JPH10147723A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition which can give a cured product improved in resistance to staining on exposure to weather by mixing a specified organic polymer with an air-curing fluoro polymer. SOLUTION: 20-70mol% fluoroolefin (a), 1-80mol% monomer (b) being copolymerizable with component (a) and having an air-curing functional group and 0-70mol% monomer (c) freer from an air-curing functional group in such amounts to give a total of components (a) and (b) of at least 30mol% are copolymerized to obtain an air-curing fluoro polymer (B) comprising units derived from component (a), units derived from component (b) and units derived from component (c) and having a number-average molecular weight of 1,000-1,000,000. An organic polymer (A) having at least one reactive silyl group on the average per molecule and having a number-average molecular weight of 1,000-50,000 is mixed with component (B) in an A/B ratio of 100:0.1 to 100:20 by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition having excellent stain resistance and its use.

[0002]

2. Description of the Related Art Several examples of a polymer having a reactive silyl group capable of forming a siloxane bond by hydrolysis and having a high molecular weight or capable of crosslinking are known in the art (for example, Japanese Patent Application Laid-Open No. 3-47820). JP-A-3-72
027, JP-A-3-79627, JP-B-61-4933.
2. JP-B-46-30711, JP-B-45-3631
9, JP-B-46-17553).

[0003] However, when the modulus of the polymer or the polymer-containing composition is reduced, the surface of the polymer becomes sticky even after the curing is completed, that is, the tack remains. When used as a polymer, it causes joint contamination such as adhesion of dust and causes damage to the appearance of the building.

For the purpose of preventing this tack, Japanese Patent Publication No. Hei 3-3710 discloses a composition in which a fluorine-containing surfactant is added to a polymer having a reactive silyl group. However, this composition has a fluorine-based surfactant dispersed throughout the system even after curing, and migration to the surface is insufficient, so expensive fluorine-based surfactants are required to reduce surface tack. It is necessary to use a large amount of the agent, which causes contamination around the sealing portion and has a large adverse effect on water resistance and storage stability, so that its practical use has been greatly restricted.

[0005]

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

[0006]

SUMMARY OF THE INVENTION The present invention is the following invention. On average, the organic polymer (A) containing one or more reactive silyl groups in the molecule and the polymerized unit (1) based on fluoroolefin are 20 to 70 based on the total polymerized unit.
Mol%, 1 to 80 mol% of the polymerized unit (2) having an air-curable functional group with respect to the total polymerized unit, and a polymerized unit other than the polymerized unit (1) having an air-curable functional group. Having no polymerized unit (3) in a proportion of 0 to 70 mol% with respect to all polymerized units, the polymerized unit (1) and the polymerized unit (2)
Curable composition characterized by containing a fluorine-containing air-curable polymer (B) having a total number of 30 mol% or more based on all polymerized units and having a number average molecular weight of 1,000 to 1,000,000.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

[Organic polymer (A)] The organic polymer (A) having an average of one or more reactive silyl groups in the molecule used in the present invention is selected from polyoxyalkylenes, polyesters and polycarbonates. Polymers with reactive silyl groups introduced at the polymer terminals, vinyl esters such as acrylates, isobutylene, butadiene, chloroprene, trifluorochloroethylene, tetrafluoroethylene, vinyl ether, ethylene, propylene, and reactive silyl groups Examples thereof include a copolymer of contained monomers.

Among the organic polymers (A), those having a particularly remarkable effect of the addition of the fluorinated air-curable polymer (B) are compounds which undergo hydrolysis and cross-linking reactions due to moisture to change into rubber-like elastic materials. It is.

In particular, an organic polymer having a reactive silyl group at a terminal or a side chain and having a main chain consisting essentially of a polyoxyalkylene chain is liquid at room temperature, and the cured product has flexibility even at a relatively low temperature. When it is held and used for a sealing material, an adhesive or the like, it has preferable characteristics. That is, preferred as the organic polymer (A) in the present invention is a polymer having on average one or more reactive silyl groups in one molecule and a main chain substantially consisting of a polyoxyalkylene chain. is there.

Such a polymer is disclosed, for example, in JP-B-45
-36319, JP-B-46-17553, JP-B-46-
30711, JP-B-61-18852, JP-A-60-6
747, JP-A-3-43449, JP-A-3-4782
5, JP-A-3-72527, JP-A-3-79627, JP-A-63-6003, JP-A-6-116466, JP-B-63-60046, JP-B-63-65086, and the like.

The polyoxyalkylene polymer used as a raw material is prepared by adding an initiator such as a hydroxy compound having one or more hydroxyl groups to a monoepoxide such as an alkylene oxide in the presence of a catalyst such as an alkali catalyst, a double metal cyanide complex catalyst, and a metal porphyrin. Hydroxyl-terminated ones produced by reacting the above are preferred. The number of functional groups of the polyoxyalkylene polymer is preferably 2 or more, and particularly preferably 2, 3 or 4.

Examples of the polyoxyalkylene polymer include a polyoxyethylene polymer, a polyoxypropylene polymer, a polyoxybutylene polymer, a polyoxyhexylene polymer, a polyoxytetramethylene polymer, and / or And copolymers.

A particularly preferred polyoxyalkylene polymer is a polyoxypropylene polymer, and more specifically, polyoxypropylene diol and polyoxypropylene triol are particularly preferred. In addition, the following (i) and (i)
When used in the method v), an olefin-terminated polyoxyalkylene polymer such as an allyl-terminated polyoxypropylene monol can also be used.

The reactive silyl group in the present invention includes:
Any silyl group that undergoes hydrolysis and crosslinking reaction in the presence of moisture to form a siloxane bond may be used, and a generally known reactive silyl group can be used. For example, a silyl group represented by Formula 1 is preferable. [Formula ^{_{1] -SiW z R 1 3-}} z

In the formula, R ¹ is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group.
Particularly preferred are a methyl group, an ethyl group, a propyl group, a propenyl group, a butyl group, a hexyl group, a cyclohexyl group, a phenyl group and the like.

W is a hydroxyl group or a hydrolyzable group, and examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group and a ketoximate group. Among these, the carbon number of the hydrolyzable group having a carbon atom is preferably 6 or less, and particularly preferably 4 or less. Preferred hydrolyzable groups include lower alkoxy groups having 4 or less carbon atoms, especially methoxy, ethoxy, propoxy and propenyloxy groups. z is 1, 2 or 3, and particularly preferably 2 or 3.

The method for introducing the reactive silyl group represented by the formula 1 into the polyoxyalkylene polymer is not particularly limited, but can be introduced, for example, by the following method.

(I) A method of reacting a polyoxyalkylene polymer having an olefin group introduced into a terminal hydroxyl group with a hydrosilyl compound represented by the formula (2). [Expression ^{_{2] HSiW z R 1 3-}} z wherein R ^1, W, z are as defined above.

Here, as a method for introducing an olefin group, a compound having a functional group and an unsaturated group capable of reacting with a hydroxyl group is reacted with a terminal hydroxyl group of a polyoxyalkylene polymer to form an ether bond, an ester bond or a urethane bond. And a method in which an olefin group is introduced into a side chain by copolymerizing an olefin group-containing epoxy compound such as allyl glycidyl ether when polymerizing an alkylene oxide.

(Ii) A method of reacting a compound represented by Formula 3 with a terminal hydroxyl group of a polyoxyalkylene polymer. [Formula 3] R ¹³ -z _- SiW _z -R ² NCO In the formula, R ¹ , W and z are the same as described above. R ² has 1 to 17 carbon atoms
Divalent hydrocarbon group.

(Iii) A terminal hydroxyl group of the polyoxyalkylene polymer is reacted with a polyisocyanate compound such as tolylene diisocyanate to give an isocyanate group terminal, and then the V group of the silicon compound represented by the formula 4 is added to the isocyanate group. How to react. [Expression _{^{4] R 1 3-z -SiW}} z -R in ² V formula ^{R 1, R 2, W,} z are as defined above. V is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary).

(Iv) A method in which an olefin group is introduced into a terminal hydroxyl group of a polyoxyalkylene polymer, and the olefin group is reacted with a mercapto group of a silicon compound represented by Formula 4 wherein V is a mercapto group.

The organic polymer (A) has at least one reactive silyl group in the molecule on average.

When an organic polymer whose main chain is essentially a polyoxyalkylene chain is used as the organic polymer (A) of the present invention, the main chain has a number average molecular weight of 1,000 to 500.
00 organic polymers can be used. When the number average molecular weight of the compound (A) is lower than 1,000, the cured product is hard and has low elongation. When the number average molecular weight exceeds 50,000, the flexibility and elongation of the cured product are not problematic, but the compound (A) The viscosity of the material itself is significantly increased, and the practicality is reduced. The number average molecular weight is preferably 8,000 to 50,000, particularly preferably 10,000 to 30,000.

[Polymerized Unit (1)] The fluorinated air-curable polymer (B) in the present invention contains 20 to 70 mol% of a polymerized unit (1) based on a fluoroolefin. The polymerized unit (1) is a polymerized unit obtained by polymerizing the fluoroolefin (a). Fluoroolefin (a) is a compound in which a hydrogen atom directly connected to a carbon atom constituting an ethylenically unsaturated group is replaced by a fluorine atom. Carbon number 2
To 6, in particular, a fluoroolefin having 2 to 4 carbon atoms is preferably employed. It may be substituted with a fluorine atom and another halogen atom. Perhaloolefins in which hydrogen atoms have been completely replaced by halogens are particularly preferred.

Specific examples include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, and hexafluoropropylene.

When the amount of the polymerized unit based on the fluoroolefin is less than 20 mol%, the stain resistance obtained by using the fluorinated air-curable polymer (B) is not sufficient, and stains and the like may be generated during long-term use. May be significant. If the polymerization unit based on fluoroolefin exceeds 70 mol%, the compatibility with the organic polymer (A) is extremely reduced. In particular, those containing 30 to 60 mol% of a polymerized unit based on a fluoroolefin are preferred.

[Polymerized Unit (2)] The fluorinated air-curable polymer (B) in the present invention has a polymerized unit (2) containing an air-curable functional group at a ratio of 1 to 80 mol%.
Since this specific functional group is contained, a naturally cured film is obtained by exposing the resin composition to the air.
It is considered that a cured product having a crosslinked bond formed on the basis of the curable site exhibits particularly excellent weather resistance, particularly stain resistance, due to the specific crosslinked structure.

The air-curable functional group in the present invention is preferably an acyl group derived from a higher fatty acid having a conjugated double bond. As the higher fatty acid having a conjugated double bond, a higher fatty acid having 12 or more carbon atoms is preferable. Examples of the higher fatty acid include eleostearic acid, vinalic acid, ricanoic acid, and conjugated linoleic acid.

The polymerized unit (2) having an air-curable functional group in the present invention is, as described later, a unit obtained by polymerizing a monomer (b) having an air-curable functional group or an air-curable functional group. After polymerization of the monomer (e) having a functional group capable of introducing a functional functional group, it is preferably a polymerized unit into which an air-curable functional group has been introduced.

Polymerized unit (2) having an air-curable functional group
Is preferably represented by Formula 5. [Equation 5]-[CR ³ R ⁴ -CR ⁵ (R ^6- (O) _p · (Q) _k · (T) _q · (U) _m · R ⁷ )]-R ³ , R ⁴ , R ⁵ Is a hydrogen atom or a group having 1 to 10 carbon atoms
A hydrocarbon group, R ⁶ is a divalent organic group, Q is a unit obtained by ring-opening polymerization of an alkylene oxide, T is a divalent organic group containing a urethane bond or an amide bond, and U is a ring-opened polymerization of a cyclic ester. A unit, R ⁷ is an air-curable functional group, p is 0 or 1, and k, q, and m are integers of 0 to 20.

Here, k, q, and m represent the total number of the polymerized units, and Q, T, and U do not necessarily indicate that the block copolymerization is performed, but may be random copolymerization. . Hereinafter, the polymerization unit constituted by Q, T and U is also referred to as a spacer.

These spacers are composed of a polyoxyalkylene chain, a polyurethane chain, a polyamide chain, a polyester chain or a copolymer chain thereof. Particularly, a polyoxyalkylene chain or a polyester chain is preferable.

As the polyoxyalkylene chain, a polyoxyalkylene chain obtained by ring-opening polymerization of an alkylene oxide having 2 to 10 carbon atoms, particularly 2 to 6 carbon atoms, is preferable. Polyoxypropylene chains obtained by ring-opening polymerization of propylene oxide are particularly preferred. As the polyester chain, a polyester chain obtained by ring-opening polymerization of a cyclic ester such as caprolactone, particularly ε-caprolactone, is particularly preferred.

On the other hand, if the distance from the polymerizable site to the air-curable site is too long, the surface of the curable composition becomes too soft, and the weather resistance and stain resistance are undesirably reduced.
Therefore, k, q, and m are limited to 0 to 20.

The polymerization unit (2) containing the air-curable functional group is contained at a ratio of 1 to 80 mol% based on all the polymerization units. If the proportion is too small, the crosslinking density decreases, and the effects of weather resistance and stain resistance on the surface of the curable composition obtained by adding the fluorinated air-curable polymer (B) decrease. If the amount is too large, the surface of the curable composition becomes too brittle. The fluorinated air-curable polymer (B) in which the polymer units (2) are contained at a ratio of 5 to 40 mol% based on all polymer units is particularly preferable.

It is essential that the total of the polymer units (1) based on the fluoroolefin and the polymer units (2) having an air-curable functional group be contained in a proportion of 30 mol% or more based on all the polymer units. It is. If the proportion of these two types of polymer units is too small, sufficient weather resistance and stain resistance will not be exhibited.

[Polymerized Unit (3)] The fluorinated air-curable polymer (B) in the present invention further comprises a polymerized unit (1) based on a fluoroolefin and a polymerized unit (2) having an air-curable functional group. It may have a polymerization unit (3). Such a polymerized unit is obtained by polymerizing a monomer (c) which is a monomer other than the fluoroolefin (a) and has no air-curable functional group.

The monomer (c) is a monomer having an ethylenically unsaturated group, wherein a hydrogen atom directly connected to a carbon atom forming the ethylenically unsaturated group is not substituted with a fluorine atom. is there. The monomer (c) is preferably a compound having a polymerizable site such as a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, or an isopropenyl group as an ethylenically unsaturated group.

Of these, compounds having a linear, branched or alicyclic alkyl group having about 1 to 15 carbon atoms are preferred. In the alkyl group, part or all of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms.

Specifically, olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic esters, methacrylic esters, isopropenyl ethers, isopropenyl esters and crotonic esters The selected monomer is preferred.

Specific compounds include vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, chloroethyl vinyl ether, and perfluoroalkyl vinyl ether; and olefins such as ethylene, propylene, 1-butene, isobutylene and cyclohexene. , Allyl alcohol, methyl allyl ether, ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, allyl ethers such as 2-hydroxyethyl allyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, Vinyl caproate, vinyl caprylate, VEOB9 and VEOB10
(Trade names of vinyl esters of branched fatty acids having 9 and 10 carbon atoms, manufactured by Shell Chemical Company), fatty acid vinyl esters such as vinyl versatate, ethyl acrylate,
Esters of acrylic acid or methacrylic acid such as methyl methacrylate, butyl acrylate, butyl methacrylate, and cyclohexyl methacrylate; crotonic esters such as methyl crotonate, ethyl crotonate, butyl crotonate, and cyclohexyl crotonate. .

Among the above monomers, particularly, vinyl ethers,
Monomers selected from vinyl esters, allyl ethers, and crotonic esters are preferred. Most preferably, vinyl ethers are used, and when they are used, the probability of alternating copolymerization with a fluoroolefin is high, which is preferable in terms of weather resistance.

Further, a reactive silyl group-containing vinyl monomer represented by the formula 6 can be used. By using an appropriate amount of these monomers, they may be mixed well with the organic polymer (A) without impairing the surface contamination resistance, and the storage stability of the composition may be improved. In addition, by exhibiting solvent solubility and preparing a solution of such a polymer, mixing with the organic polymer (A) may be facilitated in some cases.

On the other hand, when such a monomer is copolymerized, it reacts with the organic polymer (A) containing a reactive silyl group to increase the modulus of the cured product, and furthermore, the fluorinated air-curable polymer. It is not essential because it may hinder the transfer of the coalesced (B) to the surface.

[Formula 6] Y _3-n -SiR ⁸ _n R ^{9 wherein} R ⁸ is an alkyl group having 1 to 18 carbon atoms, an aryl group,
A monovalent hydrocarbon group selected from aralkyl groups. Y is a hydroxyl group or a hydrolyzable group such as a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminoxy group or a ketoximate group. R ⁹ is an organic group having a polymerizable unsaturated group. n is 0, 1 or 2.

Specific examples of the silicon compound represented by the formula 6 include a compound represented by the formula (1).

[0048]

Embedded image CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si
(CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) (CH ₂ ) ₃ Si (CH ₃ ) (O
CH _{3) 2.}

[Fluorine-containing air-curable polymer (B)] The fluorine-containing air-curable polymer (B) in the present invention has a number average molecular weight of 100,000 or less. Those having a too large number average molecular weight are present in the curable composition and are not easily transferred to the surface, and it is difficult to form a protective film on the surface. The number average molecular weight is preferably 50,000 or less, particularly preferably 30,000 or less.

On the other hand, the number average molecular weight is at least 1,000, preferably at least 2,000, and most preferably at least 5,000.

The fluorine-containing air-curable polymer (B) in the present invention can be produced by the following method or the like.

First method: fluoroolefin (a),
The monomer (b) and the monomer (c) copolymerizable with the fluoroolefin and containing an air-curable functional group are each a monomer (a) in an amount of 20 to 70 mol%, b)
1 to 80 mol%, (c) is 0 to 70 mol%, and these monomers are copolymerized so that the total of (a) and (b) is at least 30 mol%.

Second method: The polymerized unit (1) is added in an amount of 20 to 70.
Mol%, a polymerization unit (4) having a functional group capable of introducing an air-curable functional group at a ratio of 1 to 80 mol%, and a polymerization unit (1) based on a fluoroolefin with respect to all polymerization units.
And a total of polymerized units (4) in a proportion of 30 mol% or more, and a polymerized unit (3) other than the polymerized units (1) and (2) in a proportion of 0 to 70 mol%. A method of converting a functional group in the polymer (D) into an air-curable functional group.

In the first method, the monomer (b) copolymerizable with a fluoroolefin and having an air-curable functional group includes the monomer (d) having an ethylenically unsaturated group and a functional group. Compounds in which an air-curable functional group has been introduced directly or through a spacer are preferred.

As a method for obtaining the monomer (b) having an air-curable functional group, a higher fatty acid having a conjugated double bond or a derivative thereof is reacted with a monomer having a hydroxyl group or an alkali metal alkoxide thereof. After forming a spacer by a method, or a method of subjecting an alkylene oxide or cyclic ester to ring-opening polymerization in the presence of a catalyst in the hydroxyl group of a monomer, the higher fatty acid having a conjugated double bond or a derivative thereof is formed. A reaction method is preferred.

Further, a method of reacting a higher fatty acid having a conjugated double bond or a derivative thereof with a monomer having an amino group or an epoxy group, and a method of reacting a monomer having an epoxy group or a carboxyl group with an alkanolamine or a polyhydric alcohol A method of reacting a compound such as this to convert the functional group to a hydroxyl group, optionally introducing a spacer, and reacting the higher fatty acid having a conjugated double bond or a derivative thereof, can also be exemplified.

As the ethylenically unsaturated group, a vinyl group,
Allyl groups and the like are particularly preferred. Among the monomers (d), specific examples of the monomer having a hydroxyl group include hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, allyl alcohol and the like.

Examples of monomers having an epoxy group other than a hydroxyl group and a carboxyl group include glycidyl allyl ether and acrylic acid. The derivatives of higher fatty acids having a conjugated double bond include esters and acid halides.

In the first method, the polymerization ratio of the various polymerizable monomers is such that the fluoroolefin (a) is 20%.
~ 70 mol%, the monomer (b) is 1 ~ 80 mol%,
It is preferable to control so that the total of the fluoroolefin (a) and the monomer (b) is copolymerized at a ratio of 30 mol% or more based on all the monomers.

In the second method, the fluorocopolymer (D) comprises a fluoroolefin (a), a monomer (e) having a functional group capable of introducing an air-curable functional group, and a monomer (e). It is preferably obtained by reacting c).

The monomer (e) having a functional group capable of introducing an air-curable functional group is a precursor of the monomer (b) having an air-curable functional group, and includes a monomer having a hydroxyl group, Examples include a monomer having a hydroxyl group and a spacer introduced therein, and a monomer having an epoxy group, a carboxyl group, or an amino group. The fluorine-containing copolymer has a functional group derived from the functional group of these monomers, and if necessary, the functional group
After forming the spacer, an air-curable functional group is introduced.

In the second method, the polymerization ratio of the various polymerizable monomers is such that the fluoroolefin (a) is 20%.
~ 70 mol%, the monomer (e) is 1 ~ 80 mol%,
It is preferable to control so that the total of the fluoroolefin (a) and the monomer (b) is copolymerized at a ratio of 30 mol% or more based on all the monomers.

In the first method, each of the fluoroolefin (a) and the monomer (b) having an air-curable functional group or the monomer (e) having a hydroxyl group or a functional group capable of being converted to a hydroxyl group is added with 1 When polymerized one by one, the possibility of alternating copolymerization is high, especially when the monomer (b) or the monomer (e) is a vinyl-based or allyl-based compound, When the copolymerization is carried out alternately, the number of other polymerized units existing between the polymerized units (2) having an air-curable functional group becomes about one, and a film provided by the obtained polymer becomes too brittle.

Therefore, preferably, two or more different kinds of compounds are employed as either or both of the fluoroolefin (a), the monomer (b) and the monomer (e). Or fluoroolefin (a), monomer (b)
Alternatively, a method of copolymerizing a monomer copolymerizable with the monomer (e) in addition to the monomer (e) is employed, and another polymerization unit (3) is interposed between the polymerization units having an air-curable functional group in the polymer. ) Is preferably operated. Usually, the latter method of copolymerizing the monomer (c) is preferred.

In the present invention, the method of polymerizing the monomer may be any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. A polymerization initiator such as a polymerization initiator is allowed to act on a predetermined amount of monomer. Thus, polymerization is performed. Further, other various conditions can be carried out under the same conditions as in the case of conducting solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like.

[Mixing ratio] In the curable composition of the present invention, the mixing ratio of the organic polymer (A) and the fluorinated air-curable polymer (B) is (A) / (B) = 100 / by weight.
0.1 to 100/20, preferably (A) /
More preferably, (B) = 100/1 to 100/10.

[Additives, Applications] The curable composition of the present invention can be used for various applications by using the curable composition as a constituent component and blending various additives as necessary. The present invention is particularly suitable for use in elastic sealing materials and waterproofing materials. The additives that can be used are described below.

[Curing Catalyst] In curing the curable composition of the present invention, a curing accelerating catalyst for accelerating the curing reaction of the reactive silyl group may be used.

Specific examples of the curing catalyst include the following compounds. One or more of them are used.

Metal salts such as alkyl titanates, organosilicon titanates, bismuth tris (2-ethylhexoate), acidic compounds such as phosphoric acid, p-toluenesulfonic acid and phthalic acid, ethylenediamine, hexanediamine and the like Aliphatic diamines, such as aliphatic polyamines such as diethylene triamine, triethylene tetramine and tetraethylene pentamine, heterocyclic amines such as piperidine and piperazine, aromatic amines such as metaphenylenediamine, ethanolamines, triethylamine and epoxy Amine compounds such as various modified amines used as curing agents for resins.

Tin dioctanoate, dibutyltin dilaurate, dioctyltin dilaurate, the following carboxylic acid type organotin compounds and mixtures of these carboxylic acid type organotin compounds with the above amines. (nC ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ , (nC ₄ H ₉ ) ₂ Sn (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 following sulfur-containing organotin compounds: (nC ₄ H ₉ ) ₂ Sn (SCH ₂ COO), (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ COO), (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COO), (nC ₈ H ₁₇ ) _{2 Sn (SCH 2 COOCH 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.

Organic tin oxides such as (nC ₄ H ₉ ) ₂ SnO, (nC ₈ H ₁₇ ) ₂ SnO, and these organic tin oxides and ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, phthalic acid Reaction products with ester compounds such as dimethyl, diethyl phthalate and dioctyl phthalate.

The following chelate tin compounds and reaction products of these tin compounds with alkoxysilanes (provided that
acac is an acetylacetonate ligand). (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).

The following tin compounds: (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 . The amount of the curing catalyst used is 0 to 10 with respect to the organic polymer (A).
% By weight is preferred.

[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) acryloxy group-containing silanes, amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, and carboxyl group-containing silanes.

Examples of (meth) acryloxy group-containing silanes include γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ
-Methacryloxypropylmethyldimethoxysilane and the like.

The amino group-containing silanes include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxy 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.

The silanes containing a mercapto group include γ-
Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and the like.

Examples of epoxy group-containing silanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like.

The carboxyl group-containing silanes include β-
Carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) silane,
N- (N-carboxymethyl-β-aminoethyl) -γ
-Aminopropyltrimethoxysilane and the like.

A reaction product obtained by reacting two or more silane coupling agents may be used. Examples of reactants include reactants of amino group-containing silanes and epoxy group-containing silanes, reactants of amino group-containing silanes with (meth) acryloxy group-containing silanes, epoxy group-containing silanes and mercapto group-containing Examples of the reactants include silanes and mercapto group-containing silanes. These reactants are mixed with the silane coupling agent and mixed at room temperature to 150 ° C.
It is easily obtained by stirring for 1 to 8 hours in a temperature range of ° C. The above compounds may be used alone or in combination of two or more.

The amount of the adhesion-imparting agent used is determined by the amount of the organic polymer (A)
Is preferably 0 to 30% by weight.

[Solvent] When the composition of the present invention is used as a curable composition, a solvent may be added for the purpose of adjusting the viscosity and improving the storage stability of the composition. The amount of the solvent used is 0 to 100% by weight based on the organic polymer (A).
Is preferred.

Examples of such a solvent include aliphatic hydrocarbons,
Aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ester alcohols, ketone alcohols, ether alcohols, ketone ethers, ketone esters, 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 the alcohols, alkyl alcohols having 1 to 10 carbon atoms are preferable, and methanol, ethanol, isopropanol, 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 a dehydrating agent can be added as long as the curability and flexibility are not adversely affected. The use amount of the dehydrating agent is preferably 0 to 30% by weight based on the organic polymer (A).

Specifically, alkyl orthoformate such as methyl orthoformate and ethyl orthoformate, methyl orthoacetate,
Alkyl orthoacetates such as ethyl orthoacetate, hydrolyzable organic silicon compounds such as methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane, and hydrolyzable organic titanium compounds can be used. Vinyl trimethoxysilane and tetraethoxysilane are particularly preferred in view of cost and effect.

[Thixotropic agent] A thixotropic agent may be used to improve sagging. As such a thixotropic agent, hydrogenated castor oil, aliphatic amide and the like are used.

[Antiaging Agent] As the antiaging agent, generally used antioxidants, ultraviolet absorbers,
Light stabilizers are used as appropriate.

[Mixing Method] In the present invention, when the components constituting the curable composition are mixed, a known method can be employed. For example, a method in which a mixture of a liquid substance and an inorganic filler is mixed in a planetary mixer, a dehydration reaction of the mixture is performed, and a pigment component separately formed into a toner and a curing catalyst are mixed in a line mixer. Etc. are exemplified.

[Uses] The curable composition of the present invention may be used as a sealing material, an adhesive,
Can be used for applications such as waterproofing agents. The curable composition of the present invention can be used as a sealing material, a waterproofing agent, a coating material, and the like, and is particularly suitable for applications requiring surface stain resistance of a cured product.

[0092]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. Silyl-terminated polyether (A)
Is a mixture of the following polymer A1 and polymer A2 at a weight ratio of 7: 3. A1: A polymer having a number average molecular weight of 17000 in which a methyldimethoxysilylpropyl group has been introduced into 75% of the terminals of a polypropylene oxide polymer initiated with ethylene glycol. A2: A glycerin-initiated polypropylene oxide-based polymer having a number average molecular weight of 20,000 with a methyldimethoxysilylpropyl group introduced at 78% of the terminal.

Example 1 Synthesis Example 10.0 g of hydroxybutyl vinyl ether (HBVE) was placed in a 1 L flask.
(0.86 mol) and ε-caprolactone 491.3
g (4.30 mol), 178 mg of tetrabutyl titanate was further added, and the mixture was reacted under stirring at 150 ° C. for 6 hours to obtain a modified lactone HBVE having a number average molecular weight of 687.

(Example 2: Synthesis example) HBVE120.0 was placed in a pressure-resistant reactor having an inner volume of 550 cm ^{3 and having} a stainless steel stirrer.
g (1.03 mol) and 0.9 g of potassium hydroxide were weighed, and propylene oxide was gradually added thereto.
g, 3 kg / cm ² ] at 110 ° C. for 2 hours. The obtained liquid was purified with synthetic magnesia to obtain propylene oxide-modified HBVE having a number average molecular weight of 300.

Example 3: Synthesis Example 150.0 g (0.172 mol) of untreated tung oil, 10.7 g of sodium methoxide (28% methanol solution) in a 0.5 L flask (0.056 mol as sodium methoxide) ) And 142.3 g of methanol were weighed and purged with nitrogen for 5 minutes. Thereafter, the temperature was raised to 40 ° C., and the mixture was stirred for 4 hours to complete the transesterification reaction. Thereafter, methanol was distilled off using an evaporator to obtain a brown oily substance. The oil was washed with 0.1 N hydrochloric acid until neutral, then washed with ion-exchanged water, and dehydrated to obtain 101.5 g of the target methyl α-eleostearate.

Example 4: Synthesis Example 100 g (containing 0.15 mol of hydroxyl groups) of the lactone-modified HBVE obtained in Example 1 was placed in a 1 L flask and methyl α-eleostearate obtained in Example 3 was added. 43.8 g (0.15 mol) were weighed, 100 g of toluene and 288 mg of tetrabutyl titanate were further added, and the mixture was stirred for 10 hours at 80 ° C. while distilling off methanol produced at 80 ° C. under a nitrogen stream to obtain a desired air-cured mixture. A lactone-modified HBVE into which a functional functional group was introduced was obtained.

Example 5 Synthesis Example The propylene oxide-modified HBVE obtained in Example 2 was transesterified in the same manner as in Example 4 to obtain the desired propylene oxide-modified HBVE into which an air-curable functional group was introduced.

(Examples 6 to 11: Synthesis Examples) Internal volume 550 cm
³ xylene 25 in a pressure-resistant reactor with a stainless steel stirrer
2 g, ethanol 71 g, potassium carbonate 1.4 g, and azobisisobutyronitrile 2.2 g were charged, and a monomer having a composition shown in Table 1 (unit: g, parenthesis: mol%) was polymerized. Polymerization is performed using chlorotrifluoroethylene (CT
After charging monomers other than FE) or tetrafluoroethylene (TFE), residual air is removed with liquid nitrogen, then CTFE or TFE is introduced, and the temperature is gradually raised, and the temperature is maintained at 65 ° C. After the polymerization reaction was continued for 6 to 10 hours under stirring, the polymerization was stopped by cooling the reactor with water. After cooling the reactor to room temperature, unreacted monomers were withdrawn and the reactor was opened. After the polymer solution was filtered, ethanol was removed at 50 ° C. using an evaporator to obtain a xylene solution of a fluorinated copolymer.

Table 1 shows the number average molecular weight of the obtained fluorine-containing copolymer. In the table, EVE indicates ethyl vinyl ether, CHVE indicates cyclohexyl vinyl ether,
Examples 1 and 2 show the modified HBVE obtained in Examples 1 and 2.

Examples 12 to 15: Synthesis Examples Monomers having the compositions shown in Table 2 were polymerized in the same manner as in Examples 6 to 11 to obtain fluorinated copolymers. Examples 4 and 5 show the modified HBVE obtained in Examples 4 and 5.

(Examples 16 to 21: Synthesis Examples) From the fluorine-containing copolymer obtained in Examples 6 to 11 and methyl α-eleostearate obtained in Example 3, an ester was prepared by the method shown in Example 4. The exchange was performed to obtain a fluorinated copolymer having an air-curable functional group. Table 3 shows a list of the fluorinated copolymers used in each synthesis example.

Examples 22 to 29 (Examples) and Examples 30 to
32 (Comparative Example) Silyl group-containing polyether (A) 10
5 parts by weight of a fluorinated air-curable polymer shown in Tables 4 and 5 (not added only in Example 32) to 0 parts by weight (hereinafter, referred to as parts), CCR (calcium carbonate manufactured by Shiraishi Industry Co., Ltd.) 6
0 parts, Whiten SB (Calcium carbonate manufactured by Shiraishi Industry Co., Ltd.)
70 parts, 60 parts of DOP, 5 parts of Epicoat 828 (epoxy compound manufactured by Yuka Shell Epoxy), titanium oxide
5 parts, Tinuvin 327 (a benzotriazole-based ultraviolet absorber manufactured by Ciba-Geigy), 1 part, Sanol 765 (a hindered amine-based light stabilizer manufactured by Sankyo), 0.5 part, Irganox 245 (a hindered phenol manufactured by Ciba-Geigy) 1 part of hydrogenated castor oil and 4.0 parts of hydrogenated castor oil,
After mixing at 60 ° C. for 3 hours with a 2 L planetary mixer, the mixture was subjected to vacuum degassing at 10 Torr to obtain a composition.

Tin dioctanoate and laurylamine were mixed at a ratio of 3/1.
3 parts of the curing catalyst mixed in the above weight ratio was added to the above composition and kneaded well. 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.

The cured sheet was left at an angle of 45 ° on the south side of the roof of the laboratory of Asahi Glass Co., Ltd. located in Yokohama City, Kanagawa Prefecture, and the weathering resistance after six months was visually observed. The results are shown in Tables 4 and 5. The evaluation criteria were as follows: 付 着: Almost no dust adhered, Δ: Dust adhered,
X: It was determined that dust was badly attached.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

[0109]

[Table 5]

[0110]

As described above, the curable composition of the present invention has excellent surface contamination resistance upon exposure to sunlight, an elastic sealing material,
Ideal as a waterproof material.

Claims (6)

[Claims] 1. An organic polymer (A) containing on average one or more reactive silyl groups in the molecule, and a polymerized unit (1) based on a fluoroolefin are added in an amount of 2 to the total polymerized unit.
0 to 70 mol%, 1 to 80 mol% of the polymerized unit (2) having an air-curable functional group based on all polymerized units, and
Polymerized units other than the polymerized units (1) and having no air-curable functional group (3) are added in an amount of 0 to all the polymerized units.
The total of the polymerized units (1) and (2) is contained in a proportion of 30 mol% or more based on all the polymerized units, and the number average molecular weight is 1,000 to 1,000,000
A curable composition comprising the fluorine-containing air-curable polymer (B). 2. The mixing ratio of the organic polymer (A) and the fluorinated air-curable polymer (B) is expressed by weight ratio: (A) / (B) =
The curable composition according to claim 1, wherein the curable composition is 100 / 0.1 to 100/20. 3. The curable composition according to claim 1, wherein the main chain of the organic polymer (A) is essentially a polyoxyalkylene chain. 4. The organic polymer (A) has a number average molecular weight of 100.
2. The curable composition of claim 1, wherein the amount is from 0 to 50,000. 5. The curable composition according to claim 1, wherein the polymer unit (3) is a polymer unit based on a monomer selected from vinyl ethers, vinyl esters, allyl ethers, and crotonic esters. 6. The curable composition according to claim 1, wherein the air-curable functional group is an acyl group derived from a higher fatty acid having a conjugated double bond.