JPH0841356A - Curable composition - Google Patents

Abstract

PURPOSE:To improve the resistances to staining, chemicals, solvents, heat, weather, and moisture permeation of a curable compsn. CONSTITUTION:This compsn. contains 100 pts.wt. satd. hydrocarbon polymer having a hydroxyl or hydrolyzable group bonded to a silicon atom and at least one silicon-contg. group capable of cross-linking by forming a siloxane bond and 0.01-20 pts.wt. photocurable substance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to stain resistance, chemical resistance, solvent resistance, heat resistance, and weather resistance, which are useful as sealing materials and sealants for construction, automobiles, ships, roads, etc. And a curable composition having excellent moisture permeation resistance and the like.

[0002]

2. Description of the Related Art A silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by forming a siloxane bond (hereinafter referred to as "reactive silicon group").
The saturated hydrocarbon polymer having ## STR3 ## can be a liquid polymer, and can be cured at room temperature due to moisture or the like to produce a rubber-like cured product, and thus is used as an elastic sealant for construction. However, the cured product of this polymer is unfavorable because the surface of the cured product is contaminated by the adhesion of dust or the like depending on the compounding composition, curing conditions, etc., and the appearance thereof is impaired (hereinafter referred to as "contaminating property"). ), There is a problem that its use is limited.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a curable composition which exhibits a remarkable antifouling effect by improving the surface of a cured product to be non-tacky. That is, the object of the present invention is to solve the problems of the conventional curable composition as described above, to quickly cure by water in the air or the like at room temperature, and to improve the surface of the cured product to be non-adhesive. Another object of the present invention is to provide a curable composition that gives an excellent rubber-like cured product that exhibits a remarkable anti-staining effect.

[0004]

The above objects of the present invention are as follows.
(A) a saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group capable of crosslinking by forming a siloxane bond, and (B) the saturated hydrocarbon This can be achieved by a curable composition containing 0.01 to 20 parts by weight of a photocurable substance with respect to 100 parts by weight of the polymer.

The present invention will be described in detail below. In the present invention, a saturated hydrocarbon polymer having a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by forming a siloxane bond, that is, at least one reactive silicon group ( Hereinafter, a saturated hydrocarbon polymer (A) will be used. The reactive silicon group used in the present invention is a well-known functional group, and a typical example thereof is represented by the general formula (I):

[0006]

Embedded image (In the formula, R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms.
20 aralkyl group, or (R') ₃ SiO- (R'
Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different. ) Represents a triorganosiloxy group, and when two or more R ¹ and R ² are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. a is 0, 1, 2 or 3 and b is 0, 1 or 2,
a + mb ≧ 1. Also, m

[0007]

Embedded image B need not be the same. m is 0 or 1-1
It is an integer of 9. And a group represented by).

The hydrolyzable group in the general formula (1) is not particularly limited and may be a conventionally known hydrolyzable group. Specific examples thereof include a hydrogen atom, an alkoxy group and an acyloxy group. , A ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like. Among these, since the hydrolyzability is mild and easy to handle,
Alkoxy groups are particularly preferred.

This hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and (a + m
b) is preferably in the range of 1-5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.

The silicon atom forming this reactive silicon group is 1
The number may be one or two or more, but in the case of silicon atoms connected by a siloxane bond or the like, it is preferable that the number is 20 or less. In particular, the formula:

[0011]

[Chemical 3] (In the formula, R ² , X and a are the same as above.) The reactive silicon group represented by the formula is preferred because it is easily available.

At least one, preferably 1.1 to 5, reactive silicon groups are present in one molecule of the saturated hydrocarbon polymer. When the number of reactive silicon groups contained in the molecule is less than 1, the curability becomes insufficient and it becomes difficult to exhibit good rubber elasticity behavior.

The reactive silicon group may be present at the terminal of the saturated hydrocarbon polymer molecular chain, may be present inside, or may be present at both ends. In particular, when the reactive silicon group is present at the terminal of the molecular chain, the effective hydrocarbon chain content of the saturated hydrocarbon polymer component contained in the finally formed cured product is large, so that high strength and high elongation are obtained. It is preferable in that a rubbery cured product can be easily obtained. Further, these saturated hydrocarbon polymers having a reactive silicon group may be used alone or in combination of two or more kinds.

The saturated hydrocarbon polymer used in the present invention is a concept which means a polymer which does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the reactive silicon group used in the present invention. The polymer serving as the skeleton of the saturated hydrocarbon polymer having is can be obtained by the following method.

(1) A method of polymerizing an olefin compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as a main monomer. (2) A method in which a diene compound such as butadiene or isoprene is homopolymerized, or the olefin compound and the diene compound are copolymerized and then hydrogenated.

Of these polymers, isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferred because they are easy to introduce a functional group at the terminal, easy to control the molecular weight, and can increase the number of terminal functional groups. It is preferably a polymer.

In this isobutylene-based polymer, all of the monomer units may be formed of isobutylene units, and the monomer units having a copolymerizability with isobutylene are preferably contained in the isobutylene-based polymer in an amount of 50% ( % By weight, and so on)
Or less, more preferably 30% or less, particularly preferably 10% or less.
It may be contained in the range of not more than%.

As such a monomer component, for example,
Examples thereof include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinylsilanes, allylsilanes and the like. Specific examples of such a copolymer component include:
For example, 1-butene, 2-butene, 2-methyl-1-butene, 3-
Methyl-1-butene, pentene, 4-methyl-1-pentene,
Hexene, vinyl cyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyl. Dimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane Allylmethyldichlorosilane, Allyldimethylchlorosilane, Allyldimethylmethoxysilane, Allyltrimethylsilane, Diallyldichlorosilane, Dia Examples thereof include ryldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like.

When vinyl silanes or allyl silanes are used as monomers copolymerizable with these isobutylenes, the silicon content of the polymer is increased and the number of groups capable of acting as a silane coupling agent is increased, resulting in a composition. The adhesiveness of the object is improved.

Further, in the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers as well as in the case of the isobutylene-based polymer, other monomer units other than the main monomer unit are used. May be included.

Further, the saturated hydrocarbon polymer used in the present invention includes butadiene, within the range in which the object of the present invention is achieved.
A small amount, preferably 10% or less, more preferably 5% or less, particularly 1% or less of a monomer unit having a double bond remaining after polymerization such as a polyene compound such as isoprene may be contained.

The number average molecular weight of this saturated hydrocarbon polymer (A), particularly isobutylene polymer or hydrogenated polybutadiene polymer, is preferably about 500 to 100,000, and particularly preferably 1,000 to 30. Those having a liquid or fluidity of about 1,000 are preferable from the viewpoint of easy handling. Further, regarding the molecular weight distribution (M _w / M _n ), the narrower the M _w / M _n is, the more preferable the viscosity is at the same molecular weight.

A method for producing a saturated hydrocarbon polymer having a reactive silicon group will be described with reference to isobutylene polymer and hydrogenated polybutadiene polymer. Among the isobutylene-based polymers having a reactive silicon group described above, an isobutylene-based polymer having a reactive silicon group at a molecular end is a polymerization method called an inifer method (specifically serving as an initiator and a chain transfer agent called an inifer method). It can be produced by using a terminal functional type, preferably all terminal functional type isobutylene-based polymer obtained by a cationic polymerization method using the compound of 1. Such a manufacturing method is disclosed in JP-A-63 / 1988.
-6003, 63-6041, 63-2541
No. 49, No. 64-22904, and No. 64-38407.

The isobutylene-based polymer having a reactive silicon group in the molecule is obtained by adding vinylsilanes or allylsilanes having a reactive silicon group to a monomer mainly containing isobutylene and copolymerizing them. Manufactured by.

Further, in the polymerization for producing an isobutylene polymer having a reactive silicon group at the molecular end, vinylsilanes and allylsilanes having a reactive silicon group are co-produced in addition to the main component isobutylene monomer. By introducing a reactive silicon group at the terminal after the polymerization, an isobutylene polymer having a reactive silicon group at the terminal and inside the molecular chain can be produced.

Specific examples of the vinylsilanes and allylsilanes having the reactive silicon group include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, and the like. Examples thereof include allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.

Regarding the method for producing the hydrogenated polybutadiene-based polymer, for example, first, the hydroxyl group of the terminal hydroxy hydrogenated polybutadiene-based polymer is converted to an oxymetal group such as -ONa or -OK, and then the general formula (2): ^{_{CH 2 = CH-R 3 -Y}} (2) ( in the formula, Y is chlorine atom, a halogen atom such as iodine atom, R ^{3 is, -R 4 -, - R 4} -OC (= O) -, -R
^4- C (= O)-(R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and preferable specific examples thereof include an alkylene group, a cycloalkylene group, an arylene group, and an aralkylene group). A divalent organic group selected from —CH ₂ — and R ″ —Ph—CH ₂ — (R ″ is a hydrocarbon group having 1 to 10 carbon atoms and Ph is a p-phenylene group) 2
Particularly preferred are valent groups. By reacting the organic halogen compound represented by the formula (1), a hydrogenated polybutadiene polymer having a terminal olefin group (hereinafter, also referred to as a terminal olefin hydrogenated polybutadiene polymer) can be produced.

The method of converting the terminal hydroxyl group of the terminal hydroxy-hydrogenated polybutadiene polymer into an oxymetal group is as follows.
Alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ; Na
Examples thereof include a method of reacting with caustic alkali such as OH and KOH.

In the above method, a terminal olefin hydrogenated polybutadiene polymer having almost the same molecular weight as the terminal hydroxy hydrogenated polybutadiene polymer used as the starting material can be obtained, but in order to obtain a higher molecular weight polymer. Before reacting the organohalogen compound of the general formula (2), methylene chloride, bis (chloromethyl) benzene,
When the molecular weight is increased by reacting with a polyvalent organic halogen compound containing two or more halogen atoms in one molecule such as bis (chloromethyl) ether, and then reacted with the organic halogen compound represented by the general formula (2). It is possible to obtain a hydrogenated polybutadiene-based polymer having a higher molecular weight and having an olefin group at the terminal.

Specific examples of the organic halogen compound represented by the above general formula (2) include allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene and allyl (chloro). Methyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl)
Ether, 1-hexenyl (chloromethoxy) benzene,
Examples include, but are not limited to, allyloxy (chloromethyl) benzene and the like. Of these, allyl chloride is preferable because it is inexpensive and easily reacted.

Introduction of the reactive silicon group into the terminal olefin hydrogenated polybutadiene polymer is represented by, for example, the general formula (1) as in the case of the isobutylene polymer having a reactive silicon group at the terminal of the molecular chain. A hydrosilane compound having a hydrogen atom bonded to a group represented by the formula:

[0032]

[Chemical 4] (In the formula, R ² , X and a are the same as above.) The compound can be produced by addition reaction using a platinum catalyst.

Specific examples of the hydrosilane compound having a hydrogen atom bonded to the group represented by the general formula (1) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane; Alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoxymate) methylsilane Examples thereof include, but are not limited to, ketoxymate silanes such as bis (cyclohexyl ketoximate) methylsilane. Of these, halogenated silanes and alkoxysilanes are particularly preferable.

The photocurable substance of the component (B) used in the present invention is a substance which undergoes a chemical change in the molecular structure in a considerably short time by the action of light and causes a physical change such as curing. Various substances such as organic monomers, oligomers, resins or compositions containing these are known as this type of substance, and any commercially available substance can be used in the present invention. As a typical example, an unsaturated acrylic compound,
Examples thereof include polyvinyl cinnamate and azide resin.

The above-mentioned unsaturated acrylic compound is a monomer, an oligomer or a mixture thereof having one or several acrylic or methacrylic unsaturated groups, and is propylene (or butylene, ethylene) glycol di (meth). Monomers such as acrylate, neopentyl glycol di (meth) dimethacrylate or molecular weight 10,
000 or less oligoesters can be mentioned.

Examples of the above-mentioned polyvinyl cinnamate include cinnamic acid esterification products of polyvinyl alcohol, which is known as a photosensitive resin having a cinnamoyl group as a photosensitive group, and many polyvinyl cinnamate derivatives. .

The above-mentioned azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution containing a diazide compound as a photosensitizer,
“Photosensitive resin” (published on March 17, 1972, published by The Printing Society of Japan, page 93-, page 106-, page 117-) has detailed examples. These may be used alone or in combination. If necessary, a sensitizer may be added and used.

The amount of the component (B) used is 0.01 with respect to 100 parts by weight of the saturated hydrocarbon polymer of the component (A).
~ 20 parts by weight. If the amount of the component (B) used is less than 0.01 parts by weight, the effect is small, and if it exceeds 20 parts by weight, the physical properties may be adversely affected, which is not preferable.

The effect may be further enhanced by adding a sensitizer such as a ketone or a nitro compound or an accelerator such as an amine. A curing catalyst, a plasticizer, a filler, other additives, and the like may be added to the composition of the present invention, if necessary.

The curing catalyst is not specifically limited, but a commonly used curing catalyst is used. Specific examples of such a curing catalyst include, for example, tin octylate, dibutyltin dilaurate, dibutyltin maleate,
Carboxylic acid metal salt such as dibutyltin phthalate; Reaction product of organic tin oxide and ester; Tetrabutyl titanate;
Organic titanic acid esters such as organosiloxytitanium; amines, amine salts, quaternary ammonium salts, granidine compounds and the like. These curing catalysts are used in an amount of 0 to 10 parts by weight based on 100 parts by weight of the saturated hydrocarbon polymer.

Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate; dioctyl adipate, dioctyl sebacate. And non-aromatic dibasic acid esters such as; tricresyl phosphate, tributyl phosphate, and other phosphoric acid esters, and the like, and examples of the relatively high molecular weight type plasticizer include:
Polyester plasticizers such as polyesters of dibasic acid and dihydric alcohol; polyethers such as polypropylene glycol and its derivatives; poly-α-methylstyrene,
Polystyrenes such as polystyrene; process oils,
Examples include alkylbenzenes and trimellitic acids. These can be used alone or in combination. However, it is preferable to select one having good compatibility. These plasticizers are saturated hydrocarbon polymers (A) 1
20 to 200 parts by weight is used with respect to 00 parts by weight.

Specific examples of the above filler include heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, kaolin, talc, silica, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, carbon black and the like. To be When a filler is used, its amount is preferably in the range of 10 to 300 parts by weight with respect to 100 parts by weight of the saturated hydrocarbon polymer (A).

Examples of the other additives include hydrogenated castor oil, anti-sagging agents such as organic bentonite, colorants, anti-aging agents, and adhesion-imparting agents. The curable composition of the present invention thus obtained is an adhesive, a pressure-sensitive adhesive, a paint, a waterproof film, a sealant composition, a molding material,
It can be usefully used as a cast rubber material, a foam material, and the like, and the application as a sealant is particularly useful. Further, since it has excellent moisture permeation resistance, it is also useful as a material for double glazing.

[0044]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Production Example 1 Production of Saturated Hydrocarbon Polymer (A) In a four-necked flask equipped with a stirrer and a nitrogen line, 560 mL of dried methylene chloride and 116-n-hexane were mixed.
0 mL, 940 mg of α-methyl pyridine and 22 g of p-dicumyl chloride were weighed to form a uniform mixed solution, and the temperature was -70 ° C.
After cooling to room temperature, 570 mL of isobutylene monomer was charged under reduced pressure through a Molecule Sieves tube.

In the above reaction solution cooled to -70 ° C,
A polymerization catalyst solution (titanium tetrachloride 14
(mL / methylene chloride 80 mL) was added all at once to initiate polymerization. Once the temperature is raised to -54 ° C, it will be -7 in about 17 minutes.
The temperature was lowered to 0 ° C. About 20 minutes after the initiation of polymerization, 132 g of 1,9-decadiene was added, and stirring was continued at -70 ° C for 4 hours.

The turbid yellow reaction solution was mixed with 3 L of warm water (about 45
(° C), the mixture was stirred for about 2 hours, the organic layer was separated, and washing with pure water was repeated 3 times. The colorless and transparent organic layer thus obtained was concentrated under reduced pressure to obtain about 400 g of an isobutylene oligomer having vinyl groups at both ends.

Then, 400 g of the vinyl group-containing isobutylene oligomer thus obtained was added to 200 mL of n-heptane.
Dissolved in water, heated to about 70 ° C, and then added with methyldimethoxysilane 1.5 [eq / vinyl group] and platinum (vinyl siloxane) complex 1 × 10 ^-4 [eq / vinyl group] to carry out hydrosilylation reaction. I went. The reaction was traced by FT-IR, and the olefin absorption at 1640 cm ^-1 disappeared in about 4 hours.

By concentrating the reaction solution under reduced pressure, an intended isobutylene oligomer having reactive silicon groups at both ends was obtained. [Structural formula]

[0049]

[Chemical 5] Production Example 2 Production of Saturated Hydrocarbon Polymer (A) In the same manner as in Production Example 1 except that 24 g of allylmethylsilane was used in place of 1,9-decadiene in Production Example 1, the structure of the production intermediate was obtained. To obtain isobutylene oligomer. [Structural formula]

[0050]

[Chemical 6] Production Example 3 Production of Saturated Hydrocarbon Polymer (A) In a four-necked flask equipped with a stirrer and a nitrogen line, 560 mL of dried methylene chloride and 116-n-hexane were mixed.
0 mL, 940 mg of α-methyl pyridine and 22 g of p-dicumyl chloride were weighed to form a uniform mixed solution, and the temperature was -70 ° C.
After cooling to room temperature, 570 mL of isobutylene monomer was charged under reduced pressure through a Molecule Sieves tube.

In the above reaction solution cooled to -70 ° C,
A polymerization catalyst solution (titanium tetrachloride 14
(mL / methylene chloride 80 mL) was added all at once to initiate polymerization. Once the temperature is raised to -54 ° C, it will be -7 in about 17 minutes.
The temperature was lowered to 0 ° C. After the initiation of polymerization, stirring was continued for about 60 minutes. Turn the cloudy reaction solution into 3 L of warm water (approximately 45 ° C).
The mixture was placed in the flask, stirred for about 2 hours, the organic layer was separated, and washing with pure water was repeated 3 times. The colorless and transparent organic layer thus obtained was concentrated under reduced pressure to obtain about 400 g of an isobutylene oligomer having a tertiary chloro group at both ends.

Furthermore, by heating the isobutylene oligomer under reduced pressure at 170 ° C. for 2 hours,
A thermal dehydrochlorination reaction was performed to obtain an isobutylene oligomer having isopropenyl groups at both ends.

Then, 400 g of the isopropenyl group-containing isobutylene oligomer thus obtained was dissolved in 200 mL of n-heptane and heated to about 100 ° C. in a pressure vessel, and then methyldichlorosilane 1.5 [eq / eq. Vinyl group],
Platinum (vinyl siloxane complex 1 × 10 ⁻⁴ [eq / vinyl group] was added to carry out hydrosilylation reaction. FT-I
The reaction was traced by R, and the olefin absorption at 1640 cm ^-1 disappeared in about 10 hours. After cooling the reaction solution to 60 ° C., an excess amount of [/ methyldichlorosilane] methanol was added, and the mixture was stirred for about 4 hours to complete the methoxylation. By concentrating the reaction solution under reduced pressure, an intended isobutylene oligomer having reactive silicon groups at both ends was obtained. [Structural formula]

[0054]

[Chemical 7] Examples 1 to 9 To the various polymers 100 obtained in Production Examples 1 to 3 as the saturated hydrocarbon polymer (A), the photocurable substance was added in the number shown in Table 1, and then the colloidal calcium carbonate was added. (Maruo Calcium Co., Ltd., trade name Viscolite R) 120 parts,
Heavy calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., trade name Whiten SB) 20 parts, plasticizer (manufactured by Idemitsu Petrochemical Co., Ltd., trade name PS-32) 90 parts, hindered phenol anti-aging agent (Ciba Geigy) Co., Ltd., trade name Irganox 1010) 1 part, benzotriazole-based UV absorber (Ciba Geigy, trade name Tinuvin 327) 1 part, cross-linking agent (sodium hydrogen sulfate) 5 parts, tin octylate 3 parts,
After adding 1 part of laurylamine and mixing well, this mixture was passed through three small paint rolls three times to give a thickness of 5
mm sheets were made. Comparative Examples 10 to 12 For various polymers 100 obtained in Production Examples 1 to 3 as the saturated hydrocarbon polymer (A), colloidal calcium carbonate (trade name: Viscolite R, manufactured by Maruo Calcium Co., Ltd.) 120
Part, heavy calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., trade name Whiten SB), 20 parts, plasticizer (Idemitsu Petrochemical Co., Ltd.)
Made, product name PS-32) 90 parts, hindered phenol type anti-aging agent (Ciba Geigy Co., Ltd. product name Irganox 1010) 1 part, benzotriazole type ultraviolet absorber (Ciba Geigy Co., product name Tinuvin 327) 1
Parts, 5 parts of a cross-linking agent (sodium hydrogensulfate), 3 parts of tin octylate, and 1 part of laurylamine were added and mixed well,
Pass the mixture 3 times between 3 small paint rolls,
A sheet having a thickness of 5 mm was produced.

Next, Examples 1 to 9 and Comparative Examples 10 to 12
Test pieces made of various samples prepared in
After curing at 5% RH for 1 day, it was exposed to the outdoors in the Hyogo Ward district of Kobe City, Hyogo Prefecture (slope of 45 ° on the south side), and the contamination state of the surface of the test piece was observed. The results are shown in Table 1 below.

[0056]

[Table 1]

The photo-curable substances shown in Table 1 are all oligoester acrylates manufactured by Toagosei Co., Ltd. and have the following structural formulas. Aronikusu _{M-309: (CH 2 =} CHCOOCH 2 -) 3 -CCH 2 CH 3 Aronikusu _{M-400: [(CH 2} = CHCOOCH 2 -) 3 -CCH 2 -] -
O Aronix M-8060: A-[-X (-A) -Y-] _n- X (-A) ₂ (A: acrylic acid, X: polyhydric alcohol, Y: polybasic acid) Table-1 In the evaluation of the pollution state of the inside, Table-1
As can be seen from the results of, the curable composition of the present invention,
By adding the component (B), the surface contamination property is improved when it is exposed for a long period of time, and obviously the improvement effect is remarkable as compared with the case where no photocurable substance is used.

[0058]

EFFECT OF THE INVENTION In recent years, the market demand for pollution is extremely severe from the viewpoint of importance of aesthetics as well.
The curable composition of the present invention is excellent in stain resistance, chemical resistance, solvent resistance, heat resistance, weather resistance, moisture permeation resistance, etc.,
It is extremely useful as a sealant and sealant for construction, automobiles, ships and roads.

Claims (1)

[Claims] 1. A saturated hydrocarbon polymer having (A) a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group capable of being crosslinked by forming a siloxane bond, and (B) ) A curable composition comprising 0.01 to 20 parts by weight of a photocurable substance with respect to 100 parts by weight of the saturated hydrocarbon polymer.