JPH0456066B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a modified curable composition, and particularly to a curable composition having excellent adhesiveness and weather resistance. Polyethers having at least one reactive silicone functional group in the molecule are disclosed, for example, in
36319, 46-12154, 49-32673, JP-A-1987-
156599, 51-73561, 54-6096, 55-
82123, 55-123620, 55-125121, 55-
131022, 55-135135, 55-137129, etc. All of these organic polymers have performance weaknesses due to their main chain structures and the like. For example, the polymer proposed in JP-A-51-73561 has urethane bonds in the main chain and at the ends, resulting in poor weather resistance. Also, JP-A-50-156599
The proposed polymer has insufficient adhesion to various adherends, and since the main chain is polyether, there is a problem in weather resistance due to hydrogen atoms bonded to tertiary carbon. The present inventor completed the present invention as a result of intensive research to improve the drawbacks of these polymers. That is, the present invention provides (A) 100 parts by weight of polyether containing at least one reactive silicone functional group in one molecule, and (B) at least one reactive silicone functional group in one molecule. Vinyl polymer with 0.1~
The content is a curable composition containing 1000 parts by weight. The polyether having at least one reactive silicone functional group in the molecule used in the present invention is
32673, JP 50-156599, JP 51-73561, JP 54-
6096, 55-82123, 55-123620, 55-
125121, 55-131022, 55-135135, 55-
137129, etc. The reactive silicon functional groups referred to here are those that condense and react with moisture and additives, such as hydrolyzable groups and silanol groups bonded to silicon atoms, and are typically represented by the following general formula ( 1). (In the formula, R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy group, X is a hydroxyl group or a different or similar hydrolyzable group, b is 0, (c is an integer of 0, 1 or 2, m is an integer of 0 to 18). A hydrogenated silicon compound represented by the formula [In the formula, Z is -R-, -ROR-,

【formula】

【formula】

[Formula] or

[Formula] (R ¹⁰ is the same or different type of divalent carbon hydrogen group having 1 to 20 carbon atoms), a is an integer of 0 or 1] A polyether having an olefin group represented by It can be produced by addition reaction using a platinum-based compound such as an acid, a platinum alcohol compound, a platinum olefin complex, a platinum aldehyde complex, or a platinum ketone complex as a catalyst. In formula (2), R ⁶ is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms, such as an alkyl group such as methyl or ethyl; a cycloalkyl group such as cyclohexyl; an aryl group such as phenyl group; benzyl selected from aralkyl groups such _as
It also includes a triorganosiloxy group represented by SiO- (R' is the same or different group having 1 to 20 carbon atoms).
(indicates a valent hydrocarbon group). Also, in formula (2),
represents a silanol group or a different or similar hydrolyzable group; however, halogen group, hydride group, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, aminooxy group,
Examples include mercapto group and alkenyloxy group. Specific examples of the hydrogenated silicon compound represented by formula (2) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane,
Alkoxysilanes such as methyldimethoxysilane, phenyldimethoxysilane, 1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane; methyldiacetoxysilane, trimethylsiloxymethylacetoxysilane, etc. Acyloxysilanes; Ketoximate silanes such as bis(dimethylketoximate)methylsilane, bis(cyclohexylketoximate)methylsilane, bis(diethylketoximate)trimethylsiloxysilane; dimethylsilane,
Examples include hydrosilanes such as trimethylsiloxymethylsilane and 1,1-dimethyl-2,2-dimethyldisiloxane; alkenyloxysilanes such as methyltri(isopropenyloxy)silane, but are not limited to these. do not have. In this method, after reacting the hydrogenated silicon compound of formula (2) with the polyether having an olefin group of formula (3), some or all of the X groups are further replaced with other hydrolyzable groups or Can be converted to hydroxyl group. For example, when the X group is a halogen group or a hydride group, it is preferably converted into an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group, a hydroxyl group, or the like. In formula (3), R ¹⁰ is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom. Z is the same or different divalent organic group having 1 to 20 carbon atoms, preferably a hydrocarbon group and a hydrocarbon group containing an ether bond, an ester bond, a urethane bond, or a carbonate bond. A methylene group is particularly preferred.
A specific method for producing polyether having an olefin group represented by formula (3) is the method proposed in JP-A-54-6097, or the method in which allyl Examples include a method of introducing an olefin group into the side chain by adding and copolymerizing an olefin group-containing epoxy compound such as glycidyl ether. The main chain of the polyether used in the present invention essentially has the formula -R ⁵ -O- (where R ⁵ is a divalent organic group, most of which is a hydrocarbon group having 1 to 4 carbon atoms). Those having chemically bonded repeating units as shown in (most effective when) are preferred.
Specifically, R ⁵ is −CH ₂ −, −CH ₂ CH ₂ −,

【formula】

【formula】

[Formula] -CH ₂ CH ₂ CH ₂ CH ₂ - and the like. Polyethers may consist of only one type of repeating unit, or polyethers consisting of two or more types of repeating units are also effectively used. especially

[Formula] is preferred. Polyether with a molecular weight of 500 to 30,000 can be effectively used, but
Preferably, it has a molecular weight of 3,000 to 15,000. Such polyether is disclosed in Japanese Patent Application Laid-Open No.
No. 129247 and JP-A-54-6097. The polymerizable monomer used in the production of component (B) used in the present invention has the general formula (In the formula, R ¹ is a hydrogen atom, a halogen atom, or
A group selected from substituted or unsubstituted monovalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms, R ² is the same group as R ¹ , substituted or unsubstituted monovalent aromatic hydrocarbon group, alkenyl A vinyl monomer represented by a monovalent organic group having 1 to 20 carbon atoms selected from a carboxyl group, an acyloxy group, an alkoxycarbonyl group, a nitrile group, a pyridyl group, an amide group, a glycidoxy group, etc. , and general formula (In the formula, R ³ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, R ⁴ is an organic residue having a polymerizable double bond,
(n is an integer of 1, 2, or 3) It can be produced by copolymerizing one or more vinyl silicon compounds represented by the following formulas. Examples of the vinyl monomer represented by formula (4) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. , acrylic acid, methacrylic acid esters such as benzyl acrylate and benzyl methacrylate; acrylic acid,
Carboxylic acids such as methacrylic acid, itaconic acid, and fumaric acid and acid anhydrides such as maleic anhydride; Epoxy compounds such as glycidyl acrylate and glycidyl methacrylate; Amino compounds such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and aminoethyl vinyl ether. ; Acrylamide, methacrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl acrylamide, N
-Amide compounds such as butoxymethylmethacrylamide; 2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyvinyl ether, N-methylol acrylamide, Aronix
Vinyl compounds containing hydroxyl groups such as 5700 (manufactured by Toagosei Co., Ltd.); acrylonitrile, iminol methacrylate, styrene, α-methylstyrene, chlorstyrene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, vinylpyridine, Examples include butadiene, chloropyrene, isobutylene, propylene, ethylene and the like. In particular, when the cured product requires rubber elasticity, it is preferable to use acrylic esters in an amount of 50% by weight or more. Specifically, the silicon compound represented by formula (5) is:

【formula】

【formula】

[Formula] CH ₂ = CHSi(OCH ₃ ) ₃ , CH ₂ = CHSi(OCH ₂ CH ₃ ) ₃ , CH ₂ = CHSiCl ₃ ,

【formula】

Examples include, but especially

[Formula] is preferred. In addition to these, for example, silicon atoms can be
A polysiloxane compound having 30 atoms or the like can be used, as long as it has a C═C bond and a silicon atom bonded to a hydrolyzable group. These vinyl monomers and silicon compounds can be selected according to the desired quality improvement. For example, when the purpose is to improve weather resistance, ethyl acrylate, isobutyl acrylate, methyl methacrylate, etc.

So-called acrylic monomers such as [Formula] are preferable, and when the purpose is to improve adhesion, acrylamide, epoxy group-containing monomers, 2-ethylhexyl acrylate, etc.

[Formula] etc. are preferred. The vinyl monomers may be used alone or in combination of two or more.
Also, like component A, a vinyl monomer may be polymerized in advance so that an olefin group remains on the side chain or at the end, and then reacted with a silicon compound. general formula

The silicon compound represented by [Formula] is 0.001 to 50% by weight based on the vinyl monomer.
However, when used for rubber-based applications, it is preferably used in a range of 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight. Polymerization can be carried out by conventional methods, specifically methods using radical initiators, ultraviolet rays,
Methods using radiation, gamma rays, irradiation, etc. can be adopted. Specifically, as a radical initiator, benzoylper
peroxides such as benzoyl hydroperoxide, di-t-butyl peroxide, di-t-butyl hydroperoxide, acetyl peroxide, lauroyl peroxide, hydrogen peroxide, etc.; Examples include azo compounds such as nitriles; persulfates, peroxide compounds such as di-isopropyl peroxy-dicarbonate, and the like. A solvent can be used if necessary. When used, it is preferable to use a solvent that is inert to both polyether and vinyl monomers having a reactive silicone functional group, and specific examples include ethers, hydrocarbons, acetic esters, etc. . The polymerization temperature is not particularly limited, and in the case of a polymerization method and a method using a radical initiator, the optimum temperature can be set depending on the type of initiator used, but it is usually preferably carried out at 50 to 150°C. Also, if necessary, mercaptans (such as mercaptans containing silicone functional groups)
It is also possible to control the degree of polymerization of the vinyl monomer by using a chain transfer agent such as a halogen-containing compound or a halogen-containing compound. The vinyl monomer may be charged in its entirety at once, but it is also possible to charge it in portions or continuously for the purpose of adjusting the calorific value. Examples of manufacturing such linear vinyl random copolymers of component (B) are disclosed in JP-A-54-36395, JP-A-54-123192,
It is presented in 57-179210 etc. In curing the composition of the present invention, a curing catalyst may or may not be used, but when used, metal carboxylates such as dibutyltin dilaurate, dibutyltin phthalate, tin octylate, and titanium naphthenate; butyl titanate,
Examples include titanate esters such as tetraisopropyl titanate and triethanolamine titanate; amines, ammonium salts, and the like. These may be used alone or in combination. The compositions of the present invention may further contain various fillers, plasticizers,
It may contain additives and the like. As the filler, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, kaolin, talc, silica, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, carbon black, etc. are used. As the plasticizer, dioctyl phthalate, butyl benzyl phthalate, chlorinated paraffin, epoxidized soybean oil, and others are used. As additives, hydrogenated castor oil, anti-sag agents such as organic bentonite, coloring agents, anti-aging agents, etc. are used. The composition thus obtained can be usefully used as an adhesive, a pressure-sensitive adhesive, a paint, a sealant composition, a molding material, a casting rubber material, a foaming material, and the like. For example, when applied as a sealant, kneading the above curing catalyst and compound in a moisture-free state and storing it in a sealed state will provide long-term stability, and will cure quickly when exposed to moisture in the air. A one-component elastic sealing material that provides a good rubber elastic body is obtained, and the material exhibits good adhesion to various adherends and good weather resistance. The present invention will be specifically explained below with reference to examples. Reference example: 30 parts by weight of styrene, 2 parts by weight of N-methylolacrylamide, 20 parts by weight of γ-methacryloxypropyltrimethoxysilane, methyl methacrylate
37 parts by weight, 11 parts by weight of n-butyl acrylate, 100 parts by weight of xylene as a solvent, 2 parts by weight of azobisisobutyronitrile as an initiator, 2 parts by weight of n-dodecylmercaptan as a chain transfer agent at 80°C for 10 hours. Polymerized vinyl copolymer with an average molecular weight of 8000 containing hydrolyzable silyl groups in the side chain [(B)
component] was obtained. Examples 1 to 3 80% of all ends

[Formula] Polyoxypropylene with an average molecular weight of 8200 as a group, calcium carbonate, titanium oxide, dioctyl phthalate, hydrogenated castor oil, styrenated phenol as an anti-aging agent, dibutyltin dilaurate as a curing catalyst, and a reference example. The obtained copolymer was sufficiently kneaded in the predetermined amount shown in Table 1 in the absence of moisture to create a blend, and then cured on each adherend shown in Table 2 (20°C After 7 days), an adhesion test was conducted. Table 3 shows the weather resistance (a 3 mm thick sheet was cured at 23° C. for 14 days and then exposed using a Suga Test Instruments Super Long Life Sunshine Weatherometer).

【table】

[Table] * All numbers are parts by weight ** Copolymer obtained in reference example, component (B).

【table】 (
(× Adhesive surface between cured product and adherend (
(La, peel off.

[Table] Example 4 50g of an aromatic hydrocarbon solvent (trade name: Hysol 292, manufactured by Nippon Petrochemical Industries, Ltd.) was charged in advance into a reaction vessel, heated to 90°C, and then 10g of styrene, A mixed solution consisting of 20 g of n-butyl acrylate, 10 g of methyl methacrylate, 7 g of γ-methacryloxypropyltrimethoxysilane, and 3 g of azobisisobutyronitrile is added dropwise over 2 hours. 40 g of the resulting 50% by weight solution of vinyl polymer containing silicon functional groups in its side chains
80% of all terminals

[Formula] Mixed with 100 g of reactive silicone-terminated polyoxypropylene with an average molecular weight of 8200, fatty acid-treated colloidal calcium carbonate 140 g, ground calcium carbonate 30 g, titanium oxide 15 g, dioctyl lactate 70 g, water-added castor oil 6 g , oligoester acrylate (product name: Aronix M8060 manufactured by Toagosei Kagaku Co., Ltd.) 5
g, 1 g of styrenated phenol, 1 g of benzotriazole ultraviolet absorber, 3 g of tin octylate, and 1 g of laurylamine were added, passed through 3 paint rolls 3 times, and thoroughly kneaded to make a sheet approximately 3 mm thick, and heated at 23°C. After curing at 50% RH for 7 days, followed by 7 days at 50°C, the samples were placed in a sunshine weatherometer. In the cured product using only reactive silicone-terminated polyoxypropylene, cracks appeared on the surface after 1000 hours, but no abnormality was observed in the cured product sheet of this example even after 2000 hours. Example 5 100 g of a solution consisting of 94 g of n-butyl acrylate, 2 g of γ-methacryloxypropyldimethoxysilane, and 5 g of azobisisobutyronitrile
Prepare 30 g of 80 g and put 30 g into the reaction vessel.
Incubate for approximately 30 minutes at °C. The remaining 70 g of the solution was added dropwise into the resulting viscous liquid over 3 hours. 50g of the obtained polymer containing hydrolyzable silyl groups in the side chain was

[Formula] Mix with 50 g of reactive silicone-terminated polyoxypropylene with an average molecular weight of 8200, fatty acid-treated colloidal calcium carbonate 120 g, titanium oxide 30 g, dioctyl phthalate 60 g, hydrogenated castor oil 6 g, oligoester acrylate (product Name: Aronix M8060 (manufactured by Toagosei Kagaku Co., Ltd.) 5g, styrenated phenol 1g as an anti-aging agent, 1g benzotriazole ultraviolet absorber, 3 tin octylate as a curing catalyst
After thoroughly kneading 1 g of laurylamine through three paint rolls three times, a type 2 H-type test piece specified in JIS-A-5758 was prepared using glass as an adherend, and after standard curing. , a tensile test was conducted. 150% modulus; 2.8Kg/cm ² , strength at break;
It exhibited tensile properties of 4.2Kg/cm ² and elongation at break of 350%. In addition, a sheet approximately 3 mm thick was prepared from the same composition, and after standard curing, it was applied to a Sunshine Weatherometer. The cured product using only reactive silicone-terminated polyoxypropylene cracked after 1000 hours, but the cured product sheet of this example showed cracks after 1500 hours.
No abnormality was observed even after the passage of time. Example 6 50 g of a random copolymer of isobunalene and norbutylene (trade name: Idemitsu Polybutene OR: manufactured by Idemitsu Petrochemical Co., Ltd.) was placed in a reaction vessel in advance and heated to 90°C, and then 5 g of styrene was added. 15g n-butyl acrylate, 68g methyl methacrylate
A mixed solution consisting of 23 g of γ-methacryloxypropyltrimethoxysilane, 1 g of acrylamide and 1 g of azobisisobutyronitrile was added dropwise over 6 hours. 72 g of the obtained solution of vinyl polymer containing silicon functional groups in the side chain and polybutene OR was mixed with 80% of all terminals.

[Formula] 100g of reactive silicone-terminated polyoxypropylene with an average molecular weight of 8200 is mixed with fatty acid-treated colloidal calcium carbonate 100g, heavy calcium carbonate 80g, titanium oxide 40g, dioctyl phthalate 70g, oligoester acrylate (product name: Aronix M8060
7.5g styrenated phenol (manufactured by Toagosei Kagaku Co., Ltd.)
1.5g, benzotriazole UV absorber 1.5g
g, 4.5 g of tin octylate and 1.5 g of laurylamine were added, passed through a 3-pane roll three times, and thoroughly kneaded to form a sheet approximately 3 mm thick. After curing for 7 days, it was run on a Sunshine Weatherometer. The cured product using only reactive silicone-terminated polyoxypropylene had cracks on the surface after 1000 hours, but the cured product sheet of this example showed no abnormalities even after 2000 hours. Example 7 35g of dioctyl phthalate was placed in a reaction vessel and heated to 90°C, then styrene was added.
A mixed solution consisting of 15 g of n-butyl acrylate, 20 g of methyl methacrylate, 19 g of γ-methacryloxypropyltrimethoxysilane, 1 g of acrylamide and 5 g of azobisisobutyronitrile was added dropwise over 6 hours. 65.2 g of the obtained solution of vinyl polymer containing silicon functional groups in the side chain and dioctyl phthalate was mixed with 80% of the total terminals.
but Mixed with 50 g of reactive silicone-terminated polyoxypropylene with an average molecular weight of 8200 as a base, fatty acid-treated colloidal calcium carbonate 120 g, titanium oxide 30 g, dioctyl phthalate 45 g, water-added castor oil 6 g, oligoester acrylate (product name: Aronix)
M8060 (manufactured by Toagosei Kagaku Co., Ltd.) 5g, styrenated phenol 1g, benzotriazole ultraviolet absorber 1g, tin octylate 3g, laurylamine 1g
After thoroughly kneading and passing through 3 paint rolls 3 times, a sheet with a thickness of about 3 mm was created and heated at 23℃/50%RH.
After curing for 7 days at 50°C, the samples were placed in a sunshine weatherometer. Although the cured product using only reactive silicone-terminated polyoxypropylene had cracks on the surface after 1000 hours, no abnormality was observed in the cured product sheet of the present invention example even after 2000 hours. Example 8 The polyoxypropylene used in Examples 1 to 3, the compounding agents, and the vinyl copolymer obtained in the reference example were sufficiently kneaded in the predetermined amounts shown in Table 4 in the absence of moisture. A formulation was prepared.

[Table] This compound was cast as a sheet with a thickness of 2 to 3 mm, cured for 2 days at room temperature and 3 days in a constant temperature bath at 50°C, and then subjected to a tensile test. The results are shown in Table 4 and FIG. The test conditions were a JIS B No. 3 dumbbell, a tensile speed of 200 mm/min, and a temperature of 23°C. As is clear from FIG. 1, it can be seen that the composition of the present invention exhibits performance close to the performance on the additivity straight line connecting the performance when vinyl polymer and polyoxypropylene are used alone. . In general, in a mixed system of different polymers, the performance is usually far inferior to that on the additivity line, so it is clear that the composition of the present invention has excellent performance. This is presumed to be because both of the two types of polymers used in the present invention have reactive silicon functional groups. Comparative Example A polyether urethane prepolymer with an isocyanate content of 2.0% by weight using polyoxypropylene with an average molecular weight of 3000, compounding agents, and the vinyl copolymer obtained in the reference example were hydrated in the specified amounts as shown in Table 5. A formulation using polyether urethane was prepared by sufficiently kneading in the absence of polyether urethane to convert it to a polyether having reactive silicone functionality. This formulation was cured under the same conditions as in Example 8 and subjected to a tensile test. The results are also shown in Table 5. As is clear from the experiments in Table 5, compared to the case where only polyether urethane was cured as the polymer, when 50% by weight was made of vinyl copolymer, the breaking strength and elongation at break were 22% of the predicted values, respectively. %
(Predicted value is 8.1Kg/cm ² , actual value is 1.8Kg/cm ² ), 35%
(The predicted value was 176%, the actual value was 62%). On the other hand, in the case of Example 8, the corresponding predicted values were 95% (predicted value was 4.3 Kg/cm ² , actual measured value was 95%).
4.1Kg/cm ² ), 78% (predicted value is 276% actual value is 220
%), and it is clear that the deviation from the predicted value is small in the composition of the present invention, and the degree of deterioration of the tensile properties is small. In the above case, the predicted value is calculated using the arithmetic average of the value for polyether alone and the value for vinyl polymer alone. In Table 5, all numerical values indicating the blending amount are parts by weight, and the random copolymer is the copolymer obtained in the reference example, component (B).

【table】

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a diagram showing the performance of the composition of the present invention.

Claims (1)

[Claims] 1 (A) 100 parts by weight of polyether containing at least one reactive silicone functional group in one molecule, (B) at least one reactive silicone in one molecule A curable composition containing 0.1 to 1000 parts by weight of a vinyl polymer having a functional group. 2 The vinyl polymer has the general formula [Formula] (where R ¹ is hydrogen, halogen, or has a carbon number of 1
~10 substituted or unsubstituted hydrocarbon groups, ^R2 is a monovalent organic group having 1 to 20 carbon atoms that is the same as or different from ^R1 ), and a carbon-carbon double bond. The composition according to claim 1, which is a polymer that can be produced by copolymerization with a silicon compound containing a hydrolyzable group. 3 The main chain of the polyether essentially has the formula -R ⁵
The curable composition according to claim 1, which is an oxyalkylene polymer consisting of -O- ( ^R5 is a divalent alkylene group having 1 to 4 carbon atoms) and having a molecular weight of 500 to 30,000. 4 The vinyl monomer has the formula, (In the formula, R ¹ is the same as above, R ⁷ has 1 to 20 carbon atoms.
3. The curable composition according to claim 2, wherein the curable composition is a substituted or unsubstituted monovalent organic group. 5 The silicon compound has the general formula, (In the formula, R ³ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, R ⁴ is an organic residue having a polymerizable double bond,
3. The composition according to claim 2, wherein X is a hydrolyzable group and n is an integer of 1, 2, or 3.