JPS6031556A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. which gives a cured article having excellent weather resistance and high elongation, comprising a polyether contg. a reactive silicon functional group in the molecule and a (meth)acrylate polymer contg. a reactive silicon functional group at its terminal. CONSTITUTION:A curable compsn. comprises a polyether (A) contg. one or more reactive silicon functional groups per molecule and a (meth)acrylate polymer (B) contg. a reactive silicon functional group at its terminal in a weight ratio of A to B of 100/5-5/100. The use of component B in effective in increasing the space between crosslinked points formed by the reaction of component A with component B during curing, and as a result, a cured article having high elongation can be obtd. Further, a cured article having good weather resistance can be obtd.

Description

[Detailed description of the invention] FIELD OF THE INVENTION This invention relates to modified curable compositions.

More specifically, the present invention relates to a curable composition that exhibits high elongation and weather resistance after curing.

Polyethers having at least one reactive silicone functional group in the molecule are disclosed in, for example, Japanese Patent Publication No. 45-56319, Japanese Patent Publication No. 46-12154, Japanese Patent Publication No. 49-3267!1, Japanese Patent Publication No. 50-156599, Japanese Patent Publication No. 51. -73561, 54-6096, 55-13767, 55
-13768, 55-82123, 55-12
No. 3620, No. 55-125121, No. 55-431
No. 021, No. 55-131022, No. 55-1351
No. 35 and No. 55-137129, and when cured, a cured product with high elongation can be obtained.

However, these polyethers have the following performance drawbacks due to the 174 structure of the main chain. That is, for example, the polymer disclosed in JP-A No. 51-73561 has a urethane bond in the main chain, so it has poor weather resistance, while the polyether having polypropylene oxide as the main chain has If an anti-aging agent is not used, there is a problem that hydrogen atoms bonded to the 6th class carbon are easily oxidized, resulting in poor weather resistance.

In view of the above-mentioned circumstances, the present inventors conducted extensive research in order to improve the weather resistance without reducing the original high elongation properties when the polyether is cured.
) a polyether containing at least one reactive silicone functional group in one molecule; and (B) an acrylate ester polymer and/or a methacrylate ester polymer containing a reactive silicone functional group at the end of the molecule. including;
The weight ratio of m(A) component/(B) component is 10015 to 5/
By using a curable composition of No. 100, it was discovered that the above object could be achieved, and the present invention was completed.

That is, in the present invention, by using (B) #, which has a reactive silicon functional group at the end of the molecule,
Due to the reaction between component (B) and component (N or component (E) a), the distance between the ζG points during curing can be increased, and as a result, a cured product with high elongation can be obtained. By using component (A) with good elongation properties, it is possible to form a cured product with high elongation.Furthermore, component (B) is an acrylic ester polymer and/or methacrylic ester that inherently has good weather resistance. By using component (B), the composition of the present invention can also have good weather resistance when cured.Therefore, the composition of the present invention has a moisture-curable property. It is useful as a sealant or adhesive.

The polyether having at least one reactive silicone functional group in the molecule used as component (A) in the present invention is, for example, Japanese Patent Publication No. 45-56319, No. 46
-12154, No. 49-52675, JP-A-1973-
No. 156599, No. 51-73561, No. 54-6 [
No. 196, No. 55-13767, No. 55-15768
No. 55-82126, No. 55-125620,
No. 55-125121, No. 55-131021, No. 55-161022, No. 55-1! No. 15135,
56-167129 and other publications, the reactive silicon functional group referred to herein refers to a hydrolyzable group bonded to a silicon atom, a hydrolyzable group, and a 2-nol group, which are resistant to moisture. A group that condenses and reacts with additives, typically represented by the general formula (1): (wherein R1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy group) , or a hydroxyl group or a different or similar hydrolyzable group, b
C is an integer of 0.1 or 2, m is an integer of 0 to 18).

Polyethers having such reactive silicon functional groups are, for example, those having the general formula (2): (wherein R1, X, b,
c, m are the same as above) and the general formula (3): % formula % () (wherein 2 is -R-1-ROR-1-ROO-1-RO
-1 divalent hydrocarbon group of 1 to 2G) ・R2 is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, a represents D or an integer of 1) Polyethers having olefin groups are combined with platinum-based compounds such as platinum black, chloroplatinic acid, platinum alcohol compounds, platinum olefin complexes, platinum aldehyde complexes, platinum ketone complexes, etc.
It can be produced by an additional reaction.

A method for producing a polyether having a reactive silicone functional group other than the above includes (1) reacting a hydroxyl group-terminated polyether with a polyisocyanate compound such as toluene diisocyanate to form an isocyanate group-terminated polyether; General formula (4):% formula (4) (wherein, Y is an active hydrogen-containing group selected from a hydrophilic group, a carboxyl group, a mercapto group, and an amino group (primary or secondary), and d is (ii) a method of reacting the Y group of a silicon compound represented by an integer of 0.1 or 2, R1, R, and A method in which a mercapto group' of a silicon compound represented by the general formula (4) in which Y is a mercapto group is subjected to an addition reaction with the hydroxyl group of the hydroxyl group-terminated polyether (general formula: % formula % (in the formula, R1, Specific examples include a method of reacting R, X, (L is the same as above), but the present invention is not limited to these methods.

R1 in the general formula 2) is the same or different monovalent hydrocarbon group having 1 to 2D carbon atoms, and specific examples thereof include alkyl groups such as methyl and ethyl; cycloalkyl groups such as Schiff's hexyl; i phenyl group! l
Aryl groups such as '; examples include aralkyl groups such as bental group. Furthermore, R1 may be a triorganosiloxy group represented by the general formula: % (R' represents the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms). Also, in general formula (2) or silano-
/l' group or a different or similar hydrolyzable group, such as a halogen group, a hydride group, an alkoxy group, an acyloxy group, a ketoximate group, an ami7 group, an amide group, an ami/oxy group. , mercapto group, alkenyloxy group, etc. Specific examples of the hydrogenated silicon compound represented by the general formula (2) include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and trimethylsiloxydichloride.
silane halides such as silane; trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1.3. q, 5.5.7
．． Alkoxysilanes such as 7-hebutamethyl-1,1-dimethoxytetrasiloxane; acyloxysilanes such as methyldiaptoxysilane, trimethyloxymethylacetoxysilane; bis(dimethylketoximate)methylsilane, bis(Schiff Award) xylketoximate) methylsilane, bis(diethylketoxy, mate)
Ketoximate silanes such as trimethylsiloxysilane; hydetetrasilanes such as dimethylsilane, trimethylsiloxymethylsilane, and 1,1-dimethyl-2,2-dimethyldisiloxane; Examples include, but are not limited to, artenyloxysilanes.

In the method of reacting the hydrogenated silicon compound represented by the general formula (2) with the polyether having an olefin group represented by the general formula (3), after reacting them, some or all of the X groups are can be further converted into other hydrolyzable groups or hydroxyl groups. For example, when the X group is a halogen group or a hydride, it is preferable to convert it into an alkoxy group, an acyloxy group, an ami/oxy group, an alkenyloxy group, a hydroxyl group, or the like. In general formula (8), R2 is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom. 2 is carbon number 1-4
0 is preferred, and methylene group is particularly preferred.

As a specific method for producing a polyether having an olefin group represented by the general formula (3), JP-A No. 11? :154-6
Olefin groups can be added to the side chains by the method disclosed in Publication No. 097, or by adding and copolymerizing an epoxy compound containing an olefin group such as allyl glycidyl ether when polymerizing an epoxy compound such as ethylene oxide or privylene oxide. An example is how to introduce

The main chain of the polyether used in the present invention essentially has the general formula: -R3-0- (wherein, R3 is a divalent group, most of which is a carbonized group having 1 to 4 carbon atoms. Hydrogen groups are most preferred). Specific examples of R3 include -0H2-1. The molecular weight of the main chain of the polyether is 500~! +0,000 is preferred, and 6,000 to 15,000 is more preferred.

In the present invention, the acrylic ester polymer and/or methacrylic ester polymer containing a reactive silicone functional group at the molecular end used as component (B) can be produced, for example, by the following method. I can do it.

That is, using a radical/l/polymerization initiator containing a silicon functional group represented by =#≠#= (where R and XSd are the same as above),
(ii) Radical polymerization containing a silicon functional group represented by the general formula (5) e = g! using a transfer agent (meta)
Polymerizing the acrylic acid ester single mouse, (iii) (
(1v) Polymerizing the (meth)acrylic acid ester monomer using the radical polymerization initiator and radical polymerization chain transfer agent used in i) and (ii) together, (1v) carboxyl group, hydroxyl group, hapogen group, amino a radical polymerization initiator containing a functional group (0) such as a group, an epoxy group, and/or
By polymerizing a (meth)acrylic acid ester monomer using a radical polymerization chain transfer agent, a polymer having a functional group (0) at the end of the polymer molecule is produced, and the functional group (0) and tri- A functional group (a''')' is added to the end of the polymer molecule by reacting with a polyfunctional compound such as isocyanate.
;: You may produce a polymer having an isocyanate group, a carboxyl group, a hydroxyl group, a hapogen group, an amino group, an epoxy group, which can react with the functional group (0) or (C');
It has a functional group (D) such as a mercapto group or an acrylic group,
In addition, there is a method in which a silicon compound having a reactive silicon functional group represented by the general formula (5) is reacted with a functional group (0) or (C') at the end of a polymer.

The polymer containing the functional group (C) is, for example, disclosed in Japanese Patent Publication No. 46
-17437, 53-58740, JP-A-53-
It can be specifically manufactured by methods such as those disclosed in Publications No. 64242 and No. 58-69206. Also possible group (C'
), concrete examples include reacting a functional group (0) such as a carboxyl group, a hydroxyl group, or an amino group with a polyisocyanate such as toluene diisocyanate to form a polymer having a functional group (C') having an isocyanate group. Examples include, but are not limited to.

As the radical polymerization initiator containing a silicon functional group represented by the general formula (5), an azo-based or peroxide-based compound can be used.

The azo radical polymerization initiator has the general formula (6
): (In the formula, R1, X, and d are the same as above, and R4 has 2 to 2 carbon atoms.
18 (representing a divalent hydrocarbon group) is preferred, and particularly preferred is the case where X is an alkoxy group such as a methoxy group or an ethoxy group. Specific examples of such azo thread compounds include azobis-2-(6-methylcimethoxysilyl-2-cyanohexane) azobis-2-(6-)rimethoxysilylA/-2-cyanohexane), azobis-2-(6-methylcymethoxysilyl-2-cyanohexane), Examples include, but are not limited to, -(6-methyldiacetoxysilyl/l/-2-cyanohexane).

On the other hand, seven examples of peroxide-based radical polymerization initiators include, but are not limited to, the following.

As a radical polymerization chain transfer agent containing a silicon functional group represented by the general formula (5), the general formula (7)=(in the formula,
R1, x, a are the same as above, R5 is 2 having 1 to 18 carbon atoms
or a compound represented by the general formula (8): (wherein R1, R5, X, and d are the same as above). R5 has 1 to 1 carbon atoms as described above
8 is a divalent hydrocarbon group, and specific examples include groups such as methylene, ethylene, propylene, butylene, hexylene, phenylene, and cyclohexylene. R
, d, and X are the same as above, but alkoxy groups such as methoxy and ethoxy groups are particularly preferred from the viewpoint of ease of handling. Specific examples of the compound represented by the general formula (7) or (8) include (CH6
0)3S10H20I(2CH2S1(,C(an3o
)3s1aa2aH2an2s -':12, but is not limited thereto.

In the present invention, the acrylic ester polymer and/or methacrylic ester polymer used as the (n)+A component may be each polymer alone or may be a blend thereof. Alternatively, it may be a polymer obtained by polymerizing two or more types of acrylic acid alkyl ester or methacrylic acid alkyl ester. The alkyl group may be a branched alkyl group or an unbranched alkyl group. Specific examples of alkyl groups include methyl, ethyl, h-butyl, isobutyl, 1-ethylpropyl, 1-methylpentyl,
2-methylpentyl, 6-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, isooctyl, 3,5.5
-) Limethylbexyl, 2-ethylhexyl, Denru,
Examples include alkyl groups such as dodecyl.

In the present invention, acrylic acid alkyl ester and (
or) Approximately 50% of methacrylic 6☆ alkyl ester (
% by weight, hereinafter the same) may be replaced with other copolymerizable unsaturated monomers. Examples of unsaturated single ft1 bodies that can be substituted include styrenes such as styrene, α-methylstyrene, vinyltoluene, and 2-chlorostyrene; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, and 2-ethylhexyl vinyl ether.9. t4
i Acrylic acid, methacrylic acid, 2-human tetraxyethyl acrylate, 2-human tetragyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, l
tomethylaminoethyl acrylate, acrylamide,
Acrylic hexagonal compounds or methacrylic acid compounds containing functional groups such as carboxyl, hydroxyl, epoxy, amino, and amide groups such as N-methylol acrylamide; polyethylene glycol diacrylate, polyethylene glycol dimethacrylate , polypropylene glycol diacrylate, polypropylene glycol methacrylate, trimethy4-propane triacrylate, trimethylolpropane trimethacrylate, oligoester acrylate, methylene bisacrylamide, diallyl phthalate, etc. in one molecule. unsaturated monohydrogens containing two or more of; Vinyl monomers having 2 to 60 carbon atoms such as prene; vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldimethoxysilane, γ
- methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane Contains a reactive silicone functional group represented by the general formula (5) such as roxypropyltriethoxysilane, γ-acryloquinebrobylmethyldimethoxysilane, γ-acryloxypropylmethyldiethoxysilane, etc., and Examples include, but are not limited to, monomers containing polymerizable unsaturated groups.

It is preferable that one molecule of the polymer used as the component (J3) used in the present invention contains 0.1 to 3.5 reactive silicon functional groups on average, and contains 0.1 to 6.0 O,S. It is further preferable that the

In the curable composition of the present invention, the (A) component/(B) component can be used in a weight ratio of 10015 to 5/100, but the (N component/ω) component can be used in a weight ratio of 1071 to 1/10. It is more preferable to do so.

When the curable elastomer composition of the present invention is used as a sealant, plasticizers, fillers, reinforcing agents, anti-sagging agents, colorants, anti-aging agents, adhesion promoters, curing catalysts,
A physical property adjusting agent or the like may be added.

As plasticizers, dibutyl slate, diallyl phthalate, di(2-
7-talic acid esters such as ethylhexyl) phthalate, butylbenzyl phthalate, and butyl 7thalylbutyl glycolate; Non-aromatic dibasic esters such as dioctyl adipate and dioctyl sebacate; diethylene glycol dipenzoate and triethylene glycol dibenzoate Polyalkylene glycol esters such as; phosphoric acid esters such as tritalesyl phosphate and tributyl phosphate; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl, etc. alone or in combination of two or more. can be used, but is not required. Note that these plasticizers can also be blended during polymer production.

As fillers and reinforcing materials, heavy and light calcium carbonate; calcium carbonate surface-treated with fatty acids, resin acids, cationic surfactants, anionic surfactants, etc.; magnesium carbonate; talc; titanium oxide; sulfuric acid. Barium; alumina; metal powders such as aluminum, zinc, and iron; bentonite; kaolin clay; silica; quartz powder;
One or more kinds of ordinary materials such as carbon black may be used. In particular, it is possible to create a sealing material with excellent transparency by using fillers and reinforcing materials that provide transparency, such as fumed silica.

Examples of anti-sagging agents include hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate; however, depending on the purpose of use or the formulation of reinforcing materials for fillers, etc., they may not be necessary. Pigments, dyes, etc. can be used.

Various silane coupling agents such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethodisilane, and tonoalkylalkoxysilanes such as n-propyltrimethoxysilane; Alkylisopropenoxysilanes such as penoxysilane, γ-glycidoxypropylmethyldiisoprepenoxysilane; r-glycidoxyp4pylmethyldimethoxysilane, r-glycidoxyp4pyltrimethoxysilane, vinyltrimethoxysilane, Vinyldimethylmethoxysilane, r-aminopropyltrimethoxysilane 1H-(β
-aminoethyl)aminopropylmethyldimethoxysilane, r-mercaptopropyltrimethoxysilane, γ-
Sulfalkoxysilanes with functional groups such as mercaptopropylmethyldimethoxysilane; silicone faces;
Polysiloxanes and the like are added as necessary. By using the physical property adjusting agent, 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 the elongation. It has adhesive properties to other ceramics, metals, etc., and can be bonded to a wide range of materials by using various primers, so it is not necessary, but epoxy resins, phenolic resins, various silane couplings etc. By using one or more types of agents, alkyl titanates, aromatic polyisocyanates, etc., it is possible to provide adhesive properties to even more types of adherends.

As a curing catalyst, titanate esters such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as diptyltin dilaurate, diptyltin maleate, dibutyltin diacetate, tin octylate, and tin naphthenate; lead octylate; butylamine, octylamine,
Dibutylamine, monoethanolamine, jetanolamine, triethanolamine, diethylenetriamine, triethylenetetamine, oleylamine, octylamine, Schifta hexylamine, benzylamine, diethylamine, xylylenediamine, triethylenediamine, Guanidine, diphenylguanidine, 2,4.6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 1.3-
Diazabicyclo(s t < + 6> undecene-7
Amine compounds such as (DBU) or their salts such as carboxylic acids; Low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; Reaction products of excess polyamines and epoxy compounds; Silane coupling with amino groups If necessary, one or more known silanol condensation catalysts such as r-aminopropyltrimethoxysilane and N + (β-amino/ethyl)amitubucypylmethyldimethoxysilane may be used.

In addition, solvents may be added for the purpose of improving workability and reducing viscosity. Examples include ester solvents, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. These solvents may be used during polymer production.

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

Such a sealant composition may be prepared as a one-component type in which all ingredients are mixed in advance, sealed and stored, and cured by moisture in the air after loosening.Additionally, a curing catalyst, filler, and plasticizer may be added as a curing agent. It can also be prepared as a two-component type, in which components such as , water, etc. are blended in advance, and the blending agents (materials) and the polymer composition are mixed 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 depressurization etc. during blending. is preferable.

When the sealant composition is a two-component type, there is no need to mix a curing catalyst with the main component containing a polymer, so there is little worry about gelation even if the compound contains some water. If long-term storage stability is required, dehydration and drying are preferred. As a method for dehydrating and drying, suitable methods include heat drying in the case of solid materials such as powder, and vacuum dehydration in the case of liquid materials, or dehydration methods using synthetic zeolite, activated alumina, silica gel, etc. Alternatively, dehydration may be carried out by adding a small amount of an isocyanate compound and causing the isocyanate group to react with water. In addition to such dehydration drying methods, lower alcohols such as methanol and ethanol, n-propyltrimethoxysilane, vinylmethyldimethoxysilane, r-mercapdobutetravirmethyldimethoxysilane, r-mercapdobutetravirmethyldimethoxysilane, r-glycidoxypro Storage stability is further improved by adding an alfukidisilane compound such as biltrimethoxysilane.

When the composition of the present invention is used as an adhesive, the curing catalyst, anti-aging agent, plasticizer, reinforcing agent, physical property opening agent, solvent, etc. used in the sealing material may be used as necessary. Further, depending on the purpose, known additives added to ordinary pressure-sensitive adhesive compositions such as phenol resin, xylene resin, coumaron resin, petroleum resin, terpene resin, and terpene phenol resin may be blended. The adhesive composition can be widely applied to tapes, sheets, labels, foils, etc. This means that substrate materials such as, for example, films made of synthetic resins or modified natural products, paper, fabrics of all kinds, metal foils, metallized plastic foils, asbestos or glass fiber fabrics are coated with solvent-borne, emulsion-type or hot-melt types. The pressure-sensitive adhesive composition may be applied in a form, 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, waterproofing 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.

Reference example 1 The components shown in Table 1 were mixed, stirred, and uniformly dissolved.

The mixture 259 was placed in a 20 Qm 14-bottle flask equipped with a stirrer and a condenser and purged with dry nitrogen gas, and heated to 8,000 ℃ in an oil bath while passing nitrogen gas. After a few minutes, polymerization started and generated heat, but after the heat generation became mild, the remaining mixed solution was gradually added dropwise using a dropping funnel to cause polymerization. It took 6 hours to complete the dropping. The reaction was terminated when no heat generation was observed, and the polymer was removed.

The obtained polymer had a viscosity of 490F and was used in the gel vermiculum 7 (GPO) analysis method.
:The average molecular fi was 6000. The number of reactive silicone functional groups contained in one molecule of the composition was 2.4 on average, which was determined by calculation from the average molecular weight and the charged amount of the material containing reactive silicone functional groups.

Reference Examples 2 to 5 Polymers of Reference Examples 2 to 5 were prepared in the same manner as Reference Example 1 using the components shown in Table 1, and the average molecular weight and number of reactive silicon functional groups were determined. The results are shown in Table 1.

Note that aat-1 in Table 1 is Reference Example 6. 60 g of the polymer obtained in Reference Example 5 was charged into a flask with a stirrer, and then 1.29 g of the polymer obtained in Reference Example 5 was added, followed by 1.29 g of the polymer obtained in Reference Example 5, and 1.29 g of the polymer obtained in Reference Example 5. 19
was added and reacted at 100°0 for 5 hours with stirring under a flow of carbon gas. A reaction between the carboxyl groups at the end of the polymer and the isocyanate occurred, yielding a polymer with trimethoxysilyl functional groups.

The obtained polymer had an average number of reactive silicone functional groups contained in one molecule of the composition, which was determined by calculation from the average molecular weight and the amount of the reactive silicone functional group-containing material.

Reference example 7 Polypropylene glycol 3 with average molecular weight ff 13000
00g into a flask with a stirrer, and then 26g of toluene diisocyanate and diptyltin dilaure) 0.
29 was added thereto, and the mixture was reacted at 100°C for 5 hours with stirring under a nitrogen gas flow. After that, add γ-aminopropylmethyldimethoxysilane 16.3G+ and
The average molecular weight was approximately 6,500.
A polymer having a methyldimethoxysilyl group at the end was obtained.

Examples 1 to 5 Silyl group-terminated polybutyl-p-pyrene oxide, in which 80% of all terminals are reactive silicon functional groups, was mixed with the acrylate polymer obtained in Reference Examples 1 to 4.6 in the proportions shown in Table 2. .

To 100 g of the mixture, 2 Ijg of dioctyl phthalate, 209 g of rutile-type titane oxide, and 1 g of fatty acid-treated calcium carbonate were added.
00g and 0.6g of styrenated phenol were added and mixed using three paint rolls to prepare a paste. After adding 2 g of dibutyltin dilaure and 1 g of laurylamine to the obtained paste and mixing well, the paste was made to a depth of 6 mm.
The mixture was poured into a mold and cured in a dryer at 26°C x 55% RHX for 7 days and then at 50°OX for 7 days to produce a cured sheet.

From the resulting cured sheet, punch out No. 6 dumbbells specified by J-Koku 5K6601, and use an autograph at a tensile speed of 500 mm.
A tensile test was conducted under the Z force, and the elongation at break and the strength at break were measured. Further, this cured sheet was exposed to a Sunshine Weather-O-meter, and the state of deterioration of the sheet surface was observed to measure weather resistance. The results are shown in Table 2.

In addition, weather resistance is evaluated with the naked eye, and if there is no abnormality, it is evaluated as 0.
If there was an arc crack to 1, it was judged as △, and if there was a large rack, it was judged as A cured sheet was produced in the same manner as in Example 1 using the following, and its properties were evaluated. The results are shown in Table 2.

As shown in Table 2, by mixing polypropylene oxide containing a silyl group with an acrylic polymer containing a silyl functional group at the end to prepare a curable composition, high elongation at break and It can be seen that a curable composition with improved weather resistance while maintaining strength can be used.

Example 6 A cured sheet was produced in exactly the same manner as in Example 4, except that the polymer of Reference Example 7 was used instead of the silyl group-terminated polypropylene oxide, and the same as in Example 1. The characteristics were evaluated. As a result, the elongation at break was 460%, and the breaking strength was 9.4 kg/cm2, indicating high breaking strength, and the weather resistance was good with no abnormalities after 1000 hours and only a slight hair crack after 1500 hours. It had unique characteristics.

Example 7 A solution in which 10 g of the polymer of Reference Example 1 was blended with 10 g of the silyl group-terminated polypyrene oxide used in Example 1, and further terpene 7 ether resin 109 with a softening point of 115% and toluene IJ+ were added. was prepared.

Add 0.5 g of dibutyltin maleii) to the resulting solution,
It was applied to a polyester film and dried and cured for 16,000 x 10 minutes to produce an adhesive tape with an adhesive thickness of 60 μm.The adhesive strength of the resulting tape was determined by IX8021Q7-
As a result of measurement at 20°C according to 611, the adhesive strength was 58
It was 0g/19mm.

The above results show that the composition of the present invention is useful as an adhesive.

Claims (1)

[Scope of Claims] 1(A) a polyether containing at least one reactive silicone functional group in one molecule; and CB) an acrylic acid ester polymer containing a reactive silicone functional group at the end of the molecule; or) contains a methacrylate ester polymer, and the weight ratio of component (A)/component (B) is 1001.
A curable composition having a hardness of 5 to 5/100. 2. The composition according to claim 1, wherein the reactive silicon functional group is an alkoxysilyl group.