JPS6363750A - Curable composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which is useful as a sealant, an adhesive, etc. and has excellent curability, tensile characteristics and resilience and whose tack is lowly temperature-dependent, containing an org. polymer having a hydrolyzable group and an org. polymer having a silanol group. CONSTITUTION:A monomer (a) having a copolymerizable unsaturated group and a hydrolyzable silicon group, such as a vinyltrialkoxysilane is copolymerized with a vinyl monomer (b) such as ethylene, an acrylic ester, etc. to obtain an org. polymer (A) having at least one hydrolyzable group per molecule. For example, the component A is hydrolyzed in the presence of an equimolar or excess amount (based on the mol no. of the hydrolyzable group of the component A) of water and optionally, a catalyst such as a tin compd. at 0-100 deg.C to obtain an org. polymer (B) having at least one silanol group per molecule. 100pts.wt. component A is blended with 10-100pts.wt. component B and optionally, a plasticizer, a filler, a reinforcing agent, a colorant, a curing catalyst, an anti-sagging agent, a physical property modifier, etc. (C).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to an organic polymer containing a small number (at least one hydrolyzable silicon group) in the molecule and an organic polymer containing at least one silanol group in the molecule. curable compositions having improved tensile properties and curability.

[Prior Art] Conventionally, polymers containing a small number of hydrolyzable silicon groups in their molecules have been used as sealants, adhesives, adhesives,
It is used in a wide range of applications such as paints, and one of the technical challenges common to these applications is to improve the tensile properties of the cured product, that is, to increase its elongation and improve its brittleness.

In order to achieve this objective, the present inventors have developed an improvement method by adding various silicon compounds (Japanese Patent Application Laid-Open No. 53-129247
(Japanese Patent Application No. 59-156673 and Japanese Patent Application No. 59-156674) have been proposed, but these methods have a common problem. The problem with this is that the curing properties deteriorate, which limits its use.

So, the above mentioned 8! When using a polymer as an adhesive,
The problem is that the adhesive strength at around 70°C is lower than the adhesive strength at room temperature, and it decreases significantly compared to the adhesive strength at room temperature, and when it is pasted on a curved surface, spontaneous peeling occurs. There are problems with how easy it is.

[Problems to be Solved by the Invention] The present invention relates to a technology for improving the tensile properties of organic polymers containing at least one hydrolyzable silicon group in the molecule, and conventional improvement methods have resulted in poor curing properties. However, it was developed with the aim of improving this drawback and further improving the temperature dependence of adhesive strength and curved surface adhesion when used as an adhesive.

[Means for Solving the Problems] The present invention is directed to a chemical compound containing at least one hydrolyzable silicon group in its molecule. Regarding curable compositions containing a polymer and an organic polymer containing at least one silanol group in the molecule, forming such a composition improves tensile properties, curing properties, and even adhesive properties. This was based on the discovery that the temperature dependence of adhesive strength and curved surface adhesion were significantly improved when used.

[Example] Examples of the polymer forming the skeleton of the organic polymer containing at least one hydrolyzable silicon group in the molecule used in the present invention include cyclic ethers such as propylene oxide, ethylene oxide, and tetrahydro-7rane. Polyether Mffi polymer obtained by polymerization; 2 such as adipic acid
Polyester polymers produced by condensation of basic acids and glycols or ring-opening polymerization of lactones; ethylene-propylene copolymers; copolymers of polyisobutylene or imbutylene with isoprene, etc.; polychloroprene; polyisoprene Or copolymers of isoprene and butadiene, styrene, acrylonitrile, etc.; polybutadiene or copolymers of butadiene and styrene, acrylonitrile, etc.; polyolefins obtained by hydrogenating polyisoprene, polybutadiene, or copolymers of isoprene and butanoene. Polymer; polyacrylic ester obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate, or a copolymer of the acrylic ester and at least one of vinyl acetate, acrylonitrile, styrene, ethylene, etc.;
The organic polymer used in the present invention, for example, the main chain has the general formula: -
Polyethers and polyethers having a repeating unit represented by R-0- (in the formula, R represents an alkylene group having 2 to t carbon atoms) and having a hydrolyzable silicon group or a silanol group. (Graft polymers obtained by polymerizing vinyl monomers in the presence of one species; examples include polymers such as polysulfide threads.Among these, polypropylene oxide polyethers have the general formula: -R-0- Polymerization of vinyl materials such as acrylic esters, styrene, 7-crylonitrile, and vinyl acetate in the presence of polyethers such as polyethers and polypropylene oxides having repeating units represented by (wherein R is the same as above) Contains 50% or more of polymers or copolymers such as graft polymers, polyacrylic esters, or acrylic ester components, and contains vinyl monomer components such as vinyl acetate, acrylonitrile, styrene, and ethylene. A copolymer containing is preferred because it is easy to introduce a hydrolyzable silicon group to the molecular end, and it is easy to produce a liquid polymer with no dissolution exfoliation. Particularly preferred is polypropylene oxide because it is easy to handle as a product.

Honmei 1! The term "hydrolyzable silicon group" as used in this book means a group in which a hydrolyzable group is bonded to a silicon atom, which undergoes hydrolysis by moisture in the presence or absence of a silyl condensation catalyst. Specific examples of hydrolyzable groups include hydrogen atoms,
Halogen atom, alkoxy group 1. Commonly used groups include an alkoxy group, a ketoximate group, an amide group, a 7-mido group, a 7-minooxy group, a mercapto group, and a fluorenyloxy group. Among these, an alkoxy group is particularly preferred because it is mildly hydrolyzable and easy to handle.The hydrolyzable group has 1 to 3 atoms bonded to one silicon atom.

The number of silicon atoms forming the hydrolyzable silicon group may be one, or two or more, but in the case of silicon atoms connected by silotosan bond etc., the number is up to 20. is preferable.

Examples of methods for introducing hydrolyzable silicon groups into organic polymers include the following methods.

(1) Monomers having a copolymerizable unsaturated group and a hydrolyzable silicon group in the molecule, such as vinyltriflukoxysilane, methacryloyloxypropylmethylnoflukoxysilane, methacryloyloxypropyltrialkoxysilane, etc. Copolymerize with polymerizable monomers such as ethylene, propylene, isobutylene, chlorobrene, isoprene, butadiene, acrylic ester,
A monomer having a copolymerizable epoxy group and a hydrolyzable silicon group in the molecule, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc., is combined with propylene oxide or ethylene oxide. A method of copolymerization.

These methods allow the introduction of hydrolyzable silicon groups into molecular side chains.

(2) In lanocal polymerization, a mercapto group or a disulfide group, such as mercaptopropyltrialcoxinlan or norcabutopropylmethyldialphoxysilane, which can undergo a chain transfer reaction, and a hydrolyzable silicon group are added to the molecule. A method of polymerizing a radically polymerizable monomer using a silicon compound having as a chain transfer agent.

(3) Azobis-2-(6-methyljethoxysilyl-
A method of polymerizing radically polymerizable monomers using an azo or peroxide polymerization initiator containing a hydrolyzable silicon group, such as 2-anohexane).

In methods (2) and (3), hydrolyzable silicon groups are introduced at the ends of the polymer molecules.

(4) hydroxyl group at the gA chain and V (or) terminal of the polymer,
A polymer having a functional group such as a carboxyl group, a mercapto group, an epoxy group, or an incyanate group (hereinafter referred to as a Y functional group) is used, and the molecule contains a Y functional group that can react with the Y functional group. , and a method of reacting a silicon compound having a hydrolyzable silicon group with a Y functional group.

Specific reaction examples are shown in the table below, but are not limited thereto.

In particular, as polymers having a Y1r functional group used as starting materials and intermediate materials in the table, main ffI is essentially -R, such as polypropylene polyol, polyethylene polyol, polytetramethylene diol, etc.
-0- (in the formula, R is the same as the one-sided system) polyether polyols consisting of repeating units; obtained by condensation of a dibasic acid such as adipic acid with glyfur or ring-opening polymerization of lactones. Polyester polyols; Polyols of polyisobutylene or polycarboxylic acids; Polyols or polycarboxylic acids of polybutadiene or copolymers of butadiene and styrene, 7-crylonitrile, etc.; Polyolefins obtained by hydrogenating polyisoprene or polybutanoene. Polyols; Isocyanate functional group-containing polymers obtained by reacting the polycarboxylic acid and polyisocyanate; The vinyl-type unsaturated group-containing polymers obtained by the reaction are preferred, and it is more preferred that the Y functional group is located at the end of the polymer molecule.

As the silicon compound having the Y' functional group, γ-(
Silanes containing ami7 groups such as 2-7mi/2,000l)ami/propyltrimethoxysilane, γ-(2-7mi7ethyl)ami/propylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, etc. 2 groups of mercap Y group-containing silas such as amercaptopropyltrimethoxysilane, γ-mercabutobrobylmethyldimeth-disilane, etc.; γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxy Epoxysilane caps such as cyclohexyl)ethyltrimethoxysilane; vinyl-type unsaturated groups such as vinyltrinidoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-7cricoyloxypropylmethylnomethoxysilane, etc. Containing silanes; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; Incyanate-containing silanes such as γ-incyanatopropyltriethoxysilane, γ-isocyanatepropylmethyldimethoxysilane; methylnomethoxy Specific examples include hydrosilanes such as silane, trimethoxysilane, and methyljethoxysilane, but are not limited thereto.

In particular, in the combination of a polymer containing a Y functional group and a silicon compound containing a Y′ functional group, (i) a polymer having an incyanate group and a silane containing an amine 7 group or a silane containing a mercapto group is used. (11) A combination of a vinyl-type unsaturated group-containing polymer and a hydrosilane is preferable, and (ii) a combination of a polypropylene oxide having an allyl ether group at the molecular end and a hydrosilane is preferable. It is particularly preferable to combine (ii
), a platinum-based compound or the like may be used as a catalyst to carry out a hydrosilylation reaction, whereby a vinyl group and a hydrosilyl group are reacted, and a silyl group may be introduced into the polymer.

At least 1, preferably 1 in the molecule used in the present invention
．． The molecular weight of the rubber-based organic polymer having 2 to 6 hydrolyzable silicon groups is about 500 to 50,000, particularly about 1,000 to 20,000, which is particularly preferable from the viewpoint of easy handling. If the number of hydrolyzable silicon groups is less than one, curing may be insufficient and the modification effect may not be clear.

In the rubber-based organic polymer 1 having at least 1 fl of a hydrolyzable silicon group in the molecule used in the present invention, the hydrolyzable silicon group is preferably present at the end of the molecule. When the group is present, the effective network 1'tfl of the cured product increases.
Rubber elasticity becomes effective and easy to crack.

Specific examples of the above-mentioned organic polymers containing at least one hydrolyzable silicon group in the molecule include Japanese Patent Publications No. 45-36319, No. 46-12154, No. 49-32673, and Japanese Patent Publication No. 49-32673. No. 50-156599, No. 51-73561, No. 54-6096, No. 55-1
No. 3767, No. 54-13768, No. 55-8212
No. 3, No. 55-123620, No. 55-125121
No. 55-131021, No. 55-131022, No. 55-135135, No. 55-137129,
No. 57-179210, No. 58-191703J'f
, No. 59-78220, No. 59-78221, No. 59-78222, No. 59-78223, No. 59-
Examples include those disclosed in publications such as No. 168014, and these are preferably used, but the invention is not limited thereto.

At least one sila/- in the molecule used in the present invention
Organic polymers containing ru groups can be purified by hydrolyzing the hydrolyzable silicon groups of organic polymers having at least 1 WA of hydrolyzable silicon groups in the molecule.

There are no particular restrictions on the method of hydrolysis, and i1M
Generally, a method that is used for hydrolyzable groups bonded to silicon atoms may be employed, and care may be taken to avoid condensation of the silyl groups.

When the hydrolyzable group is a halogen atom, it is preferable to use an acid scavenger, and examples of acid scavengers include basic nitrogen compounds such as ammonia, triethylamine, noethylamine, pyridine, picoline, and RNt. , carbonates of alkali metals such as sodium bicarbonate, sodium RR, and potassium carbonate, and carbonates of alkaline earth metals such as RR calcium and argentium carbonate.

When the hydrolyzable group is a hydrogen atom (child 5i-It), a conventionally used catalyst such as a platinum-based compound, palladium-based compound, ronium-based compound or ruthenium-based compound is used as necessary, Hydrolysis may be carried out by adding the same mole or more of water to Mi-5i-H.

Similarly, for the hydrolyzable groups in the pond, such as alkoxy groups, aminoxy groups, alkenyloxy groups, amido groups, and ami7 groups, water is added in an amount equal to or more than the molar amount of the corresponding hydrolyzable groups. If necessary, the hydrolysis may be carried out using a conventionally used catalyst such as a tin-based compound, a chitan-based compound, an aluminum-based compound, or a zirconium-based compound.

When carrying out these reactions, it is necessary to lower the viscosity,
A solvent may be used as necessary for purposes such as controlling reaction heat. The solvent is preferably one that is inert to the hydrolyzable silicon group or silyl group used,
Specifically, aromatic hydrocarbon compounds such as benzene, toluene, and xylene, aliphatic hydrocarbon compounds such as hexane, heptane, and octane, diethyl ether, and T)I.
Examples include ether compounds such as P and Nootosan, ketone compounds such as totyl ethyl ketone, and halogenated hydrocarbon compounds such as methylene chloride and trichloroethylene.

There is no particular restriction on the reaction temperature, but it is 0 to 100°C.
It is practical to carry out the reaction at a temperature of 30 to 90°C, preferably 30 to 90°C.

An organic polymer containing at least one hydrolyzable silicon group in the molecule (hereinafter referred to as polymer A) and an organic polymer containing at least one lanol group in the molecule (hereinafter referred to as polymer B) ) may be determined depending on the intended use, that is, the target v4 density (reflected in the measured physical properties such as modulus and hardness).
It also varies greatly depending on the content of hydrolyzable silicon groups and nranol groups in Polymers A and I/B. Generally, for 100 parts (parts by weight, the same applies hereinafter) of Polymer A, Polymer B
The amount used is in the range of 10 to 1000 parts, preferably 50 to 1000 parts.
200 copies.

When the curable composition of the present invention is used as a sealant, plasticizers, fillers, reinforcing materials, anti-sagging agents, colorants, anti-aging agents, adhesion promoters, curing catalysts, physical properties, etc. Conditioners and the like may be added.

Examples of the plasticizer include dibutyl 7-talate, noheptyl 7-thalet, di(2-ethylhexyl) 7-thaleate, butylbenzyl 7-thaleate, butyl phthalyl butyl glycolate, etc., depending on the purpose of controlling physical properties and properties. 7-talic acid esters; non-aromatic dibasic acid varnishes such as nooctyl adibate and dioctyl sepacate
TR: Polyfulkylene glycol esters such as diethylene glycol nobenzoate and triethylene glycol nobenzoate; phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; flukynophenyl, n-water mter 7
Hydrocarbon oils such as Enyl can be used. These may be used alone or in combination of two or more, but are not necessarily required.

Note that these plasticizers may be added during polymer production.

The fillers and reinforcing materials include heavy or light calcium carbonate; calcium carbonate surface-treated with fatty acids, resin acids, cationic surfactants, anionic surfactants, etc.; magnesium carbonate; talc; titanium oxide; Barium sulfate; alumina; aluminum; metal powders such as zinc and iron;
Common materials include bentonite; kaolin clay; humid silica; quartz powder; and carbon black. These may be used alone or in combination of two or more. Among these, fillers and reinforcing materials that can impart transparency to the cured product, such as fumed silica, are used as sealants with excellent transparency. It is also possible to create

Examples of anti-sag agents include hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate; There is love.

As the colorant, common inorganic or organic pigments, dyes, etc. may be used as required.

As the physical property modifier, various silane coupling agents such as methylfurkoxysilanes such as methyltrimetholdisilane, trimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisoprope-7xysilane, methyl Furkylisopropenoxysilanes such as triisopropenoxysilane, γ-glycidoxypropylmethyldiisoprobe/quinsilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
Vinyltritoxysilane, vinyltmethylmethoxysilane, aminopropyltrimethoxysilane, N-(
β-7minoethyl)aminopropylmethylnomethoxysilane, γ-mercapF propyltrimethoxysilane, γ
- Alfukidisilanes having a functional group such as mercaptopropylmethyldimethoxysilane; silicone faces; polysiloxanes, etc. are added as necessary.

By using the physical property modifier, it is possible to increase the hardness of the composition of the present invention when it is cured, or to reduce the hardness and increase elongation.

The adhesion promoter is used because the polymer itself used in the present invention has adhesive properties to glass, ceramics other than glass, metals, etc., and can be bonded to a wide range of materials by using various polymers. Although not necessarily required, adhesion to a wider variety of adherends can be improved by using one or more of epoxy resins, phenolic resins, various silane coupling agents, alkyl titanates, aromatic polyisocyanates, etc. It can be improved.

As a curing catalyst, for example, tetrabutyl titanate,
Titanate esters such as tetrapropyl titanate;
Diptyltin dilaurate, butyltin maleate,
Organotin compounds such as butyltin diacetate, tin octylate, tin naphthenate; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, jetanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, Octylamine, nclohexylamine, benolamine, diethyl 7-minopropylamine, xylylennoamine, F-lyethylenediamine, guanidine, diphenylguanidine, 2,4,6-)lis(tumethyl-7minomethyl)phenol, morpholine, N-ethylmorpholine , 1.3-shi7zabishik0 (5,4゜6)
Amine compounds such as undecene-7 (DBU) or their salts with carboxylic acids; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products between excess polyamines and epoxy compounds; amine groups silane coupling agents, such as γ-7minopropyl trime)xinlan, N-(β-7minoethyl)
A known silanol condensation catalyst such as aminopropylmethylnomethoxysilane may be used as needed.

Furthermore, a solvent may be added for the purpose of improving workability and reducing viscosity, such as aromatic hydrocarbon solvents such as toluene and quinolene, and ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve acetate. , methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and other ketone solvents. These solvents may be used during polymer production.

Although it is not necessary to specifically add an anti-aging agent, ordinary antioxidants and ultraviolet absorbers may be used.

This sealant composition is a one-component type in which all ingredients are sealed and stored in advance, and cured by moisture in the air after application. Alternatively, components such as a curing catalyst, a QT agent, a plasticizer, and water may be separately blended as a curing agent in advance, and the blending agent (material) and the polymer kF! It may also be prepared as a two-component product that is mixed with Lrt and Lrt before use.

If the sealant composition is a one-component type, all the ingredients are mixed in advance, so ingredients containing moisture should be dehydrated and dried before use, or dehydrated by reducing pressure or the like during mixing. It is preferable to do so.

When the sealant composition is a 2r&separation type, there is no need to add a curing catalyst to the polymer-containing main ingredient, so even if the compound contains a small amount of water, there is little concern about delification. When stability is required for long-term storage, dehydration and drying are preferred. Dehydration and drying methods include heat drying for solid materials such as powder, and heat drying for liquid materials. For this purpose, a vacuum dehydration method or a dehydration method using synthetic zeolite, activated alumina, silica sol, etc. is suitable. In addition to this dehydration drying method, in which a small amount of incyanate compound is blended and the incyanate group is reacted with water, lower alcohols such as methanol and ethanol, n-propyltrimethoxysilane, vinyl methyl By adding flufukidisilane compounds such as dimethoxysilane, Amelcaptopropylmethyldimethoxysilane, Amelkab F propylmethyldimethoxysilane, Arglycidoxyprobyltrimethoxysilane, etc.
Furthermore, storage stability is improved.

When the composition of the present invention is used as an adhesive, the curing catalyst, anti-aging agent, plasticizer, reinforcing material, physical property modifier, solvent, etc. used in the sealing material may be used as necessary. Also, depending on the purpose, 7 enol group fat, xylene resin, Kumaron W4T6, petroleum! Known additives such as MN, terpene resin, and terpene phenol resin may be added to ordinary pressure-sensitive adhesive compositions.

The adhesive composition can be widely applied to tapes, sheets, labels, foils, etc., i.e. films made of synthetic or modified natural products, paper, cloth, metal foils, metallized plastic foils, asbestos, etc. Alternatively, the adhesive composition may be applied to a substrate material such as glass fiber cloth in a solvent type, emulsion type, or hot melt type, exposed to moisture or moisture, and cured at room temperature or by heating.

Applications of the composition of the present invention are not limited to sealants or adhesives, but can also be used for paints, adhesives, modifiers, foams, waterproof materials, spray materials, various rubber materials, and the like.

Next, the present invention will be explained in detail with reference to Examples and Comparative Examples.

Synthesis Example 1 Polypropylene oxide 503 having an average molecular weight of 8,000 and having allyl ether groups at 98% of all terminals was placed in four flasks equipped with a stirrer, and 1, 1, 1, 3.5°, 7.7°,
Add 3.5 g of 7-octamethyltetrasiloxane and
After stirring for 0 min, the catalyst solution of chloroplatinic acid (lhPtcZg
・611z01. Oywof )? human a 7 run9. Solution dissolved in Oy) 10μ! and 60″C
The mixture was allowed to react for 6 hours.

Next, after returning the reaction solution to room temperature, 10 μp of the chloroplatinic acid catalyst solution was added once again, and after stirring for 30 minutes, unreacted 1,
1,1,3,5.7,7.7-octamethyltetrasiloxane was removed. Next, water-zo, oxane solution (5.0 g of water dissolved in dioxane 4511, 12.5
z1 was added and reacted for 6 hours at 50"C. Furthermore, 20zf of toluene was added and azeotropic dehydration (90°C, 0.3zz
Hg) was removed, the water-dioxane was removed, and the group-terminated polypropylene oxide was obtained.

Synthesis Example 2 Polypropylene oxide 50.0% has an allyl ether group at 98% of all terminals and has an average molecular weight of 500. were placed in a flask equipped with a stirrer, 601 toluene was added thereto, and about 20 zz' of toluene was removed by azeotropic dehydration under reduced pressure (90°C, 0.3 zzh).The reaction solution was returned to room temperature, and then 1.3 g of dimethylchlorosilane was added. was added, and then 10 μl of chloroplatinic acid catalyst groove 1 (a solution of II□PtC15.6H201, Oy dissolved in 9.02% of tetrahydro7 run) was added, and the mixture was reacted at 40° C. for 5 hours.

After returning the reaction solution to room temperature, triethylamine 1.63
was added, and then 1.5 liters of water was added dropwise over 10 minutes while stirring (white smoke was generated and the hydrochloride was precipitated), and stirring was continued for an additional hour.

After the reaction solution was filtered under reduced pressure to remove the hydrochloride, the filtrate was concentrated under reduced pressure (90'C, 0.3zzt17) Lp
.

In order to know the reaction rate, γ chromatography method 7, 1) I N
As a result of the MR method and infrared analysis method, it was determined that 85% of the terminals of our 9, CI! .

110　Si　　C112C:IzCII20-■ A group-terminated polypropylene oxide was created.

Examples 1 to 3 and Comparative Example 1 Molecules f containing quinsilyl groups in 80% of all terminals
i 8000 polypropylene oxide (hereinafter referred to as dimethoxysilyl group-terminated polymer) and the silanol group-containing polymer obtained in Synthesis Example 1 were mixed in the proportions shown in Table 1, and 100 parts of the mixture akJ was mixed with surface fatty acid-treated carbonic acid. Add 135 parts of calcium, 5 parts of titanium oxide, 15 parts of kaolin, 7 parts of dioctyl 70i, 6 parts of hydrogenated castor oil, 3 parts of tin octylate, and 0.759 parts of laurylamine, and pass through a 3-pane F roll 3 times. After mixing thoroughly,
2 type I (type and approx. 3zz) based on JIS^5758
We also evaluated the characteristics of a thick sheet that was prepared and subjected to a specified curing process. The results are shown in Table 1.

In addition, M in Table 1. is the modulus at 50% elongation,
M15° represents monocularity at 150% elongation, TB represents strength at break, and EB represents elongation at break.

[Left below] Regarding the curability, the polymer prepared in Example 3 based on 100 parts of the dimethoxysilyl group-terminated polymer used in Table 1 showed no tack even after 5 hours at 23°C and 50% RH. Although it did not become tack-free, the samples of Examples 1-3 all became tack-free within 5 hours.

The results in Table tjIJ1 show that the modulus can be adjusted as desired by blending the silanol group-containing polymers.

Examples 4 to 9 The silanol group-containing polymer obtained in Synthesis Examples 1 to 2 and the dimethoxysilyl group-terminated polymer were mixed in the proportions shown in Table 2, and further Il! A toluene solution containing 60 parts of an i'rI-imparting resin (YS Polyster T-115 manufactured by Yasushi Kogyo Co., Ltd.) and having a solid content of 4 to 60 parts was prepared.

Add 5 parts of tylacetoacetate as a curing accelerator to this solution, and prepare a 25 μl thick base material (
The adhesive tape was applied onto Lumirror Film (manufactured by Toshishiku Co., Ltd.) using a coater so that the adhesive thickness after drying was 25 μm, and was cured in a dryer at 120° C. for 1 to 10 minutes to produce an adhesive tape.

It is also used as an adhesive tape for resistance and repulsion tests.
: Y-N 1Mu paper (EK-1 manufactured by J'il Ken Kako Co., Ltd.)
3OR) was coated with a coater so that the adhesive thickness after drying was 50 μl, cured in a dryer at 120°C for 1 to 10 minutes, and then transferred to both sides of a 25 μl thick polyester base material. was created.

Using the adhesive tape obtained as described above, curability, adhesive force (speed dependence, temperature sensitivity), tack, and repulsion resistance were measured by the following methods. The results are shown in Parts 1 and 2.

(Curing properties) After the adhesive tape was initially cured at 120°C for 1 or 2 minutes, it was immediately applied to a stainless steel plate adherend, and the adhesive tape was cured for 23 minutes.
After being left at ℃ for 10 seconds, the tensile speed was about 500 iv / 23℃.
Peeling was performed at 180 degrees after 90 inches in minutes, and the hardenability was determined by the state of the adhesive remaining on the stainless steel plate.

0. There is no adhesive residue on the stainless steel plate. Δ. There is some adhesive residue on the stainless steel plate. X. There is adhesive residue all over the stainless steel plate. 23℃
After standing for 60 minutes at 23°C, the tensile speed was 300111/
180° peel strength in minutes and tensile speed at 300 °C
The 180° peel strength at iz/min was measured.

(Tack) Measurement was performed according to the tack test method (ball rolling method) of JIS Z 023 (angle of inclination: 30°, measurement temperature: 23°C).

(IT Repulsion) One side of the produced double-sided tape was pasted on a board with a thickness of 0.2 zz, and a test piece was cut into a size of 15 xx x 120 zz. The test piece was attached to the adherend (a pipe with an outer diameter of 78 x m and l/186 iz (PVC pipe wrapped around the outer circumference of a board with a thickness of 0.5 x m)), and the vinyl tape was reverse-wound. After pressing for 15 minutes, leave it naturally (23℃, 65℃).
%R11) L, the total length of the left and right turned-up lengths (in am units) was measured.

Comparative Example 2 Adhesive tapes were produced in the same manner as Examples 4 to 9, except that the dimethoxysilyl group-terminated polymer was used alone, and the characteristics were measured. The results are also shown in Table IjS2.

Margin below E] As is clear from the results in Table 2, when the composition of the present invention is used as an adhesive, (1) curing is completed in 1 to 2 minutes after heat treatment (120°C), so curing is fast; (2) Less decrease in adhesive strength at high temperatures (70°C) (
3) Since it has the characteristic of significantly improved It repulsion, it can be used in applications that require adhesive strength at high temperatures and applications that require adhesiveness to curved surfaces.

[Effects of the Invention] When the composition of the present invention is applied to a sealant, the tensile properties (mono 1 lath and elongation V) can be freely controlled without impairing curability, and when applied to an adhesive, the tensile properties (mono 1 lath and elongation V) can be freely controlled. , the temperature dependence of adhesive force can be reduced without impairing curability, and there is also an effect of improving repulsion resistance.

Claims (1)

[Scope of Claims] 1. A curable composition containing an organic polymer containing at least one hydrolyzable silicon group in the molecule and an organic polymer containing at least one silanol group in the molecule. 2. The curable composition according to claim 1, wherein the hydrolyzable silicon group is an alkoxysilyl group. 3 Organic polymers containing hydrolyzable silicon groups and (
or) the main chain of an organic polymer containing silanol groups is
The curable composition according to claim 1, comprising a polyether having a repeating unit represented by the general formula: -R-O- (wherein R represents an alkylene group having 2 to 4 carbon atoms). 4 Organic polymers containing hydrolyzable silicon groups and (
or) the main chain of an organic polymer containing silanol groups is
The curable composition according to claim 1, which is an acrylic ester polymer or a copolymer of an acrylic ester and at least one of vinyl acetate, acrylonitrile, styrene, and ethylene. 5 Organic polymers containing hydrolyzable silicon groups and (
or) the organic polymer containing a silanol group has a main chain having a repeating unit represented by the general formula: -R-O-, and at least one of polyethers having a hydrolyzable silicon group or a silanol group. The curable composition according to claim 1, which is a polymer or copolymer obtained by polymerizing a vinyl monomer in the presence of a seed. 6. The curable composition according to claim 1, wherein the curable composition is used as a sealant. 7. The curable composition according to claim 1, wherein the curable composition is used as an adhesive.