JPH0841358A - Curable composition - Google Patents

Abstract

PURPOSE:To provide a low-cost curable compsn. which has a low toxicity and cures very rapidly. CONSTITUTION:This compsn. mainly comprises a satd. hydrocarbon polymer having a hydroxyl or hydrolyzable group bonded to a silicon atom and at least one silicon group capable of cross-linking by forming a siloxane bond, a compd. having at least one carboxyl group, and a compd. having at least one amino group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition having a fast curing rate and a low toxicity.

[0002]

2. Description of the Related Art Conventionally, 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 is cured. Various compounds are known to be useful compounds. Among these compounds, organometallic compounds such as dibutyltin dilaurate, tin octylate, lead octylate and the like are used to accelerate the curing rate.

[0003]

However, the organometallic compounds containing tin and lead are not only expensive but also highly toxic. To avoid this problem, it is conceivable to use a carboxylic acid instead of the organometallic compound. However, compared with the case of using the organometallic compound, the use of carboxylic acid markedly reduced the curing rate of the polymer, which was not practical.

In addition to the carboxylic acid, it is possible to use an amine or an amine derivative, but it has not been put into practical use for the same reason and toxicity as the carboxylic acid. The present inventors have earnestly studied to obtain a curable resin composition having a high curing rate and low toxicity, and as a result, if a carboxylic acid and an amine or an amine derivative are used in combination, a synergistic effect is exhibited. It was found that the curing rate of the polymer increases dramatically beyond the imagination when both are used alone,
The present invention has been completed. It has also been found that the combination of a specific carboxylic acid and amine improves durability, mechanical properties, and rubber properties.

[0005]

The present invention is directed to (A) a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, which can be crosslinked by forming a siloxane bond (hereinafter referred to as reactive silicon). And a curable composition containing (B) a compound having at least one carboxyl group and (C) a compound having at least one amino group.

The curable composition of the present invention has, as the component (A), a 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, that is, a reaction. A saturated hydrocarbon polymer having at least one functional silicon group (hereinafter, also referred to as saturated hydrocarbon polymer (A)) is used.

[0007] Typical examples of the reactive silicon group of the general formula (1) - [- Si ( -R 1 2-b) (- X b) -O-] m -Si (-R 2 3-a ) ( _-Xa ) (1).

In the general formula (1), 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, an aralkyl group having 7 to 20 carbon atoms, or R ′ ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R ′ may be the same or different. ) Is a triorganosiloxy group represented by R ¹ or R ²
When two or more are present, they may be the same or different. X is 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, but a + mb ≧ 1. Also, m-[-Si (-
_{^{R 1 2-b) (-}} X b) -O -] - in b need not be identical. m represents 0 or an integer of 1 to 19.

The hydrolyzable group is not particularly limited and may be a conventionally known hydrolyzable group. Specific examples thereof include a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group and an amino group. Group, amide group,
Examples thereof include commonly used groups such as aminooxy group, mercapto group and alkenyloxy group. Of these, an alkoxy group is particularly preferable because it has mild hydrolyzability and is easy to handle.

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: -Si (-R 2 3-a}} ) (. Wherein, R ^2, X and a are same as defined above) -X _a reactive silicon group represented by it 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. 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 term "saturated hydrocarbon polymer" as used herein means a polymer which does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and is a reactive silicon used in the present invention. The polymer serving as the skeleton of the saturated hydrocarbon polymer having a group 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.

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
49, 64-22904, 64-38407 and the like.

The isobutylene-based polymer having a reactive silicon group in the molecular chain is copolymerized by adding vinylsilanes or allylsilanes having a reactive silicon group to a monomer mainly containing isobutylene. Manufactured by

Further, in the polymerization at the time of producing an isobutylene polymer having a reactive silicon group at the terminal of the molecular chain,
After copolymerizing vinylsilanes or allylsilanes having a reactive silicon group in addition to the main component, isobutylene monomer, the reactive silicon group is introduced at the terminal to give reactive silicon at the terminal and inside the molecular chain. An isobutylene-based polymer having a group 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.
A hydrogenated polybutadiene-based polymer having a terminal olefin group (hereinafter, also referred to as a terminal olefin-hydrogenated polybutadiene-based polymer) can be produced by reacting an organic halogen compound represented by a valence group] .

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. Is a polyvalent organic halogen containing two or more halogen atoms in one molecule such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether before reacting with the organic halogen compound of the general formula (2). By reacting with a compound to increase the molecular weight 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 above general formula (2) include allyl chloride,
Allyl bromide, vinyl (chloromethyl) benzene,
Allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) Examples thereof include, but are not limited to, 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. in (wherein, R ^2, X and a are as defined ^{above.) H-Si (-R 2} 3-a) -X a: hydrosilane compound wherein the hydrogen atom in the group is bonded to, preferably, the general formula It is produced by subjecting the compound shown to an 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 methoxysilane, 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 compound having at least one carboxyl group (hereinafter referred to as a carboxyl group-containing compound) which is the component (B) of the present invention is not particularly limited, and various compounds can be used. Specific examples of the carboxyl group-containing compound are given below.

(1) Saturated monocarboxylic acid (a) Formic acid, acetic acid, acetoacetic acid, ethylmethylacetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethylbutyric acid, ethoxyacetic acid, valeric acid, isovaleric acid, hexanoic acid, 2-ethylhexanoic acid, octanoic acid, decanoic acid, undecanoic acid, glyoxylic acid, glycolic acid, saturated monocarboxylic acids such as gluconic acid, (b) acrylic acid, methacrylic acid, angelic acid,
Olefin monocarboxylic acids such as crotonic acid, isocrotonic acid, 10-undecenoic acid, elaidic acid, erucic acid and oleic acid, (c) acetylene monocarboxylic acids such as propiol, and (d) diolefins such as linoleic acid and linoelaidic acid. Carboxylic acids, (e) highly unsaturated monocarboxylic acids such as linolenic acid and arachidonic acid, (f) monohalogenated substitution products of monocarboxylic acids such as chloroacetic acid, 2-chloroacrylic acid and chlorobenzoic acid, (2) fats Group dicarboxylic acids (a) adipic acid, azelaic acid, ethylmalonic acid, glutaric acid, oxalic acid, malonic acid, succinic acid, saturated dicarboxylic acids such as oxydiacetic acid, (b) maleic acid, fumaric acid, acetylenedicarboxylic acid, Unsaturated dicarboxylic acids such as itaconic acid, (3) Aliphatic polycarboxylic acids (a) Tricarboxylic acids such as aconitic acid, citric acid and isocitric acid, (4) Aroma Carboxylic acid (a) Benzoic acid, 9-anthracenecarboxylic acid, atrolactic acid, anisic acid, isopropylbenzoic acid, salicylic acid, aromatic monocarboxylic acids such as toluic acid, (b) phthalic acid, isophthalic acid, carboxyphenylacetic acid, Aromatic polycarboxylic acids such as pyromellitic acid, (5) Other amino acids such as alanine, leucine, threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine, phenylalanine, tryptophan and histidine.

Any compound may be used as long as it has at least one carboxyl group in one molecule. These compounds may be used alone or in combination of two or more kinds. Among the above compounds, an aliphatic monocarboxylic acid is preferable and has 2 to 3 carbon atoms.
Is more preferable.

The compound having at least one amino group (hereinafter referred to as amino group-containing compound) which is the component (C) of the present invention is not particularly limited, and various compounds can be used. Specific examples of the amino group-containing compound are shown below.

(1) Primary amine (a) Methylamine, ethylamine, propylamine, isopropylamine, isopropylalcoholamine, butylamine, 1-ethylbutylamine, isobutylamine, pentylamine, octylamine, laurylamine, monoethanolamine, Aliphatic primary amines such as diethylaminopropylamine, oleylamine, cyclohexylamine, benzylamine, guanidine, 2-ethylhexylamine and triethylenetetramine, (b) aniline, benzylaniline, nitroaniline, phenylenediamine, toluidine, toluylamine, xylene. Aromatic primary amines such as diamines, 2,3-xylidine, anisidine, phenetidine, benzidine, benzylamine, naphthylamine, (2) secondary amines (a) dimethylamine, diethyla Minerals, diethanolamine, diethylenetriamine, dibutylamine, piperidine, diisopentylamine, pyrrolidine, morpholine, aliphatic secondary amines such as 2-ethyl-4-methylimidazole, (b) N-ethylnaphthylamine, acetanilide,
Aromatic secondary amines such as acetamidonaphthalene and diphenylguanidine, (3) tertiary amines (a) trimethylamine, triethylamine, triethanolamine, tripropylamine, tributylamine,
Aliphatic tertiary amines such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), (b) N, N-dimethylaniline, N , N-dibenzylaniline, dimethylaminobenzoic acid, aromatic tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol.

Any compound may be used as long as it has at least one amino group in one molecule. These compounds may be used alone or in combination of two or more kinds. Of the above compounds, the first
From the viewpoint of activity, amines and tertiary amines are preferable, and primary amines are more preferable.

The amount of the carboxyl group-containing compound and amino group-containing compound used is 100 parts by weight of the saturated hydrocarbon polymer as the component (A) (hereinafter, simply referred to as "part").
On the other hand, the total amount is preferably 0.01 to 20 parts,
1 to 10 parts is more preferable. If the amount used is less than 0.01 part, the curing rate may be slow, and curing may not be able to proceed sufficiently. If it exceeds 20 parts, the effect does not change so much, and not only the cost becomes unnecessarily high, but also problems such as coloring and water resistance may occur.

The compounding ratio of the carboxyl group-containing compound and the amino group-containing compound is not particularly limited, but the molar ratio (carboxyl group-containing compound / amino group-containing compound) is
0.01 to 50 is preferable, and 0.1 to 20 is more preferable. The curing rate can be adjusted by changing the compounding ratio of both.

In producing the composition of the present invention, the order in which the saturated hydrocarbon polymer, the carboxyl group-containing compound and the amino group-containing compound are added is not particularly limited. The carboxyl group-containing compound may be added first or the amino group-containing compound may be added first to the saturated hydrocarbon polymer. The saturated hydrocarbon polymer may be added to the carboxyl group-containing compound first, or the amino group-containing compound may be added first. Further, the carboxyl group-containing compound and the amino group-containing compound may be added at the same time, or both may be mixed in advance to form a salt, a complex or the like, and the method of adding this to the polymer is adopted. Good.

In the composition of the present invention, if necessary, a silanol condensation catalyst (curing catalyst), a physical property adjusting agent for improving tensile properties, a reinforcing or non-reinforcing filler, a plasticizer,
You may add and use various additives, such as an adhesion promoter, an anti-sagging agent, a coloring agent, an antiaging agent, and a flame retardant.

Specific examples of such silanol condensation catalysts include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate and octyl. Tin carboxylates such as tin acid and tin naphthenate; Reaction products of dibutyltin oxide and phthalic acid ester; Dibutyltin diacetylacetonate; Aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethyl. Organoaluminum compounds such as acetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; Lead octylate; Low molecular weight polyamites obtained from excess polyamine and polybasic acid Resin; Reaction product of excess polyamine and epoxy compound; Silanol condensation catalyst such as silane coupling agent having amino group such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane Further, other known silanol condensation catalysts such as acidic catalysts and basic catalysts can be exemplified. These catalysts may be used alone or 2
You may use together 1 or more types.

Specific examples of the above fillers and reinforcing materials include heavy and light calcium carbonate; surface treatment with fatty acids, resin acids, cationic surfactants, anionic surfactants, etc. Calcium carbonate; Magnesium carbonate; Talc; Titanium oxide; Barium sulfate; Alumina; Metal powder of aluminum, zinc, iron, etc .; Bentonite, Kaolin clay; Fumed silica; Quartz powder; White carbon,
Carbon black; talc, asbestos, glass fiber and the like which are normally used can be mentioned. In particular, it is possible to produce a sealing agent having excellent transparency by using a filler or a reinforcing material that gives transparency, such as fumed silica. These fillers may be used alone or in combination of two or more.

Specific examples of the plasticizer used for controlling physical properties and properties include dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl phthalate, butylbenzyl phthalate, butyl. Phthalates such as phthalylbutyl glycolate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; tricresyl Phosphates such as phosphate and tributyl phosphate; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl, process oils, and plasticizers such as alkylbenzenes. , Can be alone or in combination of two kinds or more, it does not necessarily need.
Further, these plasticizers may be added at the time of polymer production. However, it is preferable to select those having good compatibility.

The above antiaging agents include amine-based, phenol-based, imidazole-based, amine-aldehyde-based,
Examples thereof include amine-ketone-based, sulfur-based, phosphorus-based and other usual antioxidants, ozone deterioration inhibitors, and ultraviolet absorbers.

The curable composition of the present invention can be usefully used as an industrial elastic material, a sealing composition material, an adhesive material, a potting material, a packaging material, a waterproofing agent, a molding material, a binder and a modifier. it can. Among them, sealant,
Adhesive applications are particularly useful.

[0048]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Production Example 1 560 mL of dried methylene chloride and 116-n-hexane were placed in a four-necked flask equipped with a stirrer and a nitrogen line.
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. Polymerization catalyst solution (titanium tetrachloride 14 mL / methylene chloride 80 mL) precooled in the above reaction solution cooled to −70 ° C. under stirring.
Was added all at once to initiate the 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,
Further, stirring was continued at −70 ° C. for 4 hours. The yellowish cloudy reaction solution was placed in 3 L of warm water (about 45 ° C.), 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,
Approximately 4 isobutylene oligomers with vinyl groups at both ends
00g was obtained.

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, a target molecular weight of 5,300 having reactive silicon groups at both ends is obtained.
The isobutylene oligomer of was obtained. [Structural Formula] Me (MeO) ₂ Si (CH ₂ ) ₈ CHClCH _2- (C (Me) ₂ CH ₂ ) _n C (Me) ₂ (C ₆ H ₄ ) C (Me) _2- (CH ₂ C (Me) ₂ ) _m CH ₂ CHCl (CH ₂ ) ₈ --SiMe (OMe) ₂ Production Example 2 Production Example 2 except that 24 g of allylmethylsilane was used in place of 1,9-decadiene. 1 was repeated to obtain an isobutylene oligomer having a molecular weight of 4,400 with a partially different structure of the production intermediate.

[Structural Formula] Me (MeO) ₂ Si (CH ₂ ) ₃ (C (Me) ₂ CH ₂ ) _n -C (Me) ₂ (C ₆ H ₄ ) C (Me) _2- (CH ₂ C (Me) ₂ ) _m − − (CH ₂ ) ₃ SiMe (OMe) ₂ Production Example 3 In a four-necked flask equipped with a stirrer and a nitrogen line, 560 mL of dry 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. Polymerization catalyst solution (titanium tetrachloride 14 mL / methylene chloride 80 mL) precooled in the above reaction solution cooled to −70 ° C. under stirring.
Was added all at once to initiate the polymerization. Once the temperature was raised to -54 ° C, the temperature was lowered to -70 ° C in about 17 minutes. After the initiation of polymerization, stirring was continued for about 60 minutes. The yellowish cloudy reaction solution was placed in 3 L of warm water (about 45 ° C.), 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 a reactive silicon group at both ends and having a molecular weight of 4,300 was obtained.

[Structural Formula] Me (MeO) ₂ SiCH ₂ CH (Me) CH ₂ − − (C (Me) ₂ CH ₂ ) _n C (Me) ₂ (C ₆ H ₄ ) C (Me) ₂ − − (CH ₂ C (Me) ₂ ) _m CH ₂ CH (Me) CH ₂ — —SiMe (OMe) ₂ Example 1 As the component (A), 100 parts of the polymer obtained in Production Example 1 was used to prepare colloidal calcium carbonate. (Shiraishi Industry Co., Ltd., trade name Biscolite-R) 120 parts, process oil (PS-3
2) 90 parts, 1 part of a hindered amine anti-aging agent (Ouchi Shinko Chemical Co., Ltd., trade name Nocrac NS-6), and 5 parts of sodium sulfate hydrate as a crosslinking agent were added. Furthermore,
Add 1 part of lauryl amine and 2 parts of 2-ethylhexanoic acid, knead thoroughly, and then add 3 small paint rolls to 3 parts.
A sheet having a thickness of 3 mm was made by passing through. Then, this sheet was cured at 23 ° C./50% RH, and the time required for the sheet to cure was measured. The determination as to whether or not the resin has been cured was made by touching with a finger in accordance with the measuring method of tack free time (time required for curing) of JIS A5758. The results are shown in Table-1. Comparative Example 1 Example 1 was repeated except that 2-ethylhexanoic acid was not added and 3 parts of laurylamine was added. The results are
It is as shown in 1. Comparative Example 2 The procedure of Example 1 was repeated except that 3 parts of 2-ethylhexanoic acid was added without adding laurylamine. The results are
It is as shown in 1. Comparative Example 3 Example 1 was repeated except that 2-ethylhexanoic acid was not added and 3 parts of dibutyltin dilaurate (DTL) was added instead. The results are shown in Table-1.

Table-1 Polymer of Production Example 1: Example Comparative Example 1 1 2 3 Laurylamine (part) 1 3 0 1 2-Ethylhexanoic acid (part) 2 0 3 0 Dibutyltin dilaurate (part) 0 0 0 3 tack free time (hours) 3.7 24 <24 <5.5 As is clear from Table 1 above, when 2-ethylhexanoic acid and laurylamine are used in combination, these are used alone. The time required for curing was significantly shortened as compared with the case where it was absent, and it was cured at almost the same speed as when using dibutyltin dilaurate (DTL).

When 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, Comparative Examples 1 to 3, The same effect as in the case of Example 1 was obtained.

Examples 2 to 6 2 parts of 2-ethylhexanoic acid and laurylamine in the proportions shown in Table 2 were mixed and the tack free time was measured in the same manner as in Example 1 (23 ° C./50). % RH). The results are shown in Table-2. The results of Example 1 are also shown.

Table-2 Using the polymer of Production Example 1: Molar ratio Tack free time (2-ethylhexanoic acid / laurylamine) (hour) Example 1 2.6 3.7 Example 2 0.5 4. 0 Example 3 1.0 3.5 Example 4 1.5 3.1 Example 5 2.5 3.4 Example 6 20.0 1.6 As is clear from Table 2 above, 2- By using ethylhexanoic acid and laurylamine in combination, a curable resin composition having a very fast curing rate was obtained. Further, when the polymers obtained in Production Examples 2 and 3 were evaluated in the same manner as described above, almost the same results were obtained.

[0059]

According to the present invention, it is possible to provide a curable composition which is inexpensive and has low toxicity. Moreover, the curing rate of this curable composition is extremely high.

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. ) At least 1 carboxyl group
A curable composition containing a compound having one and (C) a compound having at least one amino group.