JP3317586B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to stain resistance, chemical resistance, solvent resistance, heat resistance, and weather resistance, which are particularly useful as sealants and sealants for buildings, automobiles, ships and roads. The present invention relates to a curable composition having excellent heat resistance and moisture permeability.

[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").
Is a polymer which can be a liquid polymer and can be cured at room temperature by moisture or the like to produce a rubber-like cured product. Therefore, it is used as an elastic sealant for construction. However, the cured product of this polymer is undesired in that the surface of the cured product is contaminated by the attachment of dust and the like, depending on the composition and curing conditions, and the appearance is impaired (hereinafter referred to as “contamination”). ), 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 anti-staining effect by improving the surface of the cured product to be non-tacky. That is, an object of the present invention is to solve the problems of the conventional curable composition as described above, and to quickly cure by moisture or the like in the air at room temperature to improve the surface of the cured product to be non-adhesive. Another object of the present invention is to provide a curable composition which gives an excellent rubber-like cured product exhibiting a remarkable effect of preventing contamination.

[0004]

The above objects of the present invention are as follows.
(A) a saturated hydrocarbon polymer having at least one silicon-containing group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond, (B) the saturated hydrocarbon polymer 0.01 to 20 parts by weight of a photocurable substance per 100 parts by weight of the polymer; and (C)
0.1 to 100 parts by weight of the saturated hydrocarbon polymer
This was achieved with a curable composition containing ２０20 parts by weight of an unsaturated compound capable of reacting with oxygen in the air.

Hereinafter, the present invention will be described in detail. In the present invention, a saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond, that is, a saturated hydrocarbon polymer having at least one reactive silicon group ( Hereinafter, a saturated hydrocarbon polymer (A) is 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 (Wherein, R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
20 aralkyl groups or (R ′) ₃ SiO— (R ′
Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's 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; b is 0, 1 or 2;
a + mb ≧ 1. In addition, m

[0007]

Embedded image B need not be the same. m is 0 or 1 to 1
It is an integer of 9. )).

The hydrolyzable group in the general formula (1) is not particularly limited, and may be a conventionally known hydrolyzable group. Specific examples include, for example, 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, an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling.

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

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

[0011]

Embedded image (In the formula, R ² , X and a are the same as described above.) A reactive silicon group represented by the formula (1) is preferable 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. If the number of reactive silicon groups contained in the molecule is less than one, 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 molecular chain of the saturated hydrocarbon polymer, may be present inside, or may be present at both. In particular, when the reactive silicon group is present at the molecular chain terminal, the effective network chain amount of the saturated hydrocarbon-based polymer component contained in the finally formed cured product increases, so that high strength and high elongation are obtained. It is preferable from the viewpoint that a rubber-like cured product is easily obtained. These saturated hydrocarbon polymers having a reactive silicon group may be used alone or in combination of two or more.

The saturated hydrocarbon polymer used in the present invention is a concept meaning a polymer which does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring. The polymer serving as the skeleton of the saturated hydrocarbon polymer having the following formula (1) can be obtained by the following method.

(1) A method in which an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene is polymerized as a main monomer. (2) A method of homopolymerizing a diene compound such as butadiene or isoprene or copolymerizing the olefin compound with a diene compound and then hydrogenating.

Among these polymers, isobutylene-based polymers and hydrogenated polybutadiene-based polymers can be easily introduced into the terminal, the molecular weight can be easily controlled, and the number of terminal functional groups can be increased. It is preferably a polymer.

In the isobutylene-based polymer, all of the monomer units may be formed of isobutylene units, and the monomer unit having copolymerizability with isobutylene is preferably 50% ( Wt%, the same applies hereinafter)
Or less, more preferably 30% or less, particularly preferably 10% or less.
% Or less.

As such a monomer component, for example,
Examples thereof include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. 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, vinylcyclohexane, 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, and γ-methacryloyloxypropylmethyldimethoxysilane.

When vinyl silanes or allyl silanes are used as monomers copolymerizable with isobutylene, the silicon content of the polymer increases, and the number of groups that can act as a silane coupling agent increases, resulting in a composition that can be obtained. The adhesiveness of the object is improved.

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

The saturated hydrocarbon polymer used in the present invention contains butadiene,
A monomer unit having a double bond remaining after polymerization, such as a polyene compound such as isoprene, may be contained in a small amount, preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less.

The number average molecular weight of the saturated hydrocarbon polymer (A), particularly the isobutylene polymer or the hydrogenated polybutadiene polymer, is preferably about 500 to 100,000, and more preferably 1,000 to 30. Those having a liquidity or fluidity of about 2,000 are preferred from the viewpoint of easy handling. Further, with respect to the molecular weight distribution ( _Mw / _Mn ), the narrower the _Mw / _Mn , the more preferable the viscosity becomes lower at the same molecular weight.

The method for producing a saturated hydrocarbon polymer having a reactive silicon group will be described with reference to the case of an isobutylene polymer and a hydrogenated polybutadiene polymer. Among the above-mentioned isobutylene-based polymers having a reactive silicon group, an isobutylene-based polymer having a reactive silicon group at a molecular terminal is a polymerization method called an inifer method (a specific method using both an initiator called a inifer and a chain transfer agent). Can be produced using a terminal functional type, preferably an all-terminal functional isobutylene-based polymer obtained by a cationic polymerization method using a compound of the formula (1). Such a manufacturing method is disclosed in
No.-6003, No.63-6041, No.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 a vinylsilane or an allylsilane having a reactive silicon group to a monomer mainly composed of isobutylene and copolymerizing the monomer. Manufactured by

Further, in the polymerization for producing an isobutylene-based polymer having a reactive silicon group at the molecular terminal, a vinylsilane or an allylsilane having a reactive silicon group other than the main component isobutylene monomer is used. By introducing a reactive silicon group into the terminal after the polymerization, an isobutylene-based polymer having a reactive silicon group at the terminal and inside the molecular chain can be produced.

Specific examples of vinylsilanes and allylsilanes having a reactive silicon group include, for example, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, Allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallylmethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like can be mentioned.

With respect to 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 ＣＨCH—R ³ —Y (2) (where Y is a halogen atom such as a chlorine atom or an iodine atom, and 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, preferably an alkylene group specific examples, a cycloalkylene group, an arylene group, and aralkylene group) represented by a divalent organic group, -CH ₂ - and _{R '' - Ph-CH 2} - (R '' is a hydrocarbon group having 1 to 10 carbon atoms, Ph is p- phenylene group.) 2 selected from
Valent groups are particularly preferred. ) To produce a hydrogenated polybutadiene polymer having a terminal olefin group (hereinafter, also referred to as a hydrogenated polybutadiene polymer having a terminal olefin).

A method for converting a terminal hydroxyl group of a terminally hydrogenated polybutadiene polymer into an oxymetal group is as follows.
Alkali metal such as Na, K; metal hydride such as NaH; metal alkoxide such as NaOCH ₃ ;
A method of reacting with a caustic alkali such as OH and KOH can be used.

In the above-described method, a hydrogenated polybutadiene-terminated olefin polymer having substantially the same molecular weight as the hydroxy-terminated polybutadiene-based polymer used as the starting material can be obtained. Before reacting the organic halogen compound of the general formula (2), methylene chloride, bis (chloromethyl) benzene,
After increasing the molecular weight by reacting with a polyvalent organic halogen compound containing two or more halogen atoms in one molecule such as bis (chloromethyl) ether, and then reacting with an organic halogen compound represented by the general formula (2) A hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at the terminal can be obtained.

Specific examples of the organic halogen compound represented by the general formula (2) include allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, 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. Of these,
Allyl chloride is preferred because it is inexpensive and easily reacts.

The introduction of the reactive silicon group into the hydrogenated polybutadiene polymer at the terminal olefin is carried out, for example, by the general formula (1) as in the case of the isobutylene polymer having a reactive silicon group at the molecular chain terminal. A hydrosilane compound in which a hydrogen atom is bonded to a group to be formed, preferably a general formula:

[0032]

Embedded image (Wherein R ² , X and a are the same as described above). The compound can be produced by an addition reaction using a platinum-based catalyst.

Specific examples of the hydrosilane compound having a hydrogen atom bonded to the group represented by the general formula (1) include, for example, 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 (dimethylketoximate) methylsilane And ketoxime silanes such as bis (cyclohexyl ketoximate) methyl silane, and the like, but are not limited thereto. Of these, halogenated silanes and alkoxysilanes are particularly preferred.

The photocurable substance (B) used in the present invention is a substance in which the molecular structure undergoes a chemical change in a very short time due to the action of light, thereby causing a physical change such as curing. Various substances such as organic monomers, oligomers, resins and compositions containing these are known as such substances, and any commercially available substance can be used in the present invention. Typical examples are unsaturated acrylic compounds,
Examples thereof include polyvinyl cinnamate and azide resins.

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

Examples of the above polyvinyl cinnamate include cinnamate ester of polyvinyl alcohol, which is known as a photosensitive resin having a cinnamoyl group as a photosensitive group, and many polyvinyl cinnamate derivatives. .

The 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 photosensitive agent,
"Photosensitive resin" (published March 17, 1972, published by the Printing Society of Japan, page 93-, page 106-, page 117-) has detailed examples, and these may be used alone or in combination. If necessary, a sensitizer may be added and used.

The amount of the component (B) is 0.01 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) is less than 0.01 part by weight, the effect is small, and if it exceeds 20 parts by weight, adverse effects may be exerted on physical properties, which is not preferable.

When a sensitizer such as a ketone or a nitro compound or an accelerator such as an amine is added, the effect may be further enhanced. Examples of the unsaturated compound (C) component capable of reacting with oxygen in the air used in the present invention include an air oxidation cured material generally referred to as a compound having an unsaturated group in a molecule which is polymerized by oxygen in the air. Is mentioned. More specifically, for example, dried oils represented by tung oil, linseed oil and the like, and various alkyd resins obtained by modifying the compound; acrylic polymers modified with a drying oil, epoxy resins, silicone resin; 1,2-polybutadiene, 1,4-polybutadiene, C ₅ -C ₈ polymers or copolymers of dienes, further various modified products of the polymer or copolymer (maleated modified product, boiled oil-modified And the like) are specific examples. Among them, liquid oil (liquid diene polymer) and modified products thereof are particularly preferable among tung oil and diene polymers.

Specific examples of the liquid diene polymer include butadiene, chloroprene, isoprene, and the like.
A liquid polymer obtained by polymerizing or copolymerizing a diene compound such as 1,3-pentadiene, or a monomer such as acrylonitrile or styrene having copolymerizability with these diene compounds is mainly composed of a diene compound. Polymers such as NBR and SBR obtained by copolymerization as well as various modified products thereof (maleated modified products, boiled oil modified products, etc.). These may be used alone or in combination of two or more. Of these liquid diene polymers, liquid polybutadiene is preferred.

The unsaturated compound (C) which can react with oxygen in the air may be used alone or in combination of two or more. The effect may be enhanced when a catalyst or a metal dryer that promotes the oxidative curing reaction is used in combination with the component (C). As these catalysts and metal dryers,
Examples thereof include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, and amine compounds.

The amount of the unsaturated compound (C) which can react with oxygen in the air is 0.1 to 20 parts by weight based on 100 parts by weight of the saturated hydrocarbon polymer as the component (A).
If the amount of the component (C) is less than 0.1 part by weight, the improvement of the contamination, which is the purpose of using an unsaturated compound that can react with oxygen in the air, is not sufficient. There is a tendency for the tensile properties and the like to be impaired. Preferably it is 1 to 10 parts by weight.

The composition of the present invention may be used by adding a curing catalyst, a plasticizer, a filler, other additives, and the like, if necessary. Specific examples of the curing catalyst are not particularly limited, and a commonly used curing catalyst is used. Specific examples of such a curing catalyst include, for example, tin octylate, dibutyltin dilaurate, dibutyltin maleate,
Metal salts of carboxylic acids such as dibutyltin phthalate; reaction products of organic tin oxides and esters; tetrabutyl titanate;
Organic titanates such as organosiloxytitanium; amines, amine salts, quaternary ammonium salts, granidine compounds and the like. These curing catalysts are used in an amount of about 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 and butyl phthalyl butyl glycolate; dioctyl adipate, dioctyl Non-aromatic dibasic acid esters such as sebacate; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; and the relatively high molecular weight type plasticizers include, for example, dibasic acid and dihydric alcohol. Polyester-based plasticizers such as polyesters; polyethers such as polypropylene glycol and derivatives thereof; polystyrenes such as poly-α-methylstyrene and polystyrene; process oils; alkylbenzenes;
And the like. These can be used alone or in combination. However, it is preferable to select one having good compatibility. These plasticizers are used in an amount of about 20 to 200 parts by weight based on 100 parts by weight of the saturated hydrocarbon polymer (A).

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

Examples of the other additives include an anti-sagging agent such as hydrogenated castor oil and organic bentonite, a coloring agent, an antioxidant, and an adhesion-imparting agent. The curable composition of the present invention thus obtained comprises an elastic sealing material, an adhesive, a pressure-sensitive adhesive, a paint, a coating film waterproofing agent, a sealant composition, a molding material, a cast rubber material, and a foam material. It can be usefully used as such. Among them, application to a sealant is particularly useful. Further, since it has excellent moisture permeation resistance, it is also useful as a material for double glazing.

[0047]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. 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 n-hexane 116 were added.
0 mL, 940 mg of α-methylpyridine and 22 g of p-dicumyl chloride were weighed to obtain a homogeneous mixed solution, and then the mixture was cooled at -70 ° C.
Then, under reduced pressure, 570 mL of isobutylene monomer was charged through a Molecular sieve tube.

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

The turbid reaction solution was mixed with 3 L of warm water (about 45 L).
C) and stirred for about 2 hours, the organic layer was separated, and the washing with pure water was repeated three 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.

Next, 400 g of the vinyl group-containing isobutylene oligomer thus obtained was added to 200 mL of n-heptane.
After heating to about 70 ° C., 1.5 [eq / vinyl group] of methyldimethoxysilane and 1 × 10 ⁻⁴ [eq / vinyl group] of a platinum (vinylsiloxane) complex were added, and a hydrosilylation reaction was performed. Was done. The reaction was followed by FT-IR, and the olefin absorption at 1640 cm ^-1 disappeared in about 4 hours.

The reaction solution was concentrated under reduced pressure to obtain the desired isobutylene oligomer having reactive silicon groups at both ends. [Structural formula]

[0052]

Embedded image 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 instead of 1,9-decadiene, the structure of the production intermediate was obtained. However, an isobutylene oligomer partially different was obtained. [Structural formula]

[0053]

Embedded image 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 n-hexane 116 were added.
0 mL, 940 mg of α-methylpyridine and 22 g of p-dicumyl chloride were weighed to obtain a homogeneous mixed solution, and then the mixture was cooled at -70 ° C.
Then, under reduced pressure, 570 mL of isobutylene monomer was charged through a Molecular sieve tube.

In the above reaction solution cooled to -70 ° C,
Under stirring, the polymerization catalyst solution (titanium tetrachloride 14
(mL / 80 mL of methylene chloride) was added all at once to initiate the polymerization. Once the temperature was raised to -54 ° C, the temperature was reduced to -7 in about 17 minutes.
The temperature was lowered to 0 ° C. After the start of the polymerization, stirring was continued for about 60 minutes. Transfer the yellow-colored reaction solution to 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 three times. The thus obtained colorless and transparent organic layer was concentrated under reduced pressure to obtain about 400 g of an isobutylene oligomer having tertiary chloro groups at both ends.

Further, the isobutylene oligomer is heated at 170 ° C. under reduced pressure for 2 hours, whereby
A thermal dehydrochlorination reaction was performed to obtain an isobutylene oligomer having an isopropenyl group at both ends.

Next, 400 g of the isobutylene-containing isobutylene oligomer thus obtained was dissolved in 200 mL of n-heptane, and the temperature was raised to about 100 ° C. in a pressure vessel. Vinyl group],
Platinum (vinylsiloxane complex 1 × 10 ⁻⁴ [eq / vinyl group]) was added to carry out a hydrosilylation reaction.
The reaction was followed 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. The reaction solution was concentrated under reduced pressure to obtain a desired isobutylene oligomer having reactive silicon groups at both ends. [Structural formula]

[0057]

Embedded image Example 1 5 parts of a photocurable substance (Toa Gosei Chemical Co., Ltd., trade name ARONIX M-309) was added to 100 parts of the polymer obtained in Production Example 1 as a saturated hydrocarbon polymer (A). After adding 5 parts of tung oil as an unsaturated compound capable of reacting with oxygen in the air, colloidal calcium carbonate (manufactured by Maruo Calcium Co., Ltd.
120 parts of Viscolite R (trade name), 20 parts of heavy calcium carbonate (trade name: Whiten SB, manufactured by Shiraishi Industry Co., Ltd.)
Process oil (made by Idemitsu Petrochemical Co., Ltd., trade name PS-
32) 90 parts, hindered phenolic antioxidant (trade name Irganox 1010, manufactured by Ciba Geigy)
1 part, 1 part of a benzotriazole-based ultraviolet absorber (trade name: Tinuvin 327, manufactured by Ciba Geigy), 5 parts of a crosslinking agent (sodium hydrogen sulfate), 3 parts of tin octylate, and 1 part of laurylamine are added and mixed well. After that, a test piece was prepared. After curing the test piece at 23 ° C./60% RH, the test piece was exposed outdoors (Kanbe 45 Chemical Co., Ltd.
Degree inclination). As a result of evaluating the surface contamination state at the sixth month, the judgment was "good". Example 2 5 parts of a photocurable substance (Toa Gosei Chemical Co., Ltd., trade name ARONIX M-309) was added to 100 parts of the polymer obtained in Production Example 1 as a saturated hydrocarbon polymer (A). Unsaturated compounds that can react with oxygen in the air (Idemitsu Petrochemical Co., Ltd.)
5 parts, R-15HT (trade name), Colloidal calcium carbonate (Viscolite R (trade name) manufactured by Maruo Calcium Co., Ltd.) 1
20 parts, heavy calcium carbonate (Shiraishi Industry Co., Ltd., trade name Whiten SB) 20 parts, process oil (Idemitsu Petrochemical Co., Ltd., trade name PS-32) 90 parts, hindered phenol-based anti-aging 1 part of an agent (manufactured by Ciba-Geigy, trade name Irganox 1010), 1 part of a benzotriazole-based ultraviolet absorber (manufactured by Ciba-Geigy, trade name: Tinuvin 327), 5 parts of a crosslinking agent (sodium hydrogen sulfate),
After 3 parts of tin octylate and 1 part of laurylamine were added and mixed well, the mixture was passed three times between three small paint rolls to produce a sheet having a thickness of about 5 mm, which was used as a test piece. After the test piece was cured at 23 ° C./60% RH, the test piece was exposed outdoors (inclination of 45 ° on the south side) at Kanebuchi Chemical Industry Co., Ltd. (within Kobe Research Laboratory). As a result of evaluating the surface contamination state at the sixth month, the judgment was "good". Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that only tung oil, which was an unsaturated compound capable of reacting with oxygen in the air, in Example 1 was removed. As a result of evaluating the surface contamination state at the sixth month, the judgment was ×
Met. Comparative Example 2 Evaluation was made in the same manner as in Example 2 except that only the unsaturated compound R-15HT capable of reacting with oxygen in the air in Example 2 was removed. As a result of evaluating the surface contamination state at the sixth month, the judgment was x.

The photocurable substance evaluated this time is an oligoester acrylate manufactured by Toa Gosei Chemical Co., Ltd. and has the following structural formula. Alonix M-309: (CH ₂ ＣＨCHCOOCH ₂
-) _2- CCH ₂ CH ₃ or R-15 of an unsaturated compound capable of reacting with oxygen in the air.
HT is a mixture of liquid 1,4-polybutadiene and 1,2-polybutadiene having a number average molecular weight of 1,000.

In the evaluation of the surface contamination state, as can be seen from the results from Examples 1 and 2 and Comparative Examples 1 and 2, the curable composition of the present invention was obtained by combining both components (B) and (C). When added for a long period of time, the surface protection of the front and rear surfaces is significantly reduced as compared with the conventional curable composition to which only one of the component (B) and the component (C) is added. It shows improvement.

Further, the polymer obtained in Production Example 2 or 3 was used in place of the polymer obtained in Production Example 1 and evaluated in the same manner as in Examples 1 and 2 and Comparative Examples 1 and 2. Example 1
The same effect as described above was obtained.

[0061]

In recent years, from the viewpoint of emphasizing aesthetics, there is a very severe market demand for pollution.
By adding both components (B) and (C), the curable composition of the present invention exhibits a remarkable anti-staining effect when exposed for a long period of time. Furthermore, it has excellent chemical resistance, solvent resistance, heat resistance, weather resistance and moisture permeability,
Particularly, it is extremely useful as a sealing material and a sealant for construction, automobile, marine, road, and the like.

Continuation of the front page (56) References JP-A-53-24347 (JP, A) JP-A-57-30707 (JP, A) JP-A-61-236809 (JP, A) JP-A-1-170658 (JP) JP-A-5-70531 (JP, A) JP-A-7-70425 (JP, A) JP-A-7-196909 (JP, A) JP-A-8-41356 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 101/10 C08L 23/00 C08F 255/00

Claims (1)

(57) [Claims] (A) a saturated hydrocarbon polymer having at least one silicon-containing group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond, (B) The saturated hydrocarbon polymer 10
Reaction with 0.01 to 20 parts by weight of the photocurable substance per 0 parts by weight and (C) 0.1 to 20 parts by weight of oxygen in the air with respect to 100 parts by weight of the saturated hydrocarbon polymer A curable composition comprising an unsaturated compound which can be used.