JPH1087957A - Curable composition improved in storage stability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition capable of stably retaining workability of sealing agents over a long period, excellent in adhesiveness and useful for elastic sealants, etc., by making the composition contain a specific saturated hydrocarbon-based polymer and an epoxy-based compound at a specific ratio. SOLUTION: This curable composition contains (A) 100 pts.wt. saturated hydrocarbon-based polymer having hydroxyl group or a hydrolyzable group bonded to silicon atom and having one or more silicon-containing groups capable of crosslinking by forming a siloxane bond and 500-50,000 molecular weight and having >=50wt.% total amount of recurring unit arising from isobutylene and (B) 0.1-20 pts.wt. epoxy-based compound having hydroxyl group or a hydrolyzable group bonded to silicon atom and having one or more silicon-containing groups capable of crosslinking by forming a siloxane bond, and further, preferably (C) 5-400 pts.wt. colloidal calcium carbonate and 0.1-100 pts.wt. water or substance capable of releasing water and 0.1-10 pts.wt. tetravalent tin-based curing catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon-containing compound having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by forming a siloxane bond. The present invention relates to a curable composition having an improved storage stability of a saturated hydrocarbon polymer having a group (hereinafter, referred to as a “reactive silicon group”).

[0002]

2. Description of the Related Art A saturated hydrocarbon polymer containing at least one reactive silicon group in a molecule undergoes a silanol condensation reaction due to moisture and the like even at room temperature, and is crosslinked by formation of a siloxane bond to form a rubber. It is known that it has an interesting property that a cured state can be obtained.

[0003] However, when this polymer is stored in the presence of moisture for a long period of time, there is a problem that storage stability is insufficient, such as skinning due to gelation of its surface. I understood. Further, the curable composition containing this polymer as a main component has a problem that its adhesiveness to various adherends such as metal and glass is insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to storage stability and adhesion of a curable composition having at least one reactive silicon group in a molecule and containing a saturated hydrocarbon polymer as a main component. The aim is to improve.

[0005]

[Means for Solving the Problems] The present inventors have conducted intensive studies to solve such problems, and as a result, by adding a specific organic compound to the polymer, the storage stability of the polymer has been improved. And that the storage stability improver of the present invention improves the adhesion to various adherends without adversely affecting the cured product of the composition, such as a decrease in physical properties. I found that I could do it.

That is, the present invention provides (A) a compound having at least one reactive silicon group in a molecule and having a molecular weight of 500 to 500;
The present invention relates to a curable composition having improved storage stability, comprising 100 parts by weight of a 50,000 saturated hydrocarbon polymer and 0.1 to 20 parts by weight of an epoxy compound (B). Hereinafter, the present invention will be described in detail.

In the present invention, a saturated hydrocarbon polymer having a reactive silicon group is used. The saturated hydrocarbon polymer having a reactive silicon group is a polymer substantially containing no carbon-carbon unsaturated bond other than the aromatic ring, for example,
Examples include polyethylene, polypropylene, polyisobutylene, hydrogenated polybutadiene, and hydrogenated polyisoprene.

The reactive silicon group is represented by the general formula (1):

[0009]

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(Wherein R ¹ and R ² each have 1 carbon atom)
20 alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms (R ') ₃ SiO-
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
R ′ are the same or different), and when two or more R ¹ or R ² are present,
They can be the same or different, X
Is a hydroxyl group or a hydrolysable 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 + ａb is 1 or more, and m

[0011]

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X in (1) may not be the same. m is 0
Or an integer of 1 to 19). Examples of the hydrolyzable group include groups generally used such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.

Of these, an alkoxy group, an amide group and an aminooxy group are preferred, but an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling. A hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and (a + Δb)
Is preferably in the range of 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 is preferably at least 20, but in the case of silicon atoms linked by a siloxane bond or the like, the number is preferably at most 20. In particular, equation (2)

[0015]

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(Wherein R ² , X and a are as defined above) are preferred because they are easily available. Specific examples of R ¹ and R ² in the general formulas (1) and (2) include, for example, an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; And an aralkyl group such as a group, and a triorganosiloxy group represented by R ′ ₃ SiO— wherein R ′ is a methyl group, a phenyl group, or the like. As R ¹ and R ² , a methyl group is particularly preferred.

The number of reactive silicon groups in one molecule of the saturated hydrocarbon polymer is at least one, preferably 1.1 to 5. If the number of reactive silicon groups contained in the molecule is less than one, the curability may be insufficient and good rubber elasticity may not be obtained. The reactive silicon group may be located at the terminal or inside the molecular chain of the saturated hydrocarbon polymer, or may be present at both. In particular, when the reactive silicon group is located at the molecular end, the amount of the effective network chain of the saturated hydrocarbon-based polymer component contained in the finally formed cured product is increased, so that a high-strength, high-elongation rubber-like It is preferable in that a cured product is easily obtained.

These saturated hydrocarbon polymers having a reactive silicon group can be used alone or in combination of two or more. The polymer constituting the skeleton of the saturated hydrocarbon polymer having a reactive silicon group used in the present invention is mainly composed of (1) an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene and the like. It can be obtained by a method of polymerizing as a monomer, (2) homopolymerizing a diene compound such as butadiene, isoprene, or the like, or copolymerizing the above olefin compound and then hydrogenating. Isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferred because a functional group can be easily introduced into the terminal, the molecular weight can be easily controlled, and the number of terminal functional groups can be increased.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units,
The monomer unit having copolymerizability with isobutylene is contained in the isobutylene-based polymer in an amount of preferably 50% or less (% by weight, the same applies hereinafter), more preferably 30% or less, particularly preferably 10% or less. Is also good. Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, and the like. Such copolymer components include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene,
Vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyl Trimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, Allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane,
Diallyldichlorosilane, diallyldimethoxysilane,
Diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like.

When vinylsilanes or allylsilanes are used as monomers copolymerizable with isobutylene, the content of silicon increases and the number of groups that can act as a silane coupling agent increases, so that the resulting composition The adhesion is improved. In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, as in the case of the isobutylene-based polymer, other monomer units are contained in addition to the main monomer unit. You may.

The saturated hydrocarbon polymer having a reactive silicon group used in the present invention includes a double bond after polymerization such as a polyene compound such as butadiene and isoprene as long as the object of the present invention is achieved. 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, preferably the isobutylene polymer or the hydrogenated polybutadiene polymer is from 500 to 5
It is preferably about 000, especially 1,000
Those having a liquid or fluidity of about 15,000 to 15,000 are preferred from the viewpoint of easy handling.

Next, a method for producing a saturated hydrocarbon polymer having a reactive silicon group will be described. Among the isobutylene-based polymers having a reactive silicon group, an isobutylene-based polymer having a reactive silicon group at a molecular chain terminal is a polymerization method called an inifer method (a specific method using both an initiator and a chain transfer agent called inifer). (Cationic polymerization method using a compound), and can be produced using a terminal-functional isobutylene-based polymer, preferably an all-terminal-functional isobutylene-based polymer. In the inifer method, a polymer having a halogen atom at a terminal is mainly obtained, and a reactive silicon group can be introduced by utilizing the reactivity of the halogen atom. For example, a dehydrohalogenation reaction of this polymer or JP-A-63-105
After obtaining a polyisobutylene having an unsaturated group at a terminal by a reaction of introducing an unsaturated group into a polymer as described in JP-A-005-005, a hydrosilane compound represented by the general formula (3) (this compound is A compound in which a hydrogen atom is bonded to a group represented by the general formula (1)), preferably by subjecting a compound represented by the general formula (4) to an addition reaction called hydrosilylation reaction using a platinum catalyst. To introduce a reactive silicon group into the polymer.

[0023]

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(In the formula, R ¹ , R ² , X, a and b are the same as described above.)

[0025]

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(In the formula, R ² , X and a are the same as described above.) Such a production method is described in, for example, Japanese Patent Publication No. 4-69659.
No., JP-B-7-10828, JP-A-63-2541
No. 49, JP-A-64-22904, JP-A-64-38
No. 407, etc. Further, the isobutylene-based polymer having a reactive silicon group in the molecular chain is produced by adding a vinylsilane or an allylsilane having a reactive silicon group to a monomer mainly composed of isobutylene and copolymerizing the monomer.

Further, in the polymerization for producing an isobutylene-based polymer having a reactive silicon group at the terminal of the molecular chain, a vinylsilane or an allylsilane having a reactive silicon group other than the main component isobutylene monomer is copolymerized. After that, by introducing a reactive silicon group to the terminal, an isobutylene-based polymer having a reactive silicon group at the terminal and in the molecular chain is produced.

Examples of vinylsilanes and allylsilanes having a reactive silicon group include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane, and allylsilane. Examples include methyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.

In the hydrogenated polybutadiene-based polymer, for example, first, a hydroxyl group of a hydroxy-terminated hydrogenated polybutadiene-based polymer is converted into an oxymetal group such as -ONa or -OK, and then, a compound represented by the general formula (5): CH ₂ = ^{CH-R 3 -Y (5)} ( in the formula, Y is a chlorine atom, a halogen atom such as iodine atom, R ³ is -R ⁴ -, - R ⁴ -OCO- or -R ⁴ -CO
A divalent organic group represented by-(R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkylene group, a cycloalkylene group, an arylene group, or an aralkylene group);
H ₂ —, —R ″ —C ₆ H ₅ —CH ₂ — (R ″ has 1 to 1 carbon atoms.
Dihydrogen group selected from the group consisting of 10 hydrocarbon groups) is particularly preferred) to form a hydrogenated polybutadiene-based polymer having a terminal olefin group (hereinafter referred to as a hydrogenated polybutadiene-based polymer having an olefinic terminal). Is also manufactured).

A method for converting a terminal hydroxyl group of a hydroxy-terminated 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 ;
A method of reacting with an alkali hydroxide such as OH and KOH is exemplified. In the above method, a terminal olefin hydrogenated polybutadiene-based polymer having substantially the same molecular weight as the terminal hydroxy-hydrogenated polybutadiene-based polymer used as a starting material can be obtained. Before reacting the organic halogen compound of the formula (5), a polyvalent organic halogen compound containing two or more halogens in one molecule such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether, etc. The molecular weight can be increased by the reaction, and the reaction with the organic halogen compound represented by the general formula (5) yields a hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at the terminal. Can be.

Specific examples of the organic halogen compound represented by the general formula (5) include, for example, 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)
Examples include, but are not limited to, benzene and allyloxy (chloromethyl) benzene. Of these, allyl chloride is preferable because it is inexpensive and easily reacts.

The introduction of the reactive silicon group into the hydrogenated polybutadiene-based polymer at the terminal olefin is carried out, for example, by the general formula (3) as in the case of the isobutylene-based polymer having a reactive silicon group at the molecular chain terminal. The compound is preferably prepared by subjecting a hydrosilane compound, preferably a compound represented by the general formula (4), to an addition reaction using a platinum-based catalyst.

Examples of the hydrosilane compound represented by the general formula (3) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane; trimethoxysilane, triethoxysilane, methyl Alkoxysilanes such as diethoxysilane, methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoxime) methylsilane and bis (cyclohexylketoxime) ) Ketoxime silanes such as methyl silane and the like, but are not limited thereto. Of these, halogenated silanes and alkoxysilanes are particularly preferred.

As described above, when the saturated hydrocarbon polymer having a reactive silicon group does not substantially contain an unsaturated bond other than an aromatic ring in the molecule, an organic polymer having an unsaturated bond or Compared with a conventional sealing agent made of a rubber-based polymer such as an oxyalkylene-based polymer, the weather resistance is significantly improved. Further, since the polymer is a hydrocarbon polymer, it has good moisture barrier properties and water resistance, and has excellent adhesion performance to various inorganic base materials such as glass and aluminum, and has a low moisture barrier property. become.

The content of the saturated hydrocarbon polymer having a reactive silicon group in the curable composition of the present invention is preferably at least 10% (weight, the same applies hereinafter), more preferably at least 20%, more preferably at least 30% Is particularly preferred. In the curable composition of the present invention, a compound containing one or more epoxy groups in one molecule is used as the component (B) in order to enhance storage stability. The epoxy compound is not particularly limited, and specifically, bisphenol A type epoxy resins,
Bisphenol F type epoxy resins, bisphenol A
D-type epoxy resin, bromide-containing epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, heterocyclic Examples thereof include epoxy resins, epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, and mixtures thereof.

In order to impart adhesiveness, the component (B) preferably has at least one reactive silicon group in the molecule, and in particular, the reactive silicon group represented by the general formula (1) or (2) Preferably, the epoxy silane coupling agent has the following formula: X in the general formula (1) or (2) is more preferably a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group or an alkenyloxy group. In the above, an alkoxy group is particularly preferred.

More specifically,

[0038]

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The following compounds can be used.
Epoxy compounds, when used in the composition of the present invention, can significantly prevent a hydrolysis reaction or the like due to moisture or the like of a reactive silicon group of a saturated hydrocarbon polymer having a reactive silicon group, By preventing a crosslinking reaction due to formation of a siloxane bond between reactive silicon groups, the storage stability of the composition can be significantly improved. In addition, the storage stability improver does not adversely affect the physical properties of the cured product after storage.

The amount of the epoxy compound is preferably from 0.1 to 20 parts, more preferably from 1 to 10 parts, and more preferably from 2 to 5 parts, per 100 parts of component (A) (the same applies hereinafter). This is particularly preferred. If the amount is less than 0.1 part, the effect of improving storage stability may not be sufficient, and if it exceeds 20 parts, the curability of the curable composition may decrease.

The composition of the present invention can be further modified by incorporating various fillers. Such fillers include reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, talc and carbon black; heavy calcium carbonate, colloidal calcium carbonate, diatomaceous earth, calcined clay, Clay, titanium oxide, bentonite, organic bentonite, ferric oxide,
Fillers such as zinc oxide and activated zinc white; fibrous fillers such as glass fibers and filaments can be used.
In order to obtain a high-strength curable composition with these fillers, reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, talc and carbon black are mainly used. When used in an amount of 1 to 100 parts with respect to 100 parts of the component (A) of the present invention, a cured product having high strength and high modulus in mechanical properties can be obtained. On the other hand, when it is desired to obtain a cured product having low modulus and high elongation, heavy calcium carbonate, colloidal calcium carbonate, diatomaceous earth, calcined clay, clay, titanium oxide, bentonite,
Fillers such as organic bentonite, ferric oxide, zinc oxide and activated zinc white may be used in the range of 5 to 400 parts per 100 parts of the component (A) of the present invention. of course,
These fillers may be used alone or in combination of two or more. The composition containing the polymer of the component (A) of the present invention, which uses colloidal calcium carbonate as a filler, is particularly poor in storage stability, but is specifically improved in storage stability by adding an epoxy compound. Is seen.

In the composition of the present invention, when a plasticizer is used in combination with a filler, the elongation of the cured product can be increased,
It is more useful because a large amount of filler can be mixed. As the plasticizer, a commonly used plasticizer can be used, but a plasticizer having good compatibility with the saturated hydrocarbon polymer used in the present invention is preferable. Specific examples of the plasticizer include, for example, polybutene, hydrogenated polybutene, α-methylstyrene oligomer, liquid polybutadiene, hydrogenated liquid polybutadiene,
Paraffin oil, naphthenic oil, atactic polypropylene and the like, among which hydrogenated polybutene containing no unsaturated bond, hydrogenated liquid polybutadiene,
Hydrocarbon compounds such as paraffin oil, naphthenic oil and atactic polypropylene are preferred.

Although the polymer of the component (A) used in the present invention is cured by moisture, it is possible to add water or a compound capable of releasing water to the composition in advance. By doing so, the composition can be rapidly cured. Examples of compounds capable of releasing water include inorganic or organic compounds having water of crystallization. As specific examples, sodium sulfate decahydrate having water of crystallization, sodium thiosulfate pentahydrate, sodium phosphate dodecahydrate,
Examples include magnesium sulfate heptahydrate and sodium tetraborate decahydrate. Water or a compound capable of releasing water is used in an amount of 0.1 to 3 based on 100 parts of the component (A) polymer.
It is good to use 0 parts, preferably 1 to 20 parts. The composition containing the polymer of the component (A) of the present invention using colloidal calcium carbonate as a filler and using water or a compound capable of releasing water has a particularly remarkable decrease in storage stability. By adding an epoxy compound, a remarkable remarkable improvement in storage stability is observed.

In the composition of the present invention, a curing catalyst can be used in combination. As the curing catalyst, II valent and I
V-valent tin-based curing catalyst, titanium-based curing catalyst, aluminum-based curing catalyst, amine-based curing catalyst, and the like. Among these, a tin-based curing catalyst having a valence of IV is particularly preferred as a curing catalyst for the composition of the present invention because of its high curing rate. That is, when an epoxy compound is added to the polymer of the component (A) of the present invention, the curing rate of the polymer of the component (A) usually decreases. The decrease is not so large, and a significantly higher curing rate can be obtained as compared with other curing catalysts.

Specific examples of the IV-valent tin-based curing catalyst include:
For example, dibutyltin bisacetylacetonate, dibutyltin dialkoxide, dibutyltin dilaurate,
Dibutyltin maleate, dibutyltin diacetate,
And the like. IV valent tin carboxylate and the like.
Specific examples of the II-valent tin-based curing catalyst include, for example, II-valent tin carboxylate salts such as tin octylate and tin naphthenate. Specific examples of the titanium-based curing catalyst include, for example, titanates such as titanium tetrabutoxide, titanium diacetylacetonate, tetrabutyl titanate, and tetrapropyl titanate. Specific examples of the aluminum-based curing catalyst include, for example, aluminum trisacetylacetonate,
Organic aluminum compounds such as aluminum trisethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate. Specific examples of amine curing catalysts include, for example, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminepropylamine, xylylenediamine , Triethylenediamine, guanidine, diphenylguanidine,
Amine compounds such as 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4,6) undecene-7 (DBU), and carboxylic acids thereof And salt.

These catalysts may be used alone,
Two or more kinds may be used in combination. The amount used is preferably 0.1 to 10 parts. When the amount of the curing catalyst is less than 0.1 part,
Curability may not be sufficient, and if it exceeds 10 parts, physical properties of a cured product may be reduced. The curing catalyst is preferably added when the composition is cured. If the composition is stored after addition, the composition is easily cured during storage.

Various additives are further added to the curable composition of the present invention, if necessary. Examples of such additives include, for example, a physical property adjusting agent for adjusting the tensile properties of the resulting cured product, an adhesion improver represented by a silane coupling agent, an antioxidant, a radical inhibitor, and an ultraviolet absorber. , Metal deactivators, ozone deterioration inhibitors, light stabilizers such as nickel compounds, phosphorus-based peroxide decomposers, lubricants, pigments,
Foaming agents, surfactants and the like.

Specific examples of such additives include, for example,
Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-1088928,
JP-A-63-254149, JP-A-64-22904
It is described in each specification of the issue. In the composition of the present invention, either a one-part composition or a two-part composition is possible, but it is preferable to use it as a two-part composition. For example, when the components (A) and (B) of the present invention are divided into a base material composed of a filler and a plasticizer and a curing agent composed of a filler, a plasticizer and a curing catalyst, the two components are mixed and used immediately before use. ,
Even after long-term storage, the initial cured physical properties can be stably exhibited.

The composition of the present invention is useful mainly as a two-part elastic sealing material, and can be used for electronic and electric, civil engineering, building,
It can be used for sealing applications on ships, automobiles, roads and the like. Furthermore, by using a primer or the like, it can be firmly adhered to a wide range of substrates such as glass, stone, ceramic, wood, synthetic resin, metal, etc., so that it can be used as an adhesive composition of various types. It is possible.

The cured product of the curable composition of the present invention has excellent weather resistance and is particularly suitable as a sealing material around glass. For example, it is suitably used as a sealing material for waterproofing a window glass of a building, a sealing agent for double-layered glass, a netted glass, a rustproofing / waterproofing sealing material for an end face (cut portion) of a laminated glass, and the like.

[0051]

EXAMPLES Next, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0052]

[Production Example] A stirring blade, a three-way cock and a vacuum line were attached to a 3 L pressure-resistant glass autoclave, and the polymerization vessel was dried by heating at 100 ° C. for 1 hour while evacuating the vacuum line. After cooling to room temperature, the pressure was returned to normal pressure with nitrogen using a three-way cock.

Then, while flowing nitrogen from one of the three-way cocks, a solvent, methylene chloride 61, dried on the autoclave by molecular sieve treatment using a syringe.
8 mL and 1001 mL of n-hexane were introduced. Next, 5 in which 15 mmol of p-DCC (the following compound) was dissolved
0 mL of methylene chloride solution was added. Subsequently, 6.0 mmol of the additive α-picoline was added.

[0054]

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Then, a liquefied gas sampling tube made of pressure-resistant glass with a needle valve containing 224 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock. Was cooled in a dry ice-acetone bath for 1 hour while stirring the inside of the polymerization vessel. After cooling, the inside was depressurized by a vacuum line, then the needle valve was opened, and isobutylene was introduced into the polymerization vessel from a pressure-resistant glass liquefied gas sampling tube.
Thereafter, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks, cooling was further continued for 1 hour with stirring, and the temperature in the polymerization vessel was raised to -70 ° C.

Next, 8.2 mL of TiCl ₄ (75 mm
1) was added from a three-way cock using a syringe to initiate polymerization, and after 1 hour, allylsilane 14.3 was added.
mL (90 mmol) was added. After further reacting for 1 hour, the reaction mixture was poured into methanol to stop the reaction. After stirring for a while, the mixture was allowed to stand and the polymer was separated by precipitation.

The polymer obtained in this manner is again converted to n
After dissolving in -hexane and washing with pure water three times, the solvent was distilled off to obtain an allyl-terminated isobutylene-based polymer. Then, the allyl-terminated isobutylene polymer thus obtained is obtained.
100 g was dissolved in 50 ml of n-heptane,
After raising the temperature to 1.5 [eq /
Vinyl group], platinum (vinylsiloxane) complex 1 × 10 ^-4
[Eq / vinyl group] was added, and a hydrosilylation reaction was performed. The reaction was followed by FT-IR, and 16 hours in about 4 hours.
The olefin absorption at 40 cm ^-1 disappeared.

The reaction solution was concentrated under reduced pressure to obtain a desired isobutylene polymer having reactive silicon groups at both ends. (The following compounds)

[0059]

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The yield was calculated from the amount of the polymer thus obtained, and the Mn and Mw / Mn were determined by the GPC method, and the terminal structure was determined by 300 MHz ¹ H-NMR analysis. Proton: 6.5 to 7.5 ppm, methyl proton bonded to a silicon atom derived from a polymer end: 0.0 to 0.1 ppm
And methoxy protons: 3.4 to 3.5) were obtained by measuring and comparing the intensity of the resonance signals. ¹ H-NMR
Is a Varian Gemini 300 (300 MHz
for ¹ H) in CDCl ₃ . The FT-IR is IR-408 manufactured by Shimadzu Corporation, and the GPC is a Waters LC Module as a liquid sending system.
1. Column was performed using Shodex K-804. Molecular weights are given as relative molecular weights to polystyrene standards. The analytical value of the polymer was Mn = 114.
16, Mw / Mn = 1.18, Fn (silyl) = 1.9
It was 5. (The number average molecular weight is in terms of polystyrene, and the number of terminal silyl functional groups (Fn (silyl)) is the number per one molecule of isobutylene polymer).

[0061]

Examples 1-4 and Comparative Example 1 Paraffin-based process oil (Diana Process PS-32, trade name, manufactured by Idemitsu Kosan Co., Ltd.) was added to 100 parts of the polymer obtained in the Production Example.
0 parts, heavy calcium carbonate (Shiraishi Calcium Co., Ltd.,
20 parts of brand name Whiten SB), 100 of colloidal calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., brand name Biscolite R) 100
Parts, Na ₂ SO ₄ .10H ₂ O 5 parts, antioxidant (Irganox 1010, trade name, manufactured by Ciba-Geigy)
Parts, 1 part of an ultraviolet absorber (Ciba Geigy Co., Ltd., trade name Tinuvin 327), 1 part of a light stabilizer (Sankyo LS-770, trade name), photocurable resin (Toagosei Co., Ltd.) Manufactured by Alonix M309), 3 parts, anti-sagging agent (Kusumoto Kasei Co., Ltd., trade name: Dispalon # 305)
3 parts, epoxy compound (Yukaka Epoxy Co., Ltd.)
And the product name Epicoat 828)
Kneaded well with three paint rolls. The viscosity of the composition before storage and after storage at 50 ° C. for 28 days was measured at a temperature of 2
The measurement was performed using a BS viscometer (rotor: No. 7, rotation speed: 10 rpm) under the conditions of 3 ° C. and a humidity of 65 ± 10%. Table 1 shows the results.

[0062]

[Table 1]

The rate of increase in viscosity in the table is (28 days (5 days)
0 ° C) (viscosity after storage / viscosity before storage).

[0064]

EXAMPLES 5-6 AND COMPARATIVE EXAMPLE 2 100 parts of the polymer obtained in the Production Example were mixed with paraffin-based process oil (Diana Process PS-32, trade name, manufactured by Idemitsu Kosan Co., Ltd.).
00 parts, heavy calcium carbonate (Maruo Calcium Co., Ltd.)
150 parts, colloidal calcium carbonate (trade name: EDS-D10A, manufactured by Shiraishi Industry Co., Ltd.)
100 parts, 50 parts of talc (trade name: Talc LMR, manufactured by Fuji Talc Industry Co., Ltd.), 5 parts of Na ₂ SO ₄ .10H ₂ O, 1 part of antioxidant (trade name: Irganox 1010, manufactured by Ciba Geigy Co., Ltd.) UV absorber (Ciba Geigy Co., Ltd.)
1 part of light stabilizer (manufactured by Sankyo Co., Ltd., trade name: SANOL LS-770), 1 part, epoxy compound (manufactured by Nippon Unicar Co., Ltd., trade name: silane coupling agent A-187) ) Was added in the number shown in Table 2 and kneaded well with a three-paint roll. The viscosity of the composition before storage and after storage at 50 ° C. for 28 days was determined at a temperature of 23 ° C.
Under the condition of a humidity of 65 ± 10%, a BS type viscometer (rotor:
No. 7, rotation speed: 10 rpm).
Table 2 shows the results.

[0065]

[Table 2]

As shown in Tables 1 and 2, the storage stability of a curable composition comprising a saturated hydrocarbon polymer having at least one reactive silicon group in the molecule is improved by adding an epoxy compound. Can be confirmed. Further, 4 parts of a curing catalyst (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220) was added to each of the formulations of Examples 5 to 6 and Comparative Example 2, and after sufficiently kneading, a tensile specified in JIS A5758 was applied. An adhesion test was performed. Table 3 shows the JIS R
The results of a tensile adhesion test using a glass plate specified in 3202 are shown.

[0067]

[Table 3]

As shown in Tables 2 and 3, the addition of the epoxy compound having at least one reactive silicon group in the molecule resulted in the formation of a curable composition comprising a saturated hydrocarbon polymer having a reactive silicon group. It can be confirmed that the storage stability is improved and the adhesiveness is improved.

[0069]

The curable composition of the present invention can improve storage stability. Further, when various additives are added to the curable composition of the present invention, it is particularly useful as an elastic sealant, and the workability of the sealant can be stably maintained over a long period of time.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 63/00 C08L 63/00 A 83/04 83/04

Claims (10)

[Claims] (A) having at least one silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond;
100 parts by weight of a saturated hydrocarbon polymer having a molecular weight of 500 to 50,000 and (B) an epoxy compound 0.1 to
A curable composition having improved storage stability, comprising 20 parts by weight. 2. The epoxy compound as the component (B) has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and has at least one silicon-containing group capable of crosslinking by forming a siloxane bond. The curable composition having improved storage stability according to claim 1. 3. The curable composition with improved storage stability according to claim 1, wherein the polymer as the component (A) is a polymer having a total amount of repeating units derived from isobutylene of 50% by weight or more. . 4. The curable composition according to claim 1, further comprising 5 to 400 parts by weight of colloidal calcium carbonate and 0.1 to 100 parts by weight of water or a substance capable of releasing water. 5. The curable composition according to claim 1, further comprising 0.1 to 10 parts by weight of an IV valent tin-based curing catalyst. (A) having at least one silicon-containing group capable of crosslinking by forming a siloxane bond, having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and having a molecular weight of 500 to 50,000. 100 parts by weight of a certain saturated hydrocarbon polymer and 0.1 to 2 epoxy compound (B)
A method for improving the storage stability of a curable composition by adding 0 parts by weight. 7. The epoxy compound as the component (B) has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and has at least one silicon-containing group which can be crosslinked by forming a siloxane bond. A method for improving the storage stability of the curable composition according to claim 6. 8. The storage stability of the curable composition according to claim 6, wherein the polymer as the component (A) is a polymer having a total amount of repeating units derived from isobutylene of 50% by weight or more. Method. 9. The storage of a curable composition according to claim 6, wherein the curable composition further comprises 5 to 400 parts by weight of colloidal calcium carbonate and 0.1 to 100 parts by weight of water or a substance capable of releasing water. How to improve stability. 10. The method for improving the storage stability of a curable composition according to claim 6, wherein the curable composition further contains 0.1 to 10 parts by weight of a tin IV curing catalyst.