 aryl group, C7-2
0 aralkyl group or R ⁴ SiO— (R ⁴ is 1 to 1 carbon atoms
20 is a monovalent hydrocarbon group, and three R ^{4 s} may be the same or different), and a triorganosiloxy group represented by the formula (2) and two or more R ² or R ³ are present. When they do, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a is 0, 1, or 2, b is 0, 1, or
2 or 3 is shown, respectively. In addition, p general formulas (3)
The groups represented by -SiR ² _2-a X _a O- (3) need not be the same. p shows the integer of 0-19. However, it is assumed that (sum of a) + b ≧ 1 is satisfied. And a group represented by).

The hydrolyzable group represented by X above includes
There is no particular limitation, and any conventionally known hydrolyzable group may be used. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group,
A mercapto group and an alkenyloxy group are preferable, and an alkoxy group is particularly preferable from the viewpoint of mild hydrolyzability and easy handling.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 (the sum of a).
+ B is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms forming the reactive silicon group may be one, and
The number may be more than one, but in the case of silicon atoms connected by a siloxane bond or the like, about 20 may be present.

The reactive silicon group represented by the general formula (4) —SiR ³ _3-b X _b (4) (wherein R ³ , X and b are the same as above) is easily available. It is preferable from the point. Specific examples of R ² and R ^{3 in} the above general formulas (2), (3) and (4) include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group and phenyl group. aryl group, and aralkyl groups such as benzyl group, R ⁴ is a methyl group, triorganosiloxy group represented by R ⁴ ₃ SiO chromatography which is a phenyl group. A methyl group is particularly preferable as R ² and R ³ .

The introduction of the reactive silicon group may be carried out by a known method. That is, for example, the following method is used. (A) An oxyalkylene polymer having a functional group such as a hydroxyl group in a molecule is reacted with an organic compound having an active group and an unsaturated group reactive with the functional group to form an oxyalkylene group containing an unsaturated group. An alkylene polymer is obtained. Alternatively, an unsaturated group-containing oxyalkylene polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound. Then, the obtained reaction product is subjected to hydrosilylation by reacting hydrosilane having a reactive silicon group. (B) A compound having a mercapto group and a reactive silicon group is reacted with the unsaturated group-containing oxyalkylene polymer obtained in the same manner as in the method (a). (C) An oxyalkylene polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule is reacted with a compound having a functional group reactive with this functional group and a reactive silicon group. Among the above methods,
The method (a) or the method (c) of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is preferable. The polymer of the component (a) may have a linear or branched structure, and its molecular weight is about 500 to 50,000, more preferably 1,
000 to 30,000. At least one reactive silicon group is contained in one molecule of the polymer, preferably 1.
It is preferable that 1 to 5 exist. If the number of reactive silicon groups contained in the molecule is less than 1, the curability will be insufficient, and if it is too large, the network structure will be too dense and good mechanical properties will not be exhibited.

Specific examples of the component (a) include JP-B-45
No. 36319, No. 46-12154, JP-A-50-
156599, 54-6096, 55-137.
No. 67, No. 55-13468, No. 57-164123.
No. 3, Japanese Patent Publication No. 3-2450, US Pat. No. 3,632,5
57, US Patent 4,345,053, US Patent 4,
366, 307, those proposed in U.S. Pat. No. 4,960,844 and the like, and JP-A-61-1976.
No. 31, No. 61-215622, No. 61-21562
No. 3, No. 61-218632, the number average molecular weight of 6,000 or more, Mw / Mn is 1.6 or less high molecular weight and narrow molecular weight distribution oxyalkylene polymer can be exemplified. It is not particularly limited to these.

The above-mentioned oxyalkylene polymer containing a reactive silicon group may be used alone or in combination of two or more kinds. An oxyalkylene polymer obtained by blending a vinyl polymer having a reactive silicon group can also be used. The method for producing an oxyalkylene polymer obtained by blending a vinyl polymer having a reactive silicon group,
JP-A-59-122541 and 63-112642.
No. 6,172,631 and the like.
A preferred specific example is an acrylic acid ester monomer unit having a reactive silicon group and a molecular chain substantially having an alkyl group having 1 to 8 carbon atoms represented by the following general formula (5) and / or A methacrylic acid ester monomer unit and an acrylic acid ester monomer unit having an alkyl group having 10 or more carbon atoms represented by the following general formula (6) and / or
In this method, a oxyalkylene polymer containing a reactive silicon group is blended with a copolymer composed of methacrylic acid alkyl ester monomer units.

-CH_Two-C (R⁶) (COOR^Five)-(5) (In the formula, R^FiveIs an alkyl group having 1 to 8 carbon atoms, R⁶Is hydrogen
Child or methyl group) -CH_Two-C (R⁶) (COOR⁷)-(6) (In the formula, R⁶Is the same as above, R⁷Is an al having 10 or more carbon atoms
R represents a general formula (5)^FiveIs, for example, a methyl group,
Ethyl group, propyl group, n-butyl group, t-butyl group,
1 to 8 carbon atoms such as 2-ethylhexyl group, preferably
1-4, more preferably 1-2 alkyl groups are mentioned.
It is. Note that R ^FiveThe alkyl group of may be a single type or two or more types.
It may be mixed on top.

R ^{7 in the} general formula (6) is, for example, a lauryl group, a tridecyl group, a cetyl group, a stearyl group, an alkyl group having 22 carbon atoms, a behenyl group or the like having 10 or more carbon atoms, usually 10 to 30, Preferred is a long-chain alkyl group having 10 to 20. In addition, the alkyl group of R ⁷ may be a single kind or a mixture of two or more kinds as in the case of R ⁵ .

The molecular chain of the vinyl-based copolymer is substantially composed of the monomer units of the formula (5) and the formula (6), and the term "substantially" as used herein means the formula present in the copolymer. It means that the total of the monomer units of (5) and formula (6) exceeds 50% by weight. The total of the monomer units of formula (5) and formula (6) is preferably 70% by weight or more. The abundance ratio of the monomer unit of formula (5) and the monomer unit of formula (6) is 9 by weight.
5: 5 to 40:60 are preferable, and 90:10 to 60: 4.
0 is more preferable.

Examples of the monomer units other than the formulas (5) and (6) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, and N-. Monomers containing amide groups such as methylol acrylamide and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; other acrylonitrile, styrene, α -Methyl styrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

The copolymer has a number average molecular weight of 500 to 1
It is preferably 0,000 from the viewpoint of easy handling. The reactive silicon group contained in the copolymer is the same as the groups represented by the above (2) and (4). The number of reactive silicon groups in the copolymer is 1 or more on average from the viewpoint of obtaining sufficient curability, more preferably 1.1 or more, and particularly 1.5.
It is preferable that they are present in an amount of 300 or more and the number average molecular weight per apparent reactive silicon group is 300 to 4,000.

Further, as a method for producing an oxyalkylene polymer prepared by blending a vinyl polymer having a reactive silicon functional group, in the presence of an oxyalkylene polymer having a reactive silicon group, A method of polymerizing a (meth) acrylic acid ester-based monomer can be used. This manufacturing method is disclosed in JP-A-59-78223 and JP-A-59-78223.
No. 168,014, JP-A-60-228516, JP-A-60-228517, and the like, but the disclosure is not limited thereto.

The silicon compound having at least one amino group and at least one trialkylsiloxy group in the molecule used in the present invention can be represented by the general formula (7).

[0021]

Embedded image

(Where Y_dIs an alkyl having an amino group
Group, R⁸Is an alkyl group having 1 to 20 carbon atoms, 6 to 2 carbon atoms
0 aryl group, C7-20 aralkyl group or
R^FourSiO- (R^FourIs a monovalent hydrocarbon group having 1 to 20 carbon atoms
And three R^FourMay be the same or different
May also be present) represents a triorganosiloxy group,
R⁸When two or more exist, even if they are the same
Well, it may be different. X is a hydroxyl group, the same kind or
Different hydrolyzable groups or --O--SiQ_ThreeBase, but Q is water
Acid group, same or different hydrolyzable group, carbon number 1-2
0 substituted or unsubstituted monovalent organic group or triol
A group selected from a ganosiloxy group, which has a hydroxyl group and the same kind.
Or contains at least one different hydrolyzable group
You. R⁹, R ^TenAnd R¹¹Each independently, permuted or
Is an unsubstituted alkyl group having 1 to 6 carbon atoms and a phenyl group
A group selected from the following is shown. c is the same as above. d, e is 1
Or 2. ) A specific example of such a compound is γ-aminop
Ropyltrimethylsiloxydiethoxysilane, N- (β-
Aminoethyl) -γ-aminopropyl trimethylsiloxy
Dimethoxysilane, N- (β-aminoethyl) -γ-amino
Propyltrimethylsiloxymethylmethoxysilane, di
Ethylene triaminopropyl trimethylsiloxy dimeth
Xysilane, N, N-dimethyl-γ-aminopropyl trime
As a specific example of tylsiloxydimethoxysilane, etc.
I can do it.

Further, such a compound can be easily synthesized by reacting a silicon compound having at least one amino group and at least one hydrolyzable group in the molecule with a trialkylsilanol compound. At least one amino group and at least one in the molecule
As the silicon compound having one hydrolyzable group, γ-aminopropyltriethoxysilane (A-1100: Nippon Unicar Co., Ltd.), N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (A-1120: Nippon Unicar) Company product), N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane (KBM-602: Shin-Etsu Chemical Co., Ltd. product), diethylenetriaminopropyltrimethoxysilane (A-1130: Nippon Unicar Company product), N, N -Dimethyl-γ-aminopropyltrimethoxysilane (D52
00: Chisso product), N, N'-bis [γ-trimethoxysilylpropyl] ethylenediamine (XS1003: Chisso product), N-benzyl-γ-aminopropyltrimethoxysilane (X-12-512: Shin-Etsu Chemical product ), N
-Phenyl-γ-aminopropyltrimethoxysilane (K
BM573: manufactured by Shin-Etsu Chemical Co., Ltd.) can be exemplified, but not limited thereto.

Examples of the trialkylsilanol compound include, but are not limited to, trimethylsilanol, triethylsilanol, triphenylsilanol and the like. If desired, various plasticizers can be used in the composition of the present invention. When these additives are used in such a manner that the total amount of the plasticizer is in the range of 0.1 to 150 parts by weight based on 100 parts by weight of the oxyalkylene polymer, preferable results can be obtained. If the amount exceeds 150 parts by weight, the liquid component increases and the improvement effect cannot be obtained.

As the plasticizer, dioctyl phthalate,
Phthalates such as diisodecyl phthalate, dibutyl phthalate and butylbenzyl phthalate; epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil and benzyl epoxy stearate; polyesters of dibasic acid and dihydric alcohol Polyester plasticizers such as; Polyethers such as polypropylene glycol and its derivatives; Polystyrenes such as poly-α-methylstyrene and polystyrene; Polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, chlorinated A plasticizer such as paraffin can be optionally used alone or in the form of a mixture of two or more kinds.

Further, the composition of the present invention may contain a silanol condensation catalyst for promoting the reaction of the reactive silicon group. Examples of such silanol condensation catalysts include titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyl tin dilaurate, dibutyl tin maleate, dibutyl tin diacetate, octyl acid tin, naphthenate tin, dibutyl tin oxide and phthalic acid. Reaction products with esters, organic tin compounds such as dibutyltin diacetylacetonate; organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; bismuth-tris (2- Reaction products of bismuth salts such as ethylhexoate) and bismuth-tris (neodecanoate) with organic carboxylic acids; zirconium tetraacetylacetonate, titanium tetraa Chelate compounds such as chill acetonate; organic lead compounds such as lead octylate; organic vanadium compound; butylamine, octylamine,
Dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (Dimethylaminomethyl) phenol, morpholine, N-
Methylmorpholine, 2-ethyl-4-methylimidazole,
1,8-diazabicyclo (5,4,0) undecene-7 (DBU)
And the like; salts with amine compounds such as carboxylic acids and the like; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; reaction products of excess polyamine and epoxy compound; The condensation catalyst is not limited thereto, and a generally used condensation catalyst can be used. These silanol catalysts may be used alone or in combination of two or more. Among these silanol condensation catalysts, organometallic compounds or a combined system of organometallic compounds and an amine compound is preferable from the viewpoint of curability.

The amount of these silanol condensation catalysts used is
Oxyalkylene polymer having reactive silicon group 10
The amount is preferably about 0.01 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight, based on 0 parts by weight. If the amount of the silanol condensation catalyst used is too small relative to the oxyalkylene-based polymer, the curing rate becomes slow, and the curing reaction does not easily proceed sufficiently. On the other hand, if the amount of the silanol condensation catalyst used is too large relative to the oxyalkylene polymer, undesirably, local heat generation or foaming occurs during curing, making it difficult to obtain a good cured product.

The composition of the present invention may further contain a dehydrating agent, a compatibilizing agent, an adhesion improving agent, a physical property adjusting agent, a storage stability improving agent, a filler, an antiaging agent, an ultraviolet absorbing agent, if necessary. Various additives such as metal deactivators, antiozonants, light stabilizers, amine radical chain inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, flame retardants, antistatic agents, silane compounds, etc. Agents can be added as appropriate.

For example, when a filler is used as an additive,
Wood flour, walnut shell flour, rice hull flour, pulp, cotton chips, mica, graphite, diatomaceous earth, clay, kaolin, clay, talc, fumed silica, precipitated silica, silicic anhydride, quartz powder, glass beads, Calcium carbonate, magnesium carbonate, titanium oxide, aluminum powder, zinc powder, asbestos, glass fiber, carbon fiber and the like can be used. These fillers may be used alone or in combination of two or more.

In addition to (a) an oxyalkylene polymer containing at least one reactive silicon group in one molecule, another polymer having a reactive silicon group, such as polydimethylsiloxane, may be added. Good. The method for preparing the composition of the present invention comprising (a) an oxyalkylene polymer and (b) component is not particularly limited, but specific examples include addition to the (a) oxyalkylene polymer, If necessary, the stirring conditions and the like may be appropriately adjusted to uniformly disperse. Besides, a method of mixing using a mixer, a roll, a kneader or the like can be adopted.

The composition obtained as described above can be applied not only to a two-pack type curable composition but also to a one-pack type curable composition. In the latter case, it is obtained by preparing the composition of the present invention in a substantially water-free state, and when stored in a sealed state, can withstand long-term storage, and when exposed to the atmosphere, cures quickly from the surface. Start. INDUSTRIAL APPLICABILITY The composition of the present invention is useful as an elastic sealing material in the fields of construction, civil engineering, industrial use, etc., and can also be used as a paint, an adhesive, an injecting agent, and a coating material.

Hereinafter, the composition of the present invention will be described in more detail with reference to Examples.

[0033]

【Example】

Example 1 An average of 2.1 methyldimethoxysilyl groups per molecule, -S, in a kneading machine (planetary type mixer) capable of being closed.
Number average molecular weight 1 containing i (CH ₃ ) (OCH ₃ ) ₂
100 parts by weight of 7,000 propylene oxide polymer,
DIDP (diisodecyl phthalate) 55 as a plasticizer
Parts by weight, surface-treated calcium carbonate as filler 1
20 parts by weight, 20 parts by weight of titanium oxide are added, 2 parts by weight of an aliphatic amide wax as an anti-sagging agent, 1 part by weight of an ultraviolet absorber, 1 part by weight of a light stabilizer are added, and the mixture is stirred under vacuum at 120 ° C. for 2 hours. And dehydrated. After cooling to room temperature, 2 parts by weight of vinyltrimethoxysilane as a viscosity stabilizer, 2 parts by weight of U-220 (product of Nitto Kasei) as a curing catalyst, and N- (β-aminoethyl) -γ-aminopropyl as a surface modifier. 3 parts by weight of trimethylsiloxydimethoxysilane was added, and the mixture was stirred at room temperature. This was filled in a closed container to obtain a one-part curable composition. In Examples 1 to 3, the following evaluations were performed on the compositions thus obtained and those immediately after production and after storage at 50 ° C. for 14 days.

3 mm of the composition obtained as described above
And cured at 23 ° C. and 55% RH. After one day, the surface of the cured product is coated with five commercially available industrial solvent-based acrylic paints (three acrylic urethane-based paints, one acrylic lacquer, one acrylic enamel 1). Seed) was coated with a brush, and after 7 days, a grid test (25 pieces) was performed at 2 mm intervals using cellophane tape made by Nichiban. The evaluation was shown as a percentage (%) of the number of grids remaining on the sealant surface with respect to the total number of grids.

The residual tack (stickiness) is measured by
A composition obtained in the same way was spread to a thickness of 3 mm and 2
After curing at 3 ° C and 55% RH for 1 day and 7 days,
It was done by touching the surface with fingers. Furthermore, the tensile properties were evaluated according to JIS K6251. The results are shown in Table 1.

[0036]

[Table 1]

Examples 2 to 3 Example 1 was repeated except that the amount of N- (β-aminoethyl) -γ-aminopropyltrimethylsiloxydimethoxysilane used in Example 1 was changed to the amount shown in Table 1. did. The results are shown in Table 1. In Examples 2 and 3, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (A-1120) was used as a general adhesion-imparting agent.

Comparative Examples 1 to 2 In Example 1, instead of N- (β-aminoethyl) -γ-aminopropyltrimethylsiloxydimethoxysilane, N- (β-aminoethyl) -γ- which is a general adhesiveness-imparting agent. Aminopropyltrimethoxysilane (A-11
The same procedure as in Example 1 was performed except that 20) was used. The results are shown in Table 1. It can be seen from Table 1 that the composition of the present invention has excellent residual tack and paint adhesion on the surface of the cured product. The adhesiveness differs depending on whether the composition is stored or not, but the detailed cause is unknown.

[0039] Example 4-8 1 Average 2.1 single methyldimethoxysilyl groups per _{molecule, -Si (CH 3) (OCH} 3) 2, propylene oxide having a number average molecular weight 17,000 containing the polymer 100
By weight, 55 parts by weight of DIDP (diisodecyl phthalate) as a plasticizer, 120 parts by weight of surface-treated colloidal calcium carbonate as a filler, and 20 parts by weight of titanium oxide are added, 2 parts by weight of an aliphatic amide wax as an anti-sagging agent, and an ultraviolet absorber 1 1 part by weight of a light stabilizer, 2 parts by weight of vinyltrimethoxysilane as a viscosity stabilizer, 2 parts by weight of U-220 (product of Nitto Kasei) as a curing catalyst, and molecules shown in Table 2 as a surface modifier. A silicon compound having at least one amino group and at least one trialkylsiloxy group was added therein and stirred at room temperature. In this example, unlike Examples 1 to 3, dehydration under vacuum and filling in a closed container were not performed.

3 mm of the composition obtained as described above
To 23 mm and cured at 55% RH, and after 1 day, apply 5 kinds of commercial solvent-based industrial paint with a brush on the surface of the cured product, and after 7 days, use Nichiban cellophane tape to 2 mm A cross-cut test (25 pieces) of intervals was performed. The evaluation was shown as a percentage (%) of the number of grids remaining on the sealant surface with respect to the total number of grids. Table 2 shows the results.

[0041]

[Table 2]

Comparative Examples 3 to 4 N- (β-aminoethyl) -γ-aminopropyltrimethylsiloxydimethoxysilane of Example 4 was not added (Comparative Example 4) or, instead of this, N- (β-aminoethyl) -γ- Aminopropyltrimethoxysilane (A
1120) was used in the same manner as in Example 4 except that 3 parts by weight (Comparative Example 3) was used. Table 2 shows the results.

[0043] Example 9, the average per Comparative Example 5 1 molecule 2.1 or methyl dimethoxy silyl _{group, -Si (CH 3) (OCH} 3) 2, propylene oxide having a number average molecular weight 17,000 containing the polymer 100
U-220 (product of Nitto Kasei Co., Ltd.) as a curing catalyst in 2 parts
By weight, N- (β-aminoethyl) -γ-aminopropyltrimethylsiloxydimethoxysilane or N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (A-1120) was added as a surface modifier, and the mixture was stirred at room temperature.
The composition obtained as described above was spread to a thickness of 3 mm, cured under the conditions of 23 ° C. and 55% RH, and after 1 day, the surface of the cured product was coated with 5 kinds of commercial industrial solvent-based paints with a brush. ,
Seven days later, using a cellophane tape manufactured by Nichiban, a cross-cut test (25 pieces) at 2 mm intervals was performed. The evaluation was shown as a percentage (%) of the number of grids remaining on the sealant surface with respect to the total number of grids. The results are shown in Table 3.

[0044]

[Table 3]

[0045]

INDUSTRIAL APPLICABILITY As described above, the present invention can provide a curable composition having excellent residual tack and paint adhesion.

Claims (1)

[Claims] 1. An oxyalkylene polymer having at least one reactive silicon group in a molecule, and (b) having at least one amino group and at least one trialkylsiloxy group in a molecule. A curable composition containing a silicon compound.