JPH0841361A - Curable composition - Google Patents

Abstract

(57) [Summary] [Structure] (A) A saturated hydrocarbon-based polymer having 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. 100 parts by weight of coalescence, (B) total amount of calcium carbonate having an average particle diameter of 1 μm or more and (C) calcium carbonate having an average particle diameter of 0.2 μm or less, 100 to 200 parts by weight,
(D) Plasticizer 40 to 150 parts by weight, (E) II-valent tin-based curing catalyst 0.5 to 10 parts by weight, and (F) Epoxy group-containing compound 2 to 40 parts by weight, A curable composition in which the component (B) accounts for 10 to 70% by weight and the component (A) accounts for 15 to 35% by weight in the total amount of the components and the component (C). [Effect] It has a particularly excellent restorability, good durability and workability, and gives a cured product excellent in strength and elongation.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a saturated hydrocarbon polymer having a silicon atom having a hydroxyl group and / or a hydrolyzable group bonded thereto and having a silicon atom-containing group capable of being crosslinked by forming a siloxane bond. A room temperature curable composition containing
In particular, the present invention relates to a room temperature curable composition which provides a cured product having excellent restorability.

[0002]

2. Description of the Related Art It has a silicon atom to which a hydroxyl group and / or a hydrolyzable group is bonded, and can be crosslinked by forming a siloxane bond, which can be cured into a rubber-like substance when exposed to humidity at room temperature in the atmosphere. A curable composition containing a saturated hydrocarbon polymer having a silicon atom-containing group (hereinafter referred to as "reactive silicon group-containing saturated hydrocarbon polymer") is a liquid composition having a low viscosity and a thixotropic property. Therefore, it is easy to handle, has good storage stability, has a fast curability during curing, does not generate gas, etc., and has a moderate viscoelastic strength.
Since it has adhesiveness to an adherend, it is known as an adhesive and, in particular, as a sealing material for joints of buildings, transportation equipment and the like.

When the above-mentioned reactive silicon group-containing saturated hydrocarbon polymer is used as a sealant for joints of building elastic sealants and transportation equipment for sealing gaps (joints), it is injected into joints. At the time of injection, it is injected in a liquid state and cured after injection to become a rubber-like cured product. In this case, the cured product is required to have various properties. Among them, when the cured product is kept in a compressed state by the mutual expansion and contraction of the structure or the like and then the compression is released, the original state is restored. Characteristic to restore (Restorability)
Is a characteristic that is particularly required.

In order to improve the restorability of the cured product of the above-mentioned curable composition, a II-valent tin organic carboxylate and / or a II-valent lead organic carboxylate as a curing catalyst and, if necessary, an acidic substance. Alternatively, a method of using a basic substance in combination has been studied, but it is not sufficient yet, and further improvement is desired.

[0005]

An object of the present invention is to provide a two-component composition containing a reactive silicon group-containing saturated hydrocarbon polymer which produces a cured product having good viscoelastic strength and excellent adhesion. Among the mold-curable compositions, it is an object of the invention to provide a room-temperature-curable composition that produces a cured product having excellent restorability, good durability, and workability.

[0006]

The above objects of the present invention are as follows.
(A) 100 parts by weight of 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 which can be crosslinked by forming a siloxane bond, and (B) Total amount of calcium carbonate having an average particle diameter of 1 μm or more and (C) calcium carbonate having an average particle diameter of 0.2 μm or less, 100 to 200 parts by weight, (D) plasticizer 40 to 150 parts by weight, (E) II-valent tin-based material It contains 0.5 to 10 parts by weight of a curing catalyst and 2 to 40 parts by weight of (F) an epoxy group-containing compound, and 10 to 70 parts by weight of the (B) component in the total amount of the (B) component and the (C) component. %, And the curable composition can account for 15 to 35% by weight of the component (A) in the total composition.

It goes without saying that the above-mentioned curable composition is satisfactory in workability and storability, and the cured product is satisfactory in strength, elongation and other required properties. Hereinafter, the present invention will be described in detail.

In the present invention, a saturated hydrocarbon system 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, a saturated hydrocarbon system having at least one reactive silicon group. A polymer (hereinafter, also referred to as “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):

[0009]

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, but a + mb ≧ 1. Also, m

[0010]

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. Of these, an alkoxy group is particularly preferable because it has mild hydrolyzability and is easy to handle.

The hydrolyzable group and the 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 number of silicon atoms forming the 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:

[0014]

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

At least one reactive silicon group is contained in one molecule of the saturated hydrocarbon polymer, preferably 1.1-5.
Exist individually. 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 above-mentioned 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 above olefin compound and a diene compound are copolymerized and then hydrogenated.

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

In the above isobutylene-based polymer, all of the monomer units may be formed of isobutylene units, and the monomer unit having copolymerizability with isobutylene is 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 in addition to 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 can be 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 the saturated hydrocarbon polymer (A), particularly isobutylene polymer and hydrogenated polybutadiene polymer, is preferably about 500 to 100,000, and particularly 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.

The method for producing the saturated hydrocarbon polymer having a reactive silicon group will be described below by taking an isobutylene polymer and a hydrogenated polybutadiene polymer as an example.

Of the above-mentioned isobutylene-based polymers having a reactive silicon group, the isobutylene-based polymer having a reactive silicon group at the molecular end is a polymerization method called an inifer method (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 polymer obtained by a cationic polymerization method using a specific compound that is also used. Such a manufacturing method is
JP-A-63-6003, 63-6041, 63
-254149, 64-38407, 64-2
It is described in each specification of No. 2904.

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 the same. Manufactured by.

Further, in the polymerization for producing an isobutylene-based 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 above-mentioned vinylsilanes and allylsilanes having a 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) is used. CH ₂ ═CH—R ³ —Y (2) (In the formula, Y is a halogen atom such as chlorine atom and 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, 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.

As a method of converting the terminal hydroxyl group of the hydroxy-terminated polybutadiene-based polymer into an oxymetal group,
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-mentioned 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 thereof include allyloxy (chloromethyl) benzene, but are not limited thereto. Of these,
Allyl chloride is preferred because it is inexpensive and easily reacted.

The 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:

[0036]

[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-based 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.

In the present invention, calcium carbonate having a particle size of 1 μm or more is used as the component (B). By using such calcium carbonate, the restoring property of the cured product is improved. The (B) component calcium carbonate preferably has an average particle size of 1 to 5 μm, and the calcium carbonate may be surface-treated with a fatty acid or the like. Examples of the calcium carbonate (B) to be calcium carbonate include heavy calcium carbonate, and examples thereof include Sunlight ^# 100, ^# 300 (above, manufactured by Takehara Chemical Industry Co., Ltd.), N.
S ^# 100, ^# 200, ^# 400, ^# 600, ^# 1000,
NN ^# 500, SS80 (above, Nitto Koka Kogyo Co., Ltd.),
EC-1, 5, MC Coat P-13, S-13, Snowlight SS, SSS, M White, Super ^# 150
0, ^# 1700, ^# 2000, ^# 2300 (above, Maruo Calcium Co., Ltd.), Whiten SB, P-10, 20, 3
0, 40, 50 (manufactured by Shiraishi Calcium Co., Ltd.) can be mentioned as commercially available products.

In the present invention, calcium carbonate having an average particle diameter of 0.2 μm or less is used as the component (C). By using such calcium carbonate, it is possible to obtain a curable composition free from sagging or the like during work. The average particle diameter is preferably 0.01 to 0.15 μm. In addition, organic substances such as fatty acids, resin acids and lignin, particularly calcium carbonate surface-treated with fatty acids are preferable.

The calcium carbonate as the component (C) includes white luster O, carmos, white luster CC, white luster CCR,
Examples thereof include those marketed under the trade names of VIGOT-15 and the like.

The calcium carbonate is used in the range of 100 to 200 parts by weight as the total amount of the component (B) and the component (C). If the amount used is less than 100 parts by weight, it is difficult to control the viscosity of the composition and it is economically disadvantageous, which is not preferable. Further, if it exceeds 200 parts by weight, the viscosity of the composition is excessively increased, the workability is deteriorated, and the durability is deteriorated, which is not preferable.

It is necessary that the component (B) is present in an amount of 10 to 70% by weight, preferably 20 to 60% by weight, based on the total amount of the components (B) and (C). Ratio is 1
If it is less than 0% by weight, the restoring force of the cured product is not sufficient, which is not preferable, and if it exceeds 70% by weight, a composition which causes sagging or the like during working is not preferable.

Examples of the plasticizer as the component (D) in the present invention include phthalates such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate; dioctyl adipate, isodecyl succinate, dibutyl sebacate and the like. Aliphatic dibasic acid esters such as; glycol esters such as diethylene glycol dibenzoate, pentaerythritol ester; aliphatic esters such as butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate, phosphoric acid Phosphate esters such as octyldiphenyl; epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and benzyl epoxy stearate; polyesters of dibasic acid and dihydric alcohol Polyethers such as polypropylene glycol and derivatives thereof; polyester plasticizers;
Polystyrene such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, chlorinated paraffins, petroleum-based softeners, alkylbenzene-based plasticizers and other plasticizers alone Alternatively, they can be optionally used in the form of a mixture of two or more kinds. However, it is preferable to select one having good compatibility.

In the present invention, it is necessary to use 40 to 150 parts by weight of a plasticizer as the component (D). If the amount used is less than 40 parts by weight, the viscosity of the composition becomes too high, and workability such as extrusion moldability is hindered, which is not preferable. If it exceeds 150 parts by weight, the change in physical properties over time due to bleeding of the plasticizer is large, and if the coating material is applied to the surface, the coating material may be deteriorated, which is not preferable.

In the present invention, II as the component (E) is used.
The tin-based curing catalyst is an important compounding agent that affects both the curing rate and the durability, and examples thereof include tin octylate, tin laurate, and tin persate, but tin octylate is particularly preferable.

The amount of the above II-valent tin-based curing catalyst used is
It is necessary to use 0.5 to 10 parts by weight. If the amount used is less than 0.5 parts by weight, the curing rate will be too slow and problems will occur in workability, such being undesirable. Further, if it exceeds 10 parts by weight, the durability, particularly the repeated fatigue property and the restoring property are adversely affected, which is not preferable.

When the curing rate of the II-valent tin-based curing catalyst alone is insufficient, an amine compound can be used as a co-catalyst. As the amine compound, for example,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, butylamine, hexylamine, octylamine, decylamine, laurylamine,
Hexamethylenediamine, triethanolamine, dibutylamine, diethanolamine, N, N, N ', N'
-Tetramethyl-1,3-butanediamine, benzylamine, cyclohexylamine, dodecamethylenediamine, dimethylethylenediamine, dimethylaminoethanol, N, N, N ', N'-tetramethylethylenediamine, triethylamine, N, N-dimethylaniline ,
Dimethylbenzylaniline and the like can be mentioned, but primary amines are preferable in view of their activity and the like, and laurylamine is particularly preferable in terms of handleability.

In the composition of the present invention, a compound having an epoxy group in one molecule is used as the component (F) in order to enhance the resilience. Specific examples of the compound include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds represented by epichlorohydrin derivatives, and mixtures thereof.
Specifically, for example, epoxidized soybean oil, epoxidized linseed oil, di- (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-
PS), epoxy octyl stearate, epoxy dibutyl stearate and the like.

It is also possible to use other fillers other than calcium carbonate in the composition of the present invention. Examples of the filler that can be used in combination include fume silica, precipitated silica, silicic acid anhydride, hydrous silicic acid, carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, and secondary oxide. Examples thereof include iron, zinc oxide, activated zinc white, shirasu balloon, asbestos, and glass fiber.

In the present invention, various thixotropic agents can be added in order to impart thixotropic properties to the composition.
As the thixotropic agent, hydrogenated castor oil, amide wax,
Aluminum stearate, calcium stearate,
Examples thereof include zinc stearate, finely divided silica, and organic bentonite. Among them, hydrogenated castor oil is particularly preferable. In the case of hydrogenated castor oil, it is preferably used in the range of 0.5 to 7 parts by weight.

In the present invention, an ultraviolet absorber may be used in order to improve durability, especially surface weather resistance. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds, and among them, benzotriazole-based compounds are particularly preferable.

For the same purpose, it is also effective to use an antioxidant in the present invention. Examples of the antioxidant include hindered phenol-based compounds, monophenol-based compounds, bisphenol-based compounds, and polyphenol-based compounds. Among them, hindered phenol-based compounds are particularly preferable.

Similarly, in the present invention, for example, tinuvin 622LD, tinuvin 144, CHIMASSORB944LD, CHIMA.
SSORB119FL (all manufactured by Japan Ciba-Geigy Co., Ltd.); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-
63, MARK LA-68 (all manufactured by Adeka Argus Chemical Co., Ltd.); Sanor LS-770, Sanor LS-765, Sanor
Hindered amine light stabilizers such as those shown in LS-292, Sanol LS-2626, Sanol LS-1114, and Sanol LS-744 (all manufactured by Sankyo Co., Ltd.) can be used.

In the present invention, it is also effective to add a compound having at least two acryl or methacryl functional groups in one molecule in order to enhance the surface weather resistance. Specifically, the compounds shown below, for example, special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233.
, Aronix M-240, Aronix M-245; Special acrylate (trifunctional) Aronix M-305, Aronix M-309, Aronix M-310, Aronix M-315
, Aronix M-320, Aronix M-325; and special acrylate (polyfunctional) Aronix M-400 (all of these Aronix are manufactured by Toagosei Chemical Industry Co., Ltd.)
Etc., but a compound containing an acrylic functional group is particularly preferable, and a compound containing an average of 3 or more acrylic functional groups in one molecule is preferable.

The compound is preferably used in the range of 0.5 to 10 parts by weight. If it is less than 0.5 part by weight, the weather resistance will not be increased, and if it exceeds 10 parts by weight, the cured product will be too hard. It is not preferable because it causes cracks.

The composition of the present invention thus obtained is a sealing agent, an adhesive, an adhesive, a paint, a waterproof coating film, a sealant composition, a molding material, a cast rubber material, a foam material. It can be usefully used as such.

[0057]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Production Example 1 A four-necked flask is equipped with a stirrer and a nitrogen line.
In this, dried methylene chloride 560 ml, n-hexane 1160 ml, α-methylpyridine 940 mg, p
-22 g of dicumyl chloride was weighed and made into a homogeneous mixed solution, then cooled to -70 ° C, and 570 ml of isobutylene monomer was charged under reduced pressure through a Molecular 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 was raised to -54 ° C, the temperature was lowered to -70 ° C in about 17 minutes.

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) and 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. Next, 400 g of the vinyl group-containing isobutylene oligomer thus obtained was dissolved in 200 ml of n-heptane and heated to about 70 ° C., and then methyldimethoxysilane 1.5 [eq / vinyl group], platinum (vinyl siloxane) A complex 1 × 10 ⁻⁴ [eq / vinyl group] was added to carry out a hydrosilylation reaction. FT-I
The reaction was traced by R, 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 a reactive silicon group at both ends and having a molecular weight of 5300 was obtained. [Structural formula]

[0062]

Embedded image Examples 1 to 7 and Comparative Examples 1 to 7 With respect to 100 parts by weight of the polymer obtained in Production Example 1, the compounding ratio (parts by weight) shown in Table 1 and Table 2 was used. A curable composition was prepared by mixing the compounding ingredients of the components (B) to (F) shown in (4).

With respect to the composition and the cured product, workability, restorability and weather resistance were measured and evaluated by the following test methods. The results are shown in Tables 1 and 2 below. The evaluation methods for the properties in the table are as follows.

* 1 Workability: The extrudability from the cartridge and the spatula breaking property were measured. * 2 Restorability: The JIS H cured product is compressed at 90 ° C for 30% for 7 days, and the resilience on the first day after decompression is measured.

* 3 Sunshine weather meter weather resistance test: Suga test machine property A sunshine weather meter test machine is used to measure the irradiation time until the surface of the cured sheet is irradiated and cracks occur.

[0066]

[Table 1]

[0067]

[Table 2]

As is clear from the results shown in Tables 1 and 2 above, the composition of the present invention contains all of the components (B) to (F), so that the composition has good restorability, workability and weather resistance. It can be seen that it exerts excellent effects in all aspects of sex.

[0069]

EFFECT OF THE INVENTION The curable composition of the present invention has particularly excellent restorability, good durability and workability, and gives a cured product excellent in strength and elongation.

Claims (1)

[Claims] 1. (A) 100 parts by weight of 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 which can be crosslinked by forming a siloxane bond. , And (B) calcium carbonate having an average particle size of 1 μm or more, and (C) an average particle size of 0.
Containing 100 to 200 parts by weight of total amount of calcium carbonate of 2 μm or less, (D) 40 to 150 parts by weight of plasticizer, (E) 0.5 to 10 parts by weight of II-based tin-based curing catalyst, and (F) containing epoxy group. 2 to 40 parts by weight of the compound, and (B)
The component (B) accounts for 10 to 70% by weight in the total amount of the component and the component (C), and the component (A) in the total composition is 15 to 35% by weight.
Curable composition characterized by occupying.