JPH09291184A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable compsn. improved in pliability, stretchability and stain resistance by using an org. polymer contg. at least one hydrolyzable silicon group and a specific fluorocopolymer. SOLUTION: An organosilicon compd. cong. an isocyanate group and a hydrolyzable silicon group is reacted with a hydroxylated polyether to obtain an org. polymer (A) having at least one hydrolyzable silicon group of the formula: -SiXa R'3-a [wherein R' is a monovalent (un)substd. 1-20C hydrocarbon group; X is a hydroxyl group or a monovalent hydrolyzable group; and a is 1 to 3] per molecule to be crosslinkable by hydrolysis. A polymerizable monomer having a polyfluorohydrocarbon group is copolymerized with a polymerizable monomer contg. a functional group capable of introducing a photosetting functional group and other polymerizable monomer to obtain a fluorocopolymer (B) having a mol.wt. of 300 to 100,000 and polymerized units each having a polyfluorohydrocarbon group and polymerized units each having a photosetting functional group. 100 pts.wt. component (A) is blended with 0.1-20 pts.wt. component (B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a room temperature curable composition which gives a cured product having excellent stain resistance.

[0002]

2. Description of the Related Art Some examples of organic polymers having a hydrolyzable silicon group capable of forming a siloxane bond by hydrolysis and having a high molecular weight or cross-linking have been known in the past (for example, Japanese Unexamined Patent Publication (Kokai) No. 47820, JP-A-3-
72027, JP-A-3-79627, JP-B-61-49
332, Japanese Patent Publication No. 46-30711, Japanese Patent Publication No. 45-363
19, Japanese Patent Publication No. 46-17553).

However, these organic polymers have the following problems. When the modulus of the cured polymer or cured composition is lowered,
Even after the curing is completed, the surface becomes sticky, that is, tack remains, and when used as a base polymer such as a sealing material, it causes joint contamination such as dust adhesion and impairs the appearance of the building.

For the purpose of preventing this tack, for example, Japanese Patent Publication No. 3-3710 discloses a technique of adding a fluorosurfactant to an organic polymer having a hydrolyzable silicon group. However, in this composition, the fluorosurfactant is dispersed throughout the system even after curing, and migration to the surface is insufficient, so expensive fluorosurfactant is needed to reduce surface tack. It is necessary to use a large amount of the agent, which causes contamination around the sealing part and has a great adverse effect on water resistance and storage stability, so that the practical use thereof is greatly limited.

[0005]

The present invention seeks to overcome the aforementioned disadvantages. That is, it is an object of the present invention to provide a composition that gives a cured product having sufficient flexibility and stretchability, but having excellent surface stain resistance.

[0006]

The present invention is the following inventions. An organic polymer (A) having at least one hydrolyzable silicon group capable of being crosslinked by hydrolysis, and a polymer unit (p) having a polyfluorohydrocarbon group and a polymer unit having a photocurable functional group. A curable composition containing the fluorine-containing copolymer (B) having (q).

An organic polymer (A) having at least one hydrolyzable silicon group crosslinkable by hydrolysis, and a polymerized unit (p) having a polyfluorohydrocarbon group,
Polymerized units (q) and (p) having a photocurable functional group,
A curable composition containing a fluorocopolymer (B) having a polymerized unit (r) other than (q).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

[Organic Polymer (A)] As the organic polymer (A) having at least one hydrolyzable silicon group (hereinafter also simply referred to as a hydrolyzable silicon group) crosslinkable by hydrolysis in the present invention, Organic polymers derived from organic polymers selected from polyethers, polyesters and polycarbonates are mentioned. Also ethylene, propylene,
Hydrolysis with polymerizable monomers such as olefins such as isobutylene, (meth) acrylic acid esters, vinyl alkyl ethers, dienes such as butadiene and chloroprene, halogenated olefins such as chlorotrifluoroethylene and tetrafluoroethylene, etc. And a hydrolyzable silicon group-containing vinyl polymer obtained by copolymerizing a polymerizable silicon group-containing polymerizable monomer. In the present invention, for example, acrylic acid and methacrylic acid may be referred to as (meth) acrylic acid for convenience.

Particularly preferred is an organic polymer derived from an organic polymer selected from polyether, polyester and polycarbonate. Of these, hydrolyzable silicon group-containing polyethers derived from polyethers are particularly preferable.

The polyether can be obtained by subjecting an initiator containing active hydrogen to a ring-opening polymerization reaction of a cyclic ether in the presence of a catalyst. Propylene oxide as a cyclic ether,
Examples include ethylene oxide, butylene oxide, epichlorohydrin, styrene oxide, and allyl glycidyl ether. Also, oxetane, tetrahydrofuran, etc. can be used. These cyclic ethers are polymerized alone or 2
It is possible to polymerize in a random form or in a block form by combining two or more kinds.

As the initiator, polyhydric alcohols, polycarboxylic acids, polyvalent active hydrogen compounds such as polyamines, terminal unsaturated group-containing monools, unsaturated phenols, unsaturated carboxylic acid-containing unsaturated groups, etc. Examples include active hydrogen compounds.

As the catalyst, alkali metals such as sodium, potassium and cesium, alkali metal compounds such as hydroxides of these alkali metals, complex metal cyanide complexes and metal porphyrin complexes can be used.

The hydrolyzable silicon group-containing polyether is
It is particularly preferred that it is derived from a hydroxyl group-containing polyether. Preferred hydroxyl group-containing polyethers include polyoxyalkylene diols, polyoxyalkylene triols and polyoxyalkylene tetraols.
Also, an allyl-terminated polyoxyalkylene monool produced by using an initiator having an unsaturated group such as an allyl group can be used.

In the present invention, the hydrolyzable silicon group means
Like a silanol group or an alkoxysilyl group, a condensation reaction is caused by moisture, a curing catalyst, or the like to promote the high molecular weight by crosslinking the organic polymer, and the group represented by the formula 1 is preferable.

[0015]

Embedded image —SiX _a R ¹ _3-a ... Formula 1

In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a monovalent hydrolyzable group, and a is an integer of 1 to 3.

The hydrolyzable silicon group-containing polyether is
When derived from a hydroxyl group-containing polyether, the hydrolyzable silicon group represented by Formula 1 is usually introduced via an organic group. Therefore, the organic polymer (A) in the present invention preferably has a group represented by formula 2.

[0018]

Embedded image —R ⁰ —SiX _a R ¹ _3-a ... Formula 2

In the formula, R ⁰ is a divalent organic group, R ¹ , X and a
Is the same as above.

Here, R ⁰ in the formula 2 has 8 carbon atoms.
The following divalent hydrocarbon groups are preferred. R in formula 1 and formula 2
¹ is preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group, and particularly preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group or a phenyl group.

X in the formulas 1 and 2 is a hydroxyl group or a monovalent hydrolyzable group, and examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an amide group,
It is an amino group, an aminooxy group, a ketoximate group or a hydride group. Of these, the hydrolyzable group having a carbon atom preferably has 6 or less carbon atoms, and particularly preferably 4 or less carbon atoms. Preferred X is an alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group or a propoxy group. In Formula 1 and Formula 2, a or 2 is preferably 2 or 3.

Examples of the method for producing the organic polymer (A) in the present invention include, but are not limited to, the following (a) to (f). In addition, (a) to (d)
It is a production example of a hydrolyzable silicon group-containing polyether,
(E) to (f) are production examples of the hydrolyzable silicon group-containing vinyl polymer.

(A) A method of reacting an organosilicon compound having an isocyanate group and a hydrolyzable silicon group with a hydroxyl group-containing polyether.

As a concrete organosilicon compound,
The compound of

[0025]

Embedded image (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NCO,
_{(CH 3 O) 3 Si (} CH 2) 3 NCO, (CH 3 O)
_{2 (CH 3) Si (CH} 2) 3 NCO, (CH 3 O) 3
_{SiNCO, (CH 3 O) 2} Si (NCO) 2.

(B) Formula HSiX _a R ¹ _3-a (wherein R ¹ ,
X and a are the same as the above), and a method in which a silicon hydride compound represented by the above and a polyether having an unsaturated group introduced at the terminal are reacted.

Here, as a method of introducing an unsaturated group,
Method in which OH of a hydroxyl group-containing polyether is OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon such as allyl chloride, or a compound having an unsaturated group and a functional group capable of reacting with a hydroxyl group Is reacted with a hydroxyl group-containing polyether to introduce an unsaturated group through an ester bond, a urethane bond, a carbonate bond or the like.

When the cyclic ether is polymerized in the production of the terminal hydroxyl group-containing polyether, a method of introducing an unsaturated group into the side chain by copolymerizing an unsaturated group-containing cyclic ether such as allyl glycidyl ether, or the initiation There is also a method of introducing an unsaturated group into the terminal by using a hydroxyl group-containing polyether produced by using a terminal unsaturated group-containing monol as an agent.

(C) A method in which a polyisocyanate such as tolylene diisocyanate is reacted with the end of the hydroxyl group-containing polyether to form an isocyanate group end, and then the W group of the silicon compound represented by the formula 3 is reacted with the isocyanate group. .

[0030]

## STR00005 ## W--R ² --SiX _a R ¹ _3-a ... Equation 3

Wherein R ¹ , X and a are the same as defined above,
R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, and W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary).

(D) A method of reacting the unsaturated group of the polyether having an unsaturated group introduced at the terminal with the mercapto group of the silicon compound represented by the formula 3 in which W is a mercapto group.

(E) A method of copolymerizing a polymerizable monomer having a hydrolyzable silicon group or an oligomer thereof with another polymerizable monomer or an oligomer thereof.

The polymerizable monomer is, for example, a compound represented by the formula 4 alone or as a mixture of two or more kinds.

[0035]

Embedded image CR ³ ₂ = CR ⁴ R ⁵ ... Formula 4

In the formula, R ³ is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group, preferably a hydrogen atom or a monovalent hydrocarbon group. R ⁴ and R ⁵ are hydrogen atom, halogen atom, alkyl group, phenyl group, alkoxy group, carboxyl group, alkoxycarbonyl group, glycidoxycarbonyl group, nitrile group, alkenyl group, acyloxy group,
It is a group selected from an amide group and a pyridyl group.

Specific examples of the polymerizable monomer include styrene-based monomers such as styrene and α-methylstyrene,
(Meth) acrylic acid, their esters or (meth)
(Meth) acrylic monomers such as acrylamide, acrylonitrile, cyano group-containing monomers such as 2,4-dicyanobutene-1, vinyl ester monomers such as vinyl acetate, diene monomers such as isoprene, butadiene, chloroprene, ethylene, propylene, Examples include olefins such as isobutylene, other unsaturated esters, halogenated olefins such as chlorotrifluoroethylene and tetrafluoroethylene, and vinyl alkyl ethers.

As the polymerizable monomer having a hydrolyzable silicon group, the compound represented by the formula 5 is used.

[0039]

## STR00007 ## X ¹ _3-n --SiR ⁶ _n R ⁷ ... Equation 5

In the formula, R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X ¹ is a hydroxyl group, a halogen atom, an alkoxy group, an acyloxy group, an amido group, an amino group or an amino group. It is a hydrolyzable group such as an oxy group, a ketoximate group, a hydride group, R ⁷ is an organic group having a polymerizable unsaturated group, and n is an integer of 0 to 2.

Specific examples of the compound represented by the formula 5 include compounds represented by Chemical formula 8 and the like.

[0042]

Embedded image CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ Si
_{(CH 3) (OCH 3)} 2, CH 2 = C (CH 3) Si
(CH ₃ ) (OCH ₃ ) ₂ .

(F) A method of polymerizing a polymerizable monomer in the presence of a chain transfer agent containing a hydrolyzable silicon group.

Specific examples of the chain transfer agent containing a hydrolyzable silicon group include the compounds of Chemical formula 9 and the like.

[0045]

Embedded image HS (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , HS
_{(CH 2) 3 Si (CH} 3) (OCH 3) 2.

The molecular weight of the organic polymer (A) is 1000-5.
000 is preferred. When a hydrolyzable silicon group-containing polyether is used as the organic polymer (A), it is preferable to use one having a molecular weight of 8,000 to 50,000. When the molecular weight is less than 8000, the cured product becomes hard,
In addition, the elongation is low, which is not preferable. Molecular weight is 500
If it exceeds 00, the flexibility and elongation of the cured product will not be a problem, but the viscosity will be remarkably increased and the practicality will be lowered. The molecular weight is particularly preferably 10,000 to 30,000.

[Fluorine-Containing Polymer (B)] [Polymerizable Monomer (a)] The fluorine-containing copolymer (B) in the present invention has a polymer unit (p) having a polyfluorohydrocarbon group. The polymerized unit (p) having a polyfluorohydrocarbon group is preferably a polymerized unit produced by polymerizing the polymerizable monomer (a) having a polyfluorohydrocarbon group.

Examples of the polymerizable unsaturated group in the polymerizable monomer (a) include vinyl group, allyl group, (meth) acryloyl group and isopropenyl group.

The polyfluorohydrocarbon group means a group in which two or more hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms. The polyfluorohydrocarbon group preferably has 2 to 40 carbon atoms, particularly 2 to 22 carbon atoms, and more preferably 4 to 18 carbon atoms. Most preferably, it is 6-14.

Regarding the number of fluorine atoms in the polyfluorohydrocarbon group, the ratio of the number of substituted fluorine atoms to the number of hydrogen atoms of the unsubstituted hydrocarbon group is 50% or more, preferably 60% or more. 80% or more is more preferable, and substantially 10
It is preferably 0%. Furthermore, some or all of the non-substituted hydrogen atoms may be replaced with chlorine atoms.

The structure of the polyfluorohydrocarbon group may be linear or branched, and is preferably linear. The polyfluorohydrocarbon group is preferably monovalent to trivalent,
It is particularly preferably monovalent or divalent.

The polyfluorohydrocarbon group may have an etheric oxygen atom or a thioetheric sulfur atom inserted between carbon-carbon bonds. Moreover, you may have unsaturated groups, such as a carbon-carbon unsaturated double bond.

The tip portion of the polyfluorohydrocarbon group is preferably a perfluorohydrocarbon group portion.
A linking part in which a polyfluorohydrocarbon group is bonded to another group and which is a fluorine atom-free organic group is referred to as a linking group. The polyfluorohydrocarbon group in the present invention may contain a linking group.

A specific example of the polyfluorohydrocarbon group containing no linking group is shown in Chemical formula 10, and a specific example of the polyfluorohydrocarbon group containing a linking group is shown in Chemical formula 11. However, m is 2-40
And 4 to 18 are preferable, and 6 to 14 are particularly preferable. p is 0 to 38, preferably 2 to 16 and 4 to 1
2 is particularly preferred. q is 0-19, 1-8 are preferable and 2-6 are especially preferable. r is 0 to 18 and 0
-7 are preferable and 1-5 are especially preferable.

[0055]

Embedded image F (CF ₂ ) _m −; H (CF ₂ ) _m −;
_{(CF 2) m -; (} CF 3) 2 CF (CF 2) p -; C
_{F 3 O [CF (CF 3} ) CF 2 O] q CF (CF 3)
_{-; C 3 F 7 O [} CF (CF 3) CF 2 O] r CF (C
_{F 3) -; (CF 3} ) 2 C = CF-; CF 3 CHFO
(CF ₂ ) ₃ −;

[0056]

Embedded image F (CF ₂ ) _m CH ₂ —; F (CF ₂ ) _m C
_{H 2 CH 2 -; F (} CF 2) m CH 2 CH 2 CH 2 -;
F (CF ₂ ) _m (CH ₂ ) ₆ −; H (CF ₂ ) _m CH _{2
-; F (CF 2) m} CH = CHCH 2 -; F (CF 2)
_{m CH 2 CHICH 2 -; F} (CF 2) m CH 2 CH
_{(OH) CH 2 -; F} (CF 2) m CH 2 CH 2 OCH
_{2 CH 2 -; F (CF} 2) m (CH 2) 6 OCH 2 CH
_{2 -; F (CF 2)} m OCH 2 CH (OH) CH 2 -;
_{(CF 3) 2 CF (CF} 2) p CH 2 CH 2 -; (CF
₃ ) ₂ CF (CF ₂ ) _p CH ₂ CHICH ₂ −; (CF
₃ ) ₂ CF (CF ₂ ) _p CH ₂ CH (OH) CH ₂ —;
CF ₃ O [CF (CF ₃ ) CF ₂ O] _q CF (CF ₃ )
_{CH 2 -; (CF 3)} 2 CH -; (CF 3) 2 C (CH
₃ ) CH ₂ —; CF ₃ CHFCF ₂ CH ₂ —; F (CF
₂ ) ₃ OCF (CF ₃ ) CH ₂ —; CHF ₂ CF ₂ OC
_{H 2 CH 2 -; CHF 2} CF 2 OCH 2 CH (OCF 2
_{CF 2 H) CH 2 -;} - CH 2 CH 2 - (CF 2) m -
_{CH 2 CH 2 -; - CH} 2 CH (OH) CH 2 O (CF
₂ ) _m OCH ₂ CH (OH) CH ₂ —;

As the polymerizable monomer (a), a compound represented by the formula 6 is preferable.

[0058]

Embedded image CH ₂ = CR ⁸ (CH ₂ ) _b —Z—R ^f0 ... Formula 6

In the formula, R ⁸ is a hydrogen atom or has 1 to 10 carbon atoms.
4 is a monovalent hydrocarbon group, b is an integer of 0 to 6, Z is a bond or a divalent organic group, and R ^f0 is a polyfluorohydrocarbon group.

Preferably Z is especially a bond, or
It is a divalent organic group selected from the group consisting of O-, -COO-, -CONH-, -NHCO- and -OCO-. Preferred as R ^{f0 is} as described above as a preferred group as the polyfluorohydrocarbon group.

Examples of the polymerizable monomer (a) include the following. Polyfluoroolefin compounds such as C ₈ F ₁₇ CH═CH ₂ . An acrylic acid polyfluoroalkyl ester represented by formula 7. Methacrylic acid polyfluoroalkyl ester represented by formula 8. Vinyl (polyfluoroalkyl) ether represented by formula 9. An allyl (polyfluoroalkyl) ether represented by formula 10. Equation 11
A polyfluoroalkylcarboxylic acid vinyl ester represented by.

[0062]

CH ₂ ═CH—COOR ^f1 ... Equation 7 CH ₂ ═C (CH ₃ ) —COOR ^f1 ... Equation 8 CH ₂ ═CH—OR ^f1 ... Equation 9 CH ₂ ═CHCH ₂ — OR ^f1 ... Formula 10 CH ₂ ═CH—OCOR ^f2 ... Formula 11 (R ^f1 and R ^f2 are polyfluorohydrocarbon groups.)

The following fluorinated amide compounds. F (CF ₂ )
_m CH ₂ NHCOCH = acrylic acid amides, such as _{CH 2, F (CF 2)} m CH 2 NHCOC (CH 3) = CH
Methacrylic acid amides such as ₂ .

R ^f1 is preferably a polyfluorohydrocarbon group containing a linking group. R ^f2 is preferably a polyfluorohydrocarbon group containing no linking group.

The fluorinated copolymer (B) in the present invention is preferably a polymer having at least 20 mol% of the polymer units (p) having a polyfluorohydrocarbon group based on all polymer units. If it is less than 20 mol%, sufficient surface stain resistance cannot be exhibited, and stains may become remarkable during long-term use, which is not preferable. In the fluorinated copolymer, the polymer unit (p) having a polyfluorohydrocarbon group is 20 to 95 mol%, particularly 3
It is preferable to have 0 to 90 mol%.

[Polymerizable Monomer (b) / (d)] In the present invention, the photocurable functional group is preferably a group selected from an acryloyl group, a methacryloyl group, a cinnamoyl group and an azido group.

The polymerized unit (q) having a photocurable functional group may be based on the following two types of polymerizable monomers. One is based on the polymerizable monomer (b) having a photocurable functional group. The other is a polymerizable monomer (d) having a functional group capable of introducing a photocurable functional group.
Is produced by introducing a photocurable functional group after copolymerizing (C) with a polymerizable monomer (a) to produce a copolymer (C). Polymerization based on the polymerizable monomer (d) It is a polymerized unit into which a photocurable functional group is introduced.

In the former case, the photocurable functional group is limited to the functional groups having no thermopolymerizable property among the groups exemplified above. Specifically, a cinnamoyl group is preferable. As the polymerizable monomer (b), the polymerizable monomer represented by the formula 12 is preferable.

[0069]

Embedded image CH ₂ = CR ⁹ (CH ₂ ) _c —Z ¹ — (CH ₂ ) _d —L Formula 12

In the formula, R ⁹ is a hydrogen atom or has 1 to 1 carbon atoms.
4, a monovalent hydrocarbon group, c and d are integers from 0 to 6, Z ¹ is a bond or a divalent organic group, and L is a photocurable functional group having no thermopolymerizable functional group. It is a base.

Specifically, for example, by reacting an unsaturated compound of the formula 12 having a hydroxyl group in place of L with a cinnamoyl chloride, a compound of the formula 12 in which L is a cinnamoyloxy group can be obtained. Examples of the compound of the formula 12 include cinnamic acid ester of allyl alcohol-alkylene oxide adduct, cinnamic acid ester of acrylic acid (2-hydroxyethyl) ester, and allyl cinnamate.

The latter polymerizable monomer (d) includes, for example, the polymerizable monomer represented by the formula 13.

[0073]

Embedded image CH ₂ = CR ⁹ (CH ₂ ) _c —Z ¹ — (CH ₂ ) _d —Y Formula 13

In the formula, R ⁹ , Z ¹ , c and d are the same as above.
Y is a group having a group capable of introducing a photocurable functional group.

Preferably Z ¹ is especially a bond,
It is an organic group containing a divalent organic group selected from the group consisting of -O-, -COO-, -CONH-, -NHCO- and -OCO-. Y is a hydroxyl group, an epoxy group, an amino group,
It is preferably a substituted or unsubstituted organic group having 1 to 20 carbon atoms having an isocyanate group or a carboxyl group. Y is preferably a hydroxyl group or an organic group having an epoxy group.

Examples of the polymerizable monomer (d) include the following. Polymerizable carboxylic acid such as (meth) acrylic acid ester. An acrylic ester represented by formula 14. Methacrylic acid ester represented by formula 15. A vinyl ether represented by formula 16. An allyl ether represented by formula 17. Carboxylic acid vinyl ester represented by Formula 18. The following amide compounds. Y ¹ NHCOCH = acrylic acid amides, such as ^{_{CH 2, Y 1 NHCOC (CH}} 3) = methacrylic acid amides, such as CH _2.

[0077]

Embedded image CH ₂ = CH-COOY ¹ ··· formula _{14 CH 2 = C (CH 3} ) -COOY 1 ··· formula ^{_{15 CH 2 = CH-OY 1}} ··· formula 16 CH ₂ = CHCH ₂ - OY ¹ ... Formula 17 CH ₂ ═CH—OCOY ¹ ... Formula 18 (Y ¹ is a group containing a group capable of introducing a photocurable functional group.)

Specific compounds include (meth) acrylic acid, (meth) acrylic acid (2-hydroxyethyl) ester, (meth) acrylic acid (3-hydroxypropyl) ester, and (meth) acrylic acid (3- Phenoxy
2-hydroxypropyl) ester, (meth) acrylic acid (3-chloro-2-hydroxypropyl) ester,
(2-hydroxyethyl) allyl ether, N-methylol acrylamide, succinic acid mono (2-methacryloyloxyethyl) ester, phthalic acid mono (2-methacryloyloxyethyl) ester, glycidyl (meth)
Acrylate, (meth) allyl glycidyl ether, a phosphorus compound of Chemical formula 17.

[0079]

CH ₂ ═CH—COOCH ₂ CH ₂ PO (O
_{H) 2, CH 2 = C} (CH 3) -COOCH 2 CH 2 P
O (OH) ₂ .

After copolymerizing the polymerizable monomer (d) with the polymerizable monomer (a) to obtain the copolymer (C),
A photocurable functional group can be introduced into (C). As the photocurable functional group, the groups listed above can be selected.

Specifically, for example, a copolymer having a hydroxyl group can be reacted with acrylic chloride or cinnamoyl chloride to produce a copolymer having an acryloyloxy group or a cinnamoyloxy group. In addition,
When introducing the photocurable functional group, a group capable of introducing the photocurable functional group may remain. Fluorine-containing copolymer (B)
Has a small amount of a group capable of introducing a photocurable functional group, the dispersibility of the fluorine-containing copolymer (B) in the organic polymer (A) is improved and the fluorine-containing copolymer (B) is improved. This is preferable because it improves the film-forming property.

The fluorine-containing copolymer (B) in the present invention preferably has at least 5 mol% of the polymer units (q) having a photocurable functional group, based on all polymer units. When the amount of the polymerized units (q) having a photocurable functional group is less than 5 mol%, a sufficient photocured film cannot be formed and stains may be remarkable during long-term use, which is not preferable.
It is particularly preferable to have 5 to 80 mol% with respect to all polymerized units. 10 to 70 mol% is preferable, and 10 to 50 mol% is particularly preferable.

[Polymerizable Monomer (c)] The fluorinated copolymer (B) in the present invention may have a polymer unit (r) other than the polymer unit (p) and the polymer unit (q). The polymerized units (r) are preferably polymerized units produced by polymerizing the polymerizable monomer (c) other than (a) and (b). Further, it may be a polymerized unit produced by polymerizing the polymerizable monomer (d) and a polymerized unit in which a photocurable functional group is not introduced.

The polymerized units (r) are fluorine-containing copolymer (B).
It also plays a role of improving the film-forming property of itself, improving the compatibility and dispersibility of the fluorine-containing copolymer (B) with the organic polymer (A), and improving the surface migration property of the curable composition. It also has the effect of improving the storage stability of the curable composition. Further, as the polymerized unit (r), a polymerized unit produced by polymerizing the polymerizable monomer (d), in which a photocurable functional group is not introduced, is added to the fluorocopolymer (B). When it is contained, as described above, the effect of improving the dispersibility of the fluorocopolymer (B) in the organic polymer (A) and the film-forming property of the fluorocopolymer (B) can be seen. .

The polymer units (r) are 0 to all polymer units.
A ratio of 75 mol% is preferable. That is, it is preferable that the total of the polymerized units (p) and the polymerized units (q) is contained in a proportion of 25 mol% or more based on all polymerized units. The ratio of these two types of polymerized units is 25 mol%
If it is less than the above range, sufficient weather resistance and surface stain resistance cannot be exhibited.

The polymerizable monomer (c) is a polymerizable monomer having neither a polyfluoroalkyl group nor a photocurable functional group. Examples of the polymerizable monomer (c) include a polymerizable monomer having a polymerizable site such as a vinyl group, an allyl group, an acryloyl group, a methacryloyl group and an isopropenyl group.

Specific examples of the polymerizable monomer (c) include a polymerizable monomer having a polyoxyalkylene chain having a molecular weight of about 100 to 3000. Specific examples thereof include polyoxypropylene glycol monoalkyl ether (meth) acrylate having a molecular weight of 100 to 3000.

Further, vinyl ethers, olefins, allyl ethers, vinyl esters, allyl esters, acrylic acid esters, methacrylic acid esters,
Examples thereof include isopropenyl ethers, isopropenyl esters, crotonic acid esters and other polymerizable monomers. Of these, compounds having a linear, branched or alicyclic alkyl group having about 1 to 15 carbon atoms are preferable. Specific compounds include the following.

Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, chloroethyl vinyl ether; ethylene, propylene, 1-butene, isobutylene, cyclohexene,
Olefins such as styrene and α-methylstyrene; allyl ethers such as methyl allyl ether, ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether; vinyl acetate, vinyl propionate,
Vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl caproate, vinyl caprylate, Veova 9 and Veova 1
0 (trade name of vinyl ester of branched fatty acid having 9 or 10 carbon atoms manufactured by Shell Chemical Co., Ltd.), fatty acid vinyl ester such as vinyl versatate; allyl ester such as allyl acetate; methyl (meth) acrylate , (Meth) acrylate, butyl (meth) acrylate,
(Meth) acrylic acid esters such as cyclohexyl (meth) acrylate; crotonic acid esters such as ethyl crotonic acid, butyl crotonic acid, and cyclohexyl crotonic acid; (meth) acrylic amides such as (meth) acrylic acid amides; Cyano group-containing monomers such as acrylonitrile and 2,4-dicyanobutene-1; isoprene,
Dienes such as butadiene; halogenated olefins such as vinyl chloride, vinylidene chloride, trifluorochloroethylene, tetrafluoroethylene and vinylidene fluoride.

Furthermore, it is also possible to use a polymerizable monomer having a hydrolyzable silicon group represented by the formula 5. However, it is not always necessary because it may react with the hydrolyzable silicon group of the organic polymer (A) to increase the modulus of the cured product or prevent the fluorine-containing copolymer (B) from transferring to the surface.

The polymerization method may be any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization, and a method of reacting a predetermined amount of a polymerizable monomer with a polymerization initiator such as a polymerization initiator or ionizing radiation is used. Polymerization takes place. Also, in the presence of an appropriate chain transfer agent, to control the molecular weight,
It is also possible to carry out the polymerization in the presence of the organic polymer (A). Other various conditions can be the same as those usually used for solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like.

The fluorine-containing copolymer (B) preferably has a molecular weight of 1,000 to 50,000. When used without a solvent such as a sealing material, those having a large molecular weight have extremely poor workability. When used without a solvent, it is preferable to employ one having a molecular weight of 15,000 or less, particularly 10,000 or less. The lower limit of the molecular weight is not particularly limited, but is usually 300 or more, preferably 1000 or more.

The weight ratio of the organic polymer (A) and the fluorine-containing copolymer (B) used is (A) / (B) = 100 /
0.1-100 / 20 is preferable. (A) / (B) = 1
00 / 0.1 to 100/10 is particularly preferable.

[Others] In the curable composition of the present invention, in addition to the organic polymer (A) and the fluorine-containing copolymer (B), a photopolymerization initiator, a filler, a plasticizer, and a curing agent which are optionally added are added. A catalyst and other additives can be added as required.

As the photopolymerization initiator, benzophenone,
Acetophenone, benzoin, 2-chlorothioxanthone, benzyl, 2-ethylanthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-
2-Methyl-1-phenylpropan-1-one can be exemplified.

[Filler] As the filler, known fillers can be used. The amount of the filler used is 0 to 1 with respect to 100 parts by weight of the total amount of the organic polymer (A) and the fluorinated copolymer (B).
000 parts by weight, especially 50 to 250% by weight is preferred. The following are specific examples of the filler. These fillers may be used alone or in combination of two or more.

Calcium carbonate, fumed silica, precipitated silica, silicic acid anhydride, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, Powdered fillers such as zinc oxide, activated zinc white, shirasu balloon, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, graphite, aluminum fine powder, flint powder, asbestos, glass fiber, glass filament, Fibrous fillers such as carbon fiber, Kevlar fiber and polyethylene fiber.

[Plasticizer] As the plasticizer, known plasticizers can be used. The amount of the plasticizer used is 0 to 100 parts by weight of the total of the organic polymer (A) and the fluorinated copolymer (B).
100 parts by weight is preferred. The following are specific examples of the plasticizer.

Dioctyl phthalate, dibutyl phthalate,
Phthalates such as butylbenzyl phthalate. Aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate. Alcohol esters such as pentaerythritol ester. Phosphate esters such as trioctyl phosphate and tricresyl phosphate. Epoxidized soybean oil, 4,
Epoxy plasticizers such as 5-epoxy dioctyl hexahydrophthalate and benzyl epoxy stearate. Chlorinated paraffin. Polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols, polyethers such as polyoxypropylene glycol and its derivatives, oligomers of polystyrene such as poly-α-methylstyrene and polystyrene, polybutadiene, butadiene- Polymer plasticizers such as acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, epoxidized polybutadiene, and other oligomers.

[Curing Accelerating Catalyst] In curing the curable composition of the present invention, a curing accelerating catalyst that accelerates the curing reaction of the hydrolyzable silyl group may be used. The following compounds may be mentioned as specific examples. One of them
Species or two or more are used. The curing accelerating catalyst is preferably used in an amount of 0 to 10 parts by weight based on 100 parts by weight of the total of the organic polymer (A) and the fluorinated copolymer (B).

Alkyl titanates, organosilicon titanates, metal salts such as bismuth tris-2-ethylhexoate, acidic compounds such as phosphoric acid, p-toluenesulfonic acid and phthalic acid, ethylenediamine, hexanediamine and the like. Aliphatic polyamines such as aliphatic diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, heterocyclic amines such as piperidine and piperazine, aromatic amines such as metaphenylenediamine, ethanolamines, triethylamine, epoxy resin Amine compounds such as various modified amines used as a curing agent for

Tin dioctylate, dibutyltin dilaurate, dioctyltin dilaurate and the carboxylic acid type organotin compounds of Chemical formula 18 and mixtures of these carboxylic acid type organotin compounds with the above amines.

[0103]

Embedded image (nC ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ ; (nC ₄ H ₉ ) ₂ S
n (OCOCH = CHCOOC ₄ H ₉ -n) ₂ ; (nC ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOCH
₃ ) ₂ ； (nC ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₄ H ₉ -n) ₂ ； (nC ₈ H ₁₇ ) ₂
Sn (OCOCH = CHCOOC ₈ H ₁₇ -iso) ₂ ;

The sulfur-containing organotin compound of Chemical formula 19

[0105]

Embedded image (nC ₄ H ₉ ) ₂ Sn (SCH ₂ COO); (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ C
OO) ； (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COO) ； (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ C
OOCH ₂ CH ₂ OCOCH ₂ S); (nC ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ -iso) ₂ ;
(nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ -iso) ₂ ; (nC ₈ H ₁₇ ) ₂ Sn (SCH
₂ COOC ₈ H ₁₇ -n) ₂ ; (nC ₄ H ₉ ) ₂ SnS;

Organotin oxides such as (nC ₄ H ₉ ) ₂ SnO and (nC ₈ H ₁₇ ) ₂ SnO, and these organotin oxides and ethyl silicates, dimethyl maleate, diethyl maleate,
Reaction products with ester compounds such as dioctyl maleate, dimethyl phthalate, diethyl phthalate and dioctyl phthalate.

The chelating tin compounds of Chemical formula 20 and reaction products of these tin compounds with alkoxysilanes (provided that
acac is an acetylacetonato ligand, and e-acac is an acetoacetate ethyl chelate ligand).

[0108]

Embedded image (nC ₄ H ₉ ) ₂ Sn (acac) ₂ ; (nC ₈ H ₁₇ ) ₂ Sn (acac)
₂ ; (nC ₄ H ₉ ) ₂ (C ₈ H ₁₇ O) Sn (acac); (nC ₄ H ₉ ) ₂ (C ₈ H ₁₇ O)
Sn (e-acac);

The tin compound of formula 21:

[0110]

(NC ₄ H ₉ ) ₂ (CH ₃ COO) SnOSn (OCOCH ₃ ) (nC ₄ H ₉ )
₂ ; (nC ₄ H ₉ ) ₂ (CH ₃ O) SnOSn (OCH ₃ ) (nC ₄ H ₉ ) ₂ ;

[Adhesiveness imparting agent] An adhesiveness imparting agent is used for the purpose of further improving the adhesiveness. Examples of these adhesiveness-imparting agents include (meth) acryloyloxy group-containing silanes, amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, and carboxyl group-containing silanes.

Examples of the (meth) acryloyloxy group-containing silanes include γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropylmethyldimethoxysilane.

As amino group-containing silanes, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane. Silane, N- (β-aminoethyl)-
γ-aminopropylmethyldimethoxysilane, N- (β
-Aminoethyl) -γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-
(N-vinylbenzyl-β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane and the like.

As the mercapto group-containing silanes, γ-
Examples include mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyldiethoxysilane. Examples of epoxy group-containing silanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropyltriethoxysilane.

As the carboxyl group-containing silanes, β-
Carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) silane,
N- (N-carboxylmethyl-β-aminoethyl)-
γ-aminopropyltrimethoxysilane and the like.

A reaction product obtained by reacting two or more kinds of silane coupling agents may be used. Examples of the reaction product are reaction products of amino group-containing silanes and epoxy group-containing silanes, reaction products of amino group-containing silanes and (meth) acryloyloxy group-containing silanes, epoxy group-containing silanes and mercapto groups. Examples thereof include a reaction product of silanes containing a silane, and a reaction product of silanes containing a mercapto group.
These reactants are easily obtained by mixing the silane coupling agent and stirring in the temperature range of room temperature to 150 ° C. for 1 to 8 hours.

The above compounds may be used alone or 2
More than one kind may be used in combination. The amount of the adhesiveness-imparting agent used is preferably 0 to 30 parts by weight based on 100 parts by weight of the total amount of the organic polymer (A) and the fluorinated copolymer (B).

[Solvent] When the composition of the present invention is used as a curable composition, a solvent may be added for the purpose of adjusting viscosity and improving storage stability of the composition. The amount of the solvent used is the organic polymer (A) and the fluorine-containing copolymer (B).
Is preferably 0 to 500 parts by weight with respect to 100 parts by weight in total.

Examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ester alcohols, ketone alcohols, ether alcohols and ketones. Ethers, ketone esters and ester ethers can be used. In particular, when alcohols are used, particularly when the composition of the present invention is stored for a long period of time, storage stability is improved, which is preferable. As alcohols, alkyl alcohols having 1 to 10 carbon atoms are preferable, and methanol, ethanol, isopropyl alcohol, isoamyl alcohol, hexyl alcohol and the like are used.

[Dehydrating Agent] In order to further improve the storage stability of the curable composition of the present invention, a small amount of dehydrating agent can be added within a range that does not adversely affect the curability and flexibility. The amount of the dehydrating agent used is preferably 0 to 30 parts by weight based on 100 parts by weight of the total of the organic polymer (A) and the fluorinated copolymer (B).

Specifically, alkyl orthoformates such as methyl orthoformate and ethyl orthoformate, alkyl orthoacetates such as methyl orthoacetate and ethyl orthoacetate, methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane and tetraethoxy. A hydrolyzable organosilicon compound such as silane, a hydrolyzable organotitanium compound, or the like may be used. Vinyl trimethoxysilane and tetraethoxysilane are particularly preferred in view of cost and effect.

[Thixotropy-imparting Agent] A thixotropy-imparting agent may be used to improve the sagging property. As such a thixotropic agent, hydrogenated castor oil, aliphatic amide and the like are used.

[Anti-aging agent] As the anti-aging agent, generally used antioxidants, ultraviolet absorbers,
Light stabilizers are used as appropriate.

[Use] The curable composition of the present invention can be used for construction or other uses such as a sealing material, an adhesive, a coating material, and a waterproofing agent.
Particularly, it is suitable for applications in which the surface of the cured product is required to have stain resistance.

[0125]

EXAMPLES Examples of the present invention will be given below, but the invention is not limited thereto. Polyethers A1 and A2 are hydrolyzable silicon group-containing organic polymers used in Examples or Comparative Examples and are the following propylene oxide polymers, respectively.

A1: An ethylene glycol-initiated polypropylene oxide polymer having an average molecular weight of 17,000, in which a dimethoxysilylpropyl group is introduced into 75% of all terminals produced by the method (b). A2: An average molecular weight of 200 in which a dimethoxysilylpropyl group was introduced into 78% of all terminals produced by the method (b) above.
A glycerin-initiated polypropylene oxide polymer of 00.

(Synthesis Example 1) Propylene oxide was polymerized with n-butanol as an initiator using a zinc hexacyanocobaltate catalyst to obtain polypropylene oxide monobutyl ether having an average molecular weight of 2000. 300 g (0.15 mol) of this compound was weighed into a 2 L flask,
500g of acetone and 17.7g of triethylamine
(0.17 mol) and 150 mg of hydroquinone monomethyl ether were added, and the mixture was stirred at 40 ° C for 10 minutes under a nitrogen stream. Then 14.5 g of acrylic acid chloride
A solution of (0.16 mol) in 100 g of acetone was added dropwise over 30 minutes. Then, raise the temperature to 57 ° C and
The reaction was completed by stirring for half an hour.

Thereafter, the ammonium salt was filtered off, and the filtrate was added dropwise to 3 L of stirred water to reprecipitate the compound. Then, the precipitated compound was washed twice with water and dried to obtain a compound c1 having an acryloyl group and a polyether chain.

(Synthesis Example 2) By the same procedure as in Synthesis Example 1, polypropylene oxide monobutyl ether having an average molecular weight of 400 was obtained. Then, acrylic acid chloride was added to this to convert the terminal hydroxyl group into an acryloyl group. A compound c2 having an acryloyl group and a polyether chain was obtained.

(Synthesis Example 3) 500 m of allyl alcohol
8.7 g (0.15 mol) was weighed into a L flask, and 100 g of acetone and 17.7 g of triethylamine.
(0.17 mol) and hydroquinone monomethyl ether (15 mg) were added, and the mixture was stirred at 40 ° C. for 10 minutes under a nitrogen stream. Then cinnamoyl chloride 26.6g
A solution of (0.16 mol) in 100 g of acetone was added dropwise over 30 minutes. Then, raise the temperature to 57 ° C and
The reaction was completed by stirring for half an hour.

Then, the ammonium salt was filtered off, and the filtrate was added dropwise to 3 L of stirred water to reprecipitate the compound. Then, the precipitated compound was washed twice with water and dried to obtain the target compound b1 having a cinnamoyl group and an allyl group.

(Synthesis Example 4) 46.16 g of the compound c1 obtained in Synthesis Example 1 and C _t F _{2t + 1} CH ₂ CH ₂ OCOCH = C
H ₂ (average value of t 9) (hereinafter referred to as compound a1) 23.
91 g and acrylic acid (2-hydroxyethyl) ester 5.36 g were placed in a 500 mL flask, dissolved in a mixed solvent of 150 g of chloroform and 150 g of isopropyl alcohol, and 1.5 g of azoisobutyronitrile was added as an initiator to 70 ° C. It was heated and polymerized for 10 hours. Then, the solvent was once removed to obtain the compound C1. Then, an acryloyl group was introduced into the polymer by the same method as in Synthesis Example 2 to obtain a fluorocopolymer B1 having an acryloyl group content of 20 mol% and a weight average molecular weight of 25,000.

Example 1 To a mixture of 70 parts by weight of polyether A1 (hereinafter referred to as “parts”) and 30 parts of polyether A2, a fluorine-containing copolymer B which is the component (B).
1 part 5 parts, white gloss CCR (Shiroishi Industry Co., Ltd. calcium carbonate) 60 parts, Whiten SB (Shiraishi Industry Co., Ltd. calcium carbonate) 70 parts, dioctyl phthalate 60 parts, Epicoat 828 (Okaka Shell Epoxy Co., Epoxy compound) 5
Part, titanium oxide 3.5 parts, Tinuvin 327 (manufactured by Ciba Geigy, UV absorber) 1 part, SANOL 765 (manufactured by Sankyo Co., light stabilizer) 0.5 part Irganox 245 (manufactured by Ciba Geigy, 1 part of antioxidant) and 4.0 parts of hydrogenated castor oil were added, and the mixture was mixed with a 2L planetary mixer to 60
After mixing at 0 ° C. for 3 hours, vacuum deaeration treatment was performed at 10 torr to obtain a composition.

3/1 tin dioctylate and lauryl amine
The curing catalyst mixed in a weight ratio of 3 parts was added to the above composition, and kneaded sufficiently. This kneaded material is 50 mm long and 15 mm wide.
0mm, placed in a mold 5mm thick, made into a sheet, 20 ℃,
The cured product sheet was obtained by placing the sample in a thermo-hygrostat of 65% humidity for 7 days.

This cured sheet was left at a 45 ° angle on the south side of the roof of the Research Institute of Asahi Glass Co., Ltd. in Yokohama City, Kanagawa Prefecture, and the stain resistance to natural exposure after six months was visually observed. Table 1 shows the results.

However, the exposure contamination evaluation is based on the following criteria. ◯: Almost no dust is observed. Δ: There is dust adhesion. ×: Dust is badly adhered

[Examples 2 to 6] Compositions were prepared in exactly the same manner as in Example 1 except that the following fluorine-containing copolymers B2 to B6 were used in place of B1 as the component (B). In the same manner as in Example 1, the exposure resistance to natural exposure was evaluated. The results are shown in Table 1.

[Comparative Example 1] A composition was prepared in the same manner as in Example 1 except that the component (B) was not included, and the stain exposure resistance was evaluated. Table 2 shows the results.

[Comparative Example 2] A composition was prepared in the same manner as in Example 1 except that the fluoropolymer (compound C1) shown in Synthesis Example 4 before the introduction of the acryloyl group was used in place of B1. The thing was created and the pollution resistance by natural exposure was evaluated. Table 2 shows the results.

[Comparative Examples 3 to 5] D1 which is a fluorinated surfactant shown below in place of the component (B) used in the examples.
Compositions were prepared in the same manner as in Examples except that the compounds of D3 to D3 were used, and the stain resistance to natural exposure was evaluated. Table 2 shows the results
Shown in

The component (B) used in the examples is as follows. B2: Compound a1, compound c2 obtained in Synthesis Example 2 and acrylic acid (2-hydroxyethyl) ester were added to 40/3.
After copolymerization at 0/30 (molar ratio), the hydroxyl groups in the molecule are acryloylated with acrylic acid chloride. Acryloyl group content 27 mol%, weight average molecular weight 3000
0.

B3: After compound a1, acrylic acid stearyl ester and acrylic acid (2-hydroxyethyl) ester were copolymerized at 35/25/40 (molar ratio),
Acryloylated hydroxyl groups in the molecule with acrylic acid chloride. Acryloyl group content 36 mol%, weight average molecular weight 9000.

B4: Compound a1, butyl acrylate and acrylic acid (2-hydroxyethyl) ester were copolymerized at 35/50/15 (molar ratio), and then hydroxyl groups in the molecule were acryloylated with acrylic acid chloride. What I did. Acryloyl group content 14 mol%, weight average molecular weight 9000.

B5: Compound a1, compound b1 obtained in Synthesis Example 3 and acrylic acid stearyl ester were added to 40/20.
A copolymer obtained by copolymerizing at a molar ratio of / 40. Acryloyl group content 20 mol%, weight average molecular weight 12000. B6: 40/20/40 (molar ratio) of compound a1, compound b1 obtained in Synthesis Example 3 and butyl acrylate
A copolymer obtained by copolymerization with. Acryloyl group content 20 mol%, weight average molecular weight 8000.

The structural formulas of the compounds used in Comparative Examples are as follows. D1: C _t F _{2t + 1} COO- NH ⁴⁺ (average value of t: 9). D2: C _t F _{2t + 1} CONH (CH ₂ ) ₃ N ⁺ (CH ₃ )
₃ I ⁻ (average value of t: 9). _{D3: C t F 2t + 1} CONH (CH 2 CH 2 0) 21 CH 3
(Average value of t 9).

[0146]

[Table 1]

[0147]

[Table 2]

As can be seen from the comparison between Example and Comparative Example 1, as the component (B), B1 to B1 were added to the organic polymer (A).
The composition to which B6 is added has better stain resistance of the cured product upon exposure to light, as compared with the case where the component (B) is not added. On the other hand, the compounds of Comparative Examples 2 to 5 were prepared by adding, in place of the component (B), fluorine-containing surfactants D1 to D3 containing ionic and nonionic hydrophilic groups, which correspond (B ) It was revealed that the composition was poor in stain resistance during exposure to light as compared with the composition containing the component.

[0149]

EFFECTS OF THE INVENTION The curable composition of the present invention is excellent in surface stain resistance during exposure to sunlight and is most suitable as an elastic sealing material and a waterproof material.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C08F 290/04 MRN C08F 290/04 MRN 290/06 MRS 290/06 MRS

Claims (11)

[Claims] 1. An organic polymer (A) having at least one hydrolyzable silicon group capable of being crosslinked by hydrolysis, a polymerized unit (p) having a polyfluorohydrocarbon group, and a photocurable functional group. A curable composition containing a fluorine-containing copolymer (B) having a polymerized unit (q) having a group. 2. An organic polymer (A) having at least one hydrolyzable silicon group capable of crosslinking by hydrolysis in the molecule, and a polymerized unit (p) having a polyfluorohydrocarbon group,
Polymerized units (q) and (p) having a photocurable functional group,
A curable composition containing a fluorocopolymer (B) having a polymerized unit (r) other than (q). 3. The curable composition according to claim 1, wherein the photocurable functional group is a group selected from an acryloyl group, a methacryloyl group, a cinnamoyl group and an azido group. 4. The curable composition according to claim 1, wherein the fluorinated copolymer (B) is a polymer having at least 20 mol% of polymerized units (p) having a polyfluorohydrocarbon group. 5. The curable composition according to claim 1, wherein the fluorinated copolymer (B) is a polymer having at least 5 mol% of polymerized units (q) having a photocurable functional group. 6. The fluorine-containing copolymer (B) is a polymerizable monomer (a) having a polyfluorohydrocarbon group, a polymerizable monomer (b) having a photocurable functional group, and optionally (a), ( The curable composition according to any one of claims 1 to 5, which is a fluorine-containing copolymer obtained by copolymerizing a polymerizable monomer (c) other than b). 7. A fluorine-containing copolymer (B), a polymerizable monomer (a) having a polyfluorohydrocarbon group, a polymerizable monomer (d) containing a functional group capable of introducing a photocurable functional group, and a necessary component. By copolymerizing a polymerizable monomer (c) other than (a) and (b) with a fluorine-containing copolymer (C)
A fluorine-containing copolymer obtained by introducing a photo-curable functional group into at least a part of the functional group capable of introducing a photo-curable functional group in (C).
The curable composition according to any one of 5 above. 8. The weight ratio of the organic polymer (A) and the fluorinated copolymer (B) is (A) / (B) = 100 /.
Curable composition in any one of Claims 1-7 which is 0.1-100 / 20. 9. The molecular weight of the organic polymer (A) is 1000-5.
The curable composition according to any one of claims 1 to 8, which is 0000. 10. The fluorine-containing copolymer (B) has a molecular weight of 30.
The curable composition according to any one of claims 1 to 9, which is 0 to 100,000. 11. The curable composition according to claim 1, wherein the hydrolyzable silicon group is a group represented by formula 1. ## STR1 -SiX _a R ¹ _3-a ··· Formula 1 Formula, R ¹ is a monovalent hydrocarbon group substituted or unsubstituted 1 to 20 carbon atoms, X is a hydroxyl group or a monovalent hydrolyzable Sexual group,
a is an integer of 1 to 3.