JPH09310015A - Curable composition improved in adhesion to coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, excellent in adhesion to a coating material and further residual tack on the surface of a cured product and useful as a sealing compound, etc., by incorporating a specific silylamine compound in an oxyalkylene polymer. SOLUTION: This curable composition improved in adhesion to a coating material is obtained by incorporating (B) a silylamine compound containing a reactive silicon group in (A) an oxyalkylene polymer containing at least one reactive silicon group in one molecule. Furthermore, the silyl group is preferably a trialkylsilyl group bonded to nitrogen atom of amino group in the component B and, e.g. a compound of the formula [R<8> and R<9> are each H, a (substituted) 1-20C alkyl, a 6-20C aryl or a 7-20C aralkyl; R<10> is a (substituted)bifunctional hydrocarbon; R<3> is a 1-20C alkyl, a 6-20C aryl, etc.; X is hydroxyl group or a hydrolyzable group; (b) is 0 or 1-3] is preferably used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a moisture-curable composition having excellent paint adhesion and a method for improving the paint adhesion.

[0002]

2. Description of the Related Art Reactive silicon groups include, for example, -Si (O
CH ₃ ) ₃ is hydrolyzed by moisture or the like in the air, and is subjected to a silanol condensation reaction with another reactive silicon group via —Si (OH) ₃ or the like to form a siloxane bond (Si—O).
A group that produces —Si). (CH ₃ O) ₃ Si ~ ~ ~ ~ ~ ~ ~ ~ Si (OCH ₃ ) ₃ → [(HO) ₃ Si ~ ~ ~ ~ ~ ~ ~ ~ Si (OH) ₃ ] → (~ ~ ~ ~ SiO) ₃ Si ~~~~~~~~ Si (OSi ~~~) ₃ Therefore, the polymer having a reactive silicon group crosslinks and cures even at room temperature in the presence of moisture. Among such polymers, an oxyalkylene polymer such as polyoxypropylene having a main chain skeleton has a property of becoming a rubber elastic body by being hardened in a liquid state having a high viscosity at room temperature. Widely used in wood. Sealing material is filled and installed in the gaps (joints) of building materials such as wall materials,
It is used for hardening and closing the gap to keep it watertight and airtight. It may be desirable to apply a paint to the surface of the cured product of the sealing material, but the adhesion between the paint and the sealant surface is not always sufficient, especially when a solvent-based paint is used. There was a problem.

[0003]

The object of the present invention is to provide a cured product containing an oxyalkylene polymer having a reactive silicon group, which has a large adhesive force between the coating material and the sealant surface when the coating material is applied to the surface of the cured product. To provide a sex composition.

[0004]

As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by using a silylamine compound, and has completed the present invention. That is, the present invention contains (a) an oxyalkylene polymer containing at least one reactive silicon group in one molecule, and (b) a curable composition containing a reactive silicon group-containing silylamine compound. To a curable composition.

The cured product of the composition of the present invention is characterized in that it is excellent in coating adhesion and also in that the residual tack on the surface of the cured product is excellent. Further, the present invention provides (a) a surface of a cured product of a curable composition containing (a) an oxyalkylene polymer containing at least one reactive silicon group in one molecule, and (b) a reactive silicon group-containing silylamine compound. The present invention also relates to a method of applying a coating material to the surface of a curable composition containing an oxyalkylene polymer containing at least one reactive silicon group in one molecule, characterized in that the coating material is applied to

[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 ₃ SiO— (R ⁴ has 1 carbon atom
To 20 monovalent hydrocarbon groups, and three R ^{4 s} may be the same or different), and R ² or R ³ is 2 or more. When present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and X is 2
When there are more than one, they may be the same or different. a is 0, 1 or 2, b is 0,
1, 2 or 3 are shown respectively. Further, p groups represented by the general formula (3) and a in —SiR ² _2-a X _a O— (3) do not have to 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.

Of 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 as the component (a) may be linear or branched and has a molecular weight of 50.
0 to 50,000, more preferably 1,000 to 3
It is 0000. At least one reactive silicon group is preferably present in one molecule of the polymer, and preferably 1.1 to 5 reactive silicon groups are present. 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 number of alkyl groups may be one or more.
You may use together.

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. The alkyl group of R ⁷ may be one type or two or more types in combination, as in the case of R ⁵ .

The molecular chain of the vinyl-based copolymer is substantially composed of the monomer units of the formulas (5) and (6). This means that the total of the monomer units of formula (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 unit other than the formula (5) and the formula (6) which may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, 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 reactive silicon group-containing silylamine compound used in the present invention is a compound having a reactive silicon group and an amino group, and three hydrogen atoms or carbon atoms are contained in one silicon atom as a substituent of the amino group. A compound in which a silicon atom-containing group to which a hydrogen group is bonded is present. As an example of such a compound, a compound represented by the general formula (7) can be shown.

R⁸ _ThreeSi-NR⁹-R^Ten-SiR^Three _3-bX_b (7) (In the formula, R⁸Is a hydrogen atom, substituted or unsubstituted carbon number
An alkyl group having 1 to 20 and an aryl group having 6 to 20 carbon atoms.
A group selected from aralkyl groups having 7 to 20 carbon atoms
And they may be the same or different,
R⁹Is a hydrogen atom, or a substituted or unsubstituted C1-20
Alkyl group, aryl group having 6 to 20 carbon atoms or charcoal
A group selected from aralkyl groups having a prime number of 7 to 20, R^TenIs
A substituted or unsubstituted divalent hydrocarbon group, R^Three ,
X and b are the same as above. ) R⁸, R⁹Examples of include, for example, methyl group, ethyl group
Such as an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, etc.
Any cycloalkyl group, aryl group such as phenyl group,
Examples thereof include aralkyl groups such as benzyl group. R⁸And
R⁹Of these, a methyl group is particularly preferable. R^TenAs an example of
Is -CH_Two-, -CH_TwoCH_Two-, -CH_TwoCH_TwoCH_Two
-, -CH_TwoCH (CH_Three)-, -CH_TwoCH (C_TwoH_Five)
-, -CH _TwoC (CH_Three)_Two-, -CH_TwoCH_TwoCH_TwoCH_Two
-And the like.

Examples of such a reactive silicon group-containing silylamine compound include, for example, Me ₃ SiNHC ₃ H ₆ Si.
(OEt) ₃ , Me ₃ SiNHC ₃ H ₆ Si (OMe) ₃ ,
_{Me 3 SiNHC 2 H 4 NHC 3} H 6 Si (OMe) 3, Me
₃ SiNHC ₂ H ₄ N (SiMe ₃ ) C ₃ H ₆ Si (OMe)
₃ , Me ₃ SiNHC ₂ H ₄ NHC ₃ H ₆ SiMe (OMe)
₂ , Me ₃ SiNHC ₂ H ₄ N (SiMe ₃ ) C ₃ H ₆ SiM
e (OMe) ₂ , Me ₃ SiNHC ₂ H ₄ NHC ₂ H ₄ NHC
₃ H ₆ Si (OMe) ₃ , Me ₃ SiNHC ₂ H ₄ N (SiM
e ₃ ) C ₂ H ₄ NHC ₃ H ₆ Si (OMe) ₃ , Me ₃ SiN
HC ₂ H ₄ N (SiMe ₃ ) C ₂ H ₄ N (SiMe ₃ ) C ₃ H _{6
Si (OMe) 3, Me 3} SiN (CH 2 Ph) C 3 H 6 S
i (OMe) ₃ , Me ₃ SiN (Ph) C ₃ H ₆ Si (OM
e) ₃ , (MeO) ₃ SiC ₃ H ₆ N (SiMe ₃ ) C ₂ H _{4
NHC 3 H 6 Si (OMe)} 3, (MeO) 3 SiC 3 H 6 N
(SiMe ₃ ) C ₂ H ₄ N (SiMe ₃ ) C ₃ H ₆ Si (OM
e) _{3 and the} like can be increased, but the invention is not limited thereto.

When these reactive silicon group-containing silylamine compounds are used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the oxyalkylene polymer, preferable results are obtained. If the amount is less than 0.1 part by weight, the effect is difficult to obtain, and if it exceeds 10 parts by weight, it is economically disadvantageous. 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.

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. The amount of the filler used is preferably about 1 to 200 parts by weight, more preferably about 10 to 150 parts by weight, based on 100 parts by weight of the oxyalkylene polymer having a reactive silicon group.

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) a reactive silicon group-containing silylamine is not particularly limited, but specific examples include (a) an oxyalkylene polymer. (B) Reactive silicon group-containing silylamine may be added to the above, and if necessary, stirring conditions may be appropriately adjusted and uniformly dispersed. Further, a dispersibility improver may be used in combination, if necessary. In addition, a method of dissolving and mixing each component by using a mixer, a roll, a kneader or the like can be adopted. The curable composition comprising (a) an oxyalkylene polymer and (b) a reactive silicon group-containing silylamine is not particularly limited in physical properties after curing, but 100% tensile property of the cured product is 0.5 MPa or more. The curable composition described above is preferable because it exhibits good paint adhesion without impairing other mechanical properties.

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 1-2 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
Parts by weight, 55 parts by weight of DIDP (diisodecylphthalate) as a plasticizer, 100 parts by weight of surface-treated colloidal calcium carbonate as a filler, 20 parts by weight of titanium oxide, 2 parts by weight of aliphatic amide wax as an anti-sagging agent, 1 part by weight of an ultraviolet absorber. , 1 part by weight of light stabilizer, Me ₃ SiNHC ₂ H ₄ N (SiMe ₃ ) C ₃ H ₆ Si (O
Add 1 or 5 parts by weight of Me) ₃ (silylamine A) and 2 parts by weight of U-220 (product of Nitto Kasei Co., Ltd.) as a curing catalyst, and after sufficiently kneading, pass through a small 3 paint roll 3 times to cure A composition was obtained.

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 cured product of the composition obtained in the same manner was evaluated for tensile properties according to JIS K6251. The results are shown in Table 1. Table 1 Examples Comparative Examples 1 2 3 4 5 1 2 3 3 Additives Silylamine A 5 1------Silylamine B--3-----Silylamine C---4----Silylamine D-- --4---Amine A------3-Amine B-------3 Paint adhesion (%) 90 70 60 77 39 0 0 0 100% Stress at extension (MPa) 0.61 0.67 0.69 0.38 0.41 0.45 0.75 0.77 Strength at break (MPa) 1.90 2.20 1.67 1.42 1.65 1.49 2.39 1.81 Elongation at break (%) 460 500 370 710 720 560 460 340 Silylamine A: Me ₃ SiNHC ₂ H ₄ N (SiMe ₃ ) C ₃ H ₆ Si (OMe) ₃ Silylamine B: (MeO) ₃ SiC ₃ H ₆ N (SiMe ₃ ) C ₂ H ₄ N (SiMe ₃ ) C ₃ H ₆ Si (OMe) ₃ Silylamine C: Me ₃ SiN (CH ₂ Ph) C ₃ H ₆ Si (OMe) ₃ silylamine D: Me ₃ SiN (Ph) C ₃ H ₆ Si (OMe) ₃ amine A: NH ₂ C ₂ H ₄ NHC ₃ H ₆ Si (OMe) ₃ , N- (beta over aminoethyl) - .gamma.-aminopropyltrimethoxysilane amine _{B: (MeO) 3 SiC 3} H 6 NHC 2 H 4 NHC 3 H 6 Si (OMe) 3, N, N'- bis [3- (Torimetoki As silyl) propyl] ethylenediamine Example 3 paint adhesion improving _{agent, (MeO) 3 SiC 3 H} 6 N
(SiMe ₃ ) C ₂ H ₄ N (SiMe ₃ ) C ₃ H ₆ Si (OM
e) The same procedure as in Example 1 was carried out except that 3 parts by weight of ₃ (silylamine B) was used. The results are shown in Table 1.

Example 4 Me ₃ SiN (CH ₂ Ph) C was used as a paint adhesion improver.
Example 1 was repeated except that 4 parts by weight of ₃ H ₆ Si (OMe) ₃ (silylamine C) was used. The results are shown in Table 1. Example 5 Me ₃ SiN (Ph) C ₃ H ₆ was used as a paint adhesion improver.
Example 1 was repeated except that 4 parts by weight of Si (OMe) ₃ (silylamine D) was used. The results are shown in Table 1.

Comparative Examples 1 to 3 A silyl group-containing silylamine compound was not added as a paint adhesion improving agent, or a hydrolyzable silyl group-containing amine compound N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (amine A ) Is 3 parts by weight or N,
Example 1 was carried out in the same manner as in Example 1 except that 3 parts by weight of N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine (amine B) was used. The results are shown in Table 1.

Example 6 100 parts by weight of a propylene oxide polymer having an average number of 8,000 and a number average molecular weight of 8,000 containing 1.4 methyldimethoxysilyl groups per molecule and -Si (CH ₃ ) (OCH ₃ ) ₂ . 55 parts by weight of DIDP (diisodecyl phthalate) as a plasticizer, 100 parts by weight of surface-treated colloidal calcium carbonate as a filler, 20 parts by weight of titanium oxide, 2 parts by weight of aliphatic amide wax as an anti-sagging agent, 1 part by weight of an ultraviolet absorber, light stabilizer 1 parts by _{weight, Me 3 SiNHC 2 H 4 N} (SiMe 3) as coating adhesion improving agent C ₃ H ₆ S
5 parts by weight of i (OMe) ₃ (silylamine A) and 2 parts by weight of U-220 (product of Nitto Kasei) as a curing catalyst were added,
After sufficiently kneading, the mixture was passed through a small three-piece paint roll three times to obtain a curable composition.

3 mm of the composition obtained as described above
To a thickness of 23 ° C. and cured at 55% RH at 23 ° C., and after 1 day, coat the surface of the cured product with 5 types of commercial solvent-based paints and 4 types of commercial water-based paints with a brush, and after 7 days Using a Nichiban cellophane tape, 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. Table 2 shows the results. Table 2 Examples Comparative Examples 6 7 4 Additives Silylamine A 55 -Amine A--3 Paint adhesion (%) Water-based paint 100 100 55 Solvent-based paint 48 67 0 100% Stress at extension (MPa) 0.18 0.21 0.23 Breaking Tensile strength (MPa) 1.04 1.05 1.36 Elongation at break (%) 710 820 740 Silylamine A: Me ₃ SiNHC ₂ H ₄ N (SiMe ₃ ) C ₃ H ₆ Si (OMe) ₃ amine A: NH ₂ C ₂ H ₄ NHC ₃ H ₆ Si (OMe) ₃ N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane Example 7 Propylene oxide containing an average of 1.4 methyldimethoxysilyl groups per molecule and a number average molecular weight of 8,000. Number average molecular weight of 9.00 containing 50 parts by weight of polymer and an average of 2.2 methyldimethoxysilyl groups per molecule
A mixture of 50 parts by weight of a propylene oxide polymer of 0 was used, and Me ₃ SiNHC ₂ H ₄ N was used as a paint adhesion improver.
Example 5 was carried out in the same manner as in Example 5 except that 5 parts by weight of (SiMe ₃ ) C ₃ H ₆ Si (OMe) ₃ (silylamine A) was used. Table 2 shows the results.

Comparative Example 4 A silyl group-containing silylamine compound was not added as a coating adhesion improver, and instead, a hydrolyzable silyl group-containing amine compound, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, was added to the composition. Example 5 except that parts by weight were used
It carried out similarly to. Table 2 shows the results.

[0041]

Industrial Applicability As described above, the present invention can provide a composition having excellent paint adhesion. Also, a method with improved paint adhesion can be provided. Further, the cured product of the present invention is also characterized in that the surface residual tack is excellent.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C09D 171/02 PLQ C09D 171/02 PLQ C09K 3/10 C09K 3/10 G

Claims (3)

[Claims] 1. A curable composition comprising (a) an oxyalkylene polymer containing at least one reactive silicon group in one molecule, and (b) a silylamine compound containing a reactive silicon group. 2. The curable composition according to claim 1, wherein the silyl group in the silylamine compound is a trialkylsilyl group bonded to the nitrogen atom of an amino group. 3. A cured product of a curable composition containing (a) an oxyalkylene polymer containing at least one reactive silicon group in one molecule, and (b) a silylamine compound containing a reactive silicon group. A method of applying a coating material to the surface of an oxyalkylene polymer-containing curable composition containing at least one reactive silicon group in one molecule, which comprises applying the coating material to the surface.