JPS6236066B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a primer composition for an acrylic modified urethane sealant. In recent years, with the remarkable progress in technology and diversification of needs in the construction industry, the Japanese Industrial Standard JISA5758-1979 regarding architectural sealants has been revised, and five types of durability classifications have been defined: 9030, 8020, 7020, 7010, and 7005. Polyurethane sealant also
It is now possible to apply 9030 as a durable sealant. However, conventional polyurethane sealants have poor heat resistance, and in reality, acrylic-modified polyurethane sealants are the most effective.
It can be said that it complies with the durability classification of JISA5758-1979. Although the acrylic modified urethane sealant has various advantages and is therefore in practical use, the present inventor believes that, although the acrylic modified urethane sealant has various advantages and is therefore in practical use, the primer used when applying the sealant is of the same quality as the sealant. The present invention was developed based on the realization that acrylic-modified urethane resins are being used in a conventional manner, and are not necessarily used in a way that immediately meets the needs of customers. In other words, it is generally considered appropriate to use a primer for sealants that is similar to the sealant, taking into consideration its adhesion to the sealant.
When it is decided to mix urethane resin as a primer, the target material can be used within a limited range of conditions that do not expose the general drawbacks of urethane resins, such as poor heat resistance and susceptibility to photodeterioration. Good conditions must be set for each material to be sealed, and a high degree of skill is required.
From this point of view, the present inventor sought to provide a sealant primer composition that is fully applicable to acrylic-modified urethane sealants without incorporating a urethane resin. , (b) General formula

[Formula] (In the formula, R ¹ means an alkyl group having 1 to 4 carbon atoms.) A methacrylate compound represented by (iii) styrene or the general formula

[Formula] (In the formula, n is an integer from 1 to 3 indicating the number of methyl groups substituted on the benzene nucleus.) A styrene derivative represented by the following general formula:

[Formula] [In the formula, R ² is H or a methyl group, X is COOH,

【formula】

[Formula] (m is an integer from 2 to 4) or CO-Y {Y is
NH ₂ , NHCH ₂ OR ³ (R ³ is H or carbon number 1 to
4 alkyl group) or (CH ₂ ) _l -N(R ⁴ ) ₂
(l is an integer of 1 to 4, R ⁴ is an alkyl group having 1 to 4 carbon atoms)}. Acrylic whose main component is a mixture of a copolymer obtained by copolymerizing a monomer mixture containing 70% by weight or more of the compound represented by ]; and a silane coupling agent in an amount corresponding to 20% by weight or less Primer composition for modified urethane sealant, (a) acrylonitrile or methacrylonitrile, (b) general formula

[Formula] (In the formula, R ¹ means an alkyl group having 1 to 4 carbon atoms.) A methacrylate compound represented by (iii) styrene or the general formula

[Formula] (In the formula, n is an integer from 1 to 3 indicating the number of methyl groups substituted on the benzene nucleus.) A styrene derivative represented by (d) General formula

[Formula] [In the formula, R ² is H or a methyl group, X is COOH,

【formula】

[Formula] (m is an integer from 2 to 4) or CO-Y {Y is
NH ₂ , NHCH ₂ OR ³ (R ³ is H or carbon number 1 to
4 alkyl group) or (CH ₂ ) _l -N(R ⁴ ) ₂
(l is an integer of 1 to 4, R ⁴ is an alkyl group having 1 to 4 carbon atoms)}. ] and (e) triallylisocyanuric acid, a copolymer obtained by copolymerization from a monomer mixture containing 70% by weight or more; and a silane coupling in an amount equivalent to 20% by weight or less thereof. A primer composition for an acrylic modified urethane sealant, the main component of which is a mixture with an acrylonitrile or methacrylonitrile (b) general formula

[Formula] (In the formula, R ¹ means an alkyl group having 1 to 4 carbon atoms.) A methacrylate compound represented by (iii) styrene or the general formula

[Formula] (In the formula, n is an integer from 1 to 3 indicating the number of methyl groups substituted on the benzene nucleus.) A styrene derivative represented by (d) General formula

[Formula] [In the formula, R ² is H or a methyl group, X is COOH,

【formula】

[Formula] (m is an integer from 2 to 4) or CO-Y {Y is
NH ₂ , NHCH ₂ OR ³ (R ³ is H or carbon number 1 to
4 alkyl group) or (CH ₂ ) _l -N(R ⁴ ) ₂
(l is an integer of 1 to 4, R ⁴ is an alkyl group having 1 to 4 carbon atoms)}. ], (e) triallylisocyanuric acid, and (f) general formula

[Formula] [In the formula, Z is (CH ₂ ) _p or

[Formula] (p is an integer from 1 to 4, q is an integer from 1 to 10),
R ⁵ represents H or a methyl group, and R ⁶ represents an alkyl group having 1 to 10 carbon atoms. ] The main component is a mixture of a copolymer obtained by copolymerizing a monomer mixture containing 70% by weight or more of a silane compound represented by the above; and a silane coupling agent in an amount equivalent to 20% by weight or less of the copolymer; A primer composition for an acrylic modified urethane sealant is provided. Here, the compound (d) more specifically includes acrylic acid, methacrylic acid, and derivatives thereof such as hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate,
Hydroxyalkyl acrylate or hydroxyalkyl methacrylate such as hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, derivatives thereof N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-propoxymethylacrylamide, N
- N-alkoxymethylacrylamide or N-alkoxymethylmethacrylamide such as butoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, N-propoxymethylmethacrylamide, N-butoxymethylmethacrylamide, and glycidyl acrylate , glycidyl methacrylate, etc. Among these, 2-hydroxyethyl methacrylate in particular showed good results in the water resistance test described below. In addition, specifically as the silane compound (f),
γ-acryloxypropyltrimethoxysilane,
γ-acryloxypropyltriethoxysilane,
γ-acryloxypropyltripropoxysilane, γ-acryloxypropyltributoxysilane, γ-methacryloxypropyltrismethoxyethoxysilane, γ-methacryloxypropyltrisethoxyethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxyethoxysilane Examples include roxypropyltriethoxysilane, γ-methacryloxypropyltributylsilane, δ-methacryloxybutyltrimethoxysilane, trimethoxyvinylsilane, and triethoxyvinylsilane. When mixing the compounds corresponding to (a), (b), (c), (d), (e), and (f) above to form a monomer mixture,
Select one or more compounds corresponding to (a), (b), (c), (d), (e), and (f), respectively (hereinafter, the selected compounds or compound groups will be , using the codes to which they belong, (a) component, (b) component, (c) component, (d) component,
(E)
component (expressed as (F) component), according to the mixing ratio shown below. In other words, the mixing ratio of each component cannot be determined unconditionally because it depends on the type of acrylic modified sealant to which the target primer is applied, but in general, component (a) is a mixture of all monomers. In
Component (B) is mixed to account for 10 to 40% by weight, preferably 15 to 30% by weight, and component (B) accounts for 20% by weight of the total monomers.
~70% by weight, preferably 40 to 60% by weight, component (c) 2 to 30% by weight, preferably 5 to 20% by weight, (d)
The components are mixed in amounts of 3 to 40% by weight, preferably 5 to 30% by weight. In addition, component (E) is the total amount of components (B) to (D).
To 100 parts by weight, add an amount not exceeding 100 parts by weight, preferably 50 parts by weight or less, and similarly when adding component (F), the total amount of components (A) to (D) to 100 parts by weight. in an amount not exceeding 100 parts by weight, preferably
Add up to 50 parts by weight. If the amount of component (a) is too small, heat resistance, hot water resistance, and oil resistance will be insufficient, and if it is too large, weather resistance and normal adhesiveness will be insufficient. Furthermore, if the amount of component (b) is too small or too large, the normal adhesiveness will be insufficient. Furthermore, if the amount of component (c) is too low, heat resistance and boiling water resistance will be insufficient; if it is too high, oil resistance and normal adhesion will be insufficient; if component (d) is too low, the adhesion with the sealant will be poor. If it is too large, the hot water resistance will be insufficient. The addition of component (e) and component (f) is effective in improving the adhesion and hot water resistance of the target object, but the former (e)
If the amount of the component is too large, gelation may occur during copolymer synthesis, the solution viscosity of the copolymer will increase, workability will decrease, and the normal adhesion of the target product will also decrease. On the other hand, if the amount of the latter (f) component is too large, the affinity for the target sealant will decrease and the adhesiveness will also tend to decrease. Monomers other than components (a) to (f) should not be added if possible, but ethylene, propylene, butene,
Alkylene compounds such as butadiene, acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, stearyl acrylate, and lauryl acrylate, long chain alkyls such as 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate. Vinyl compounds such as methacrylate, vinyl acetate, vinyl propionate, and vinyl chloride, unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, and their esters account for 30% by weight of the total monomers.
It is permissible as long as it does not exceed. In preparing the sealant primer composition of the present invention, the monomers mixed as described above are first subjected to bulk polymerization, solution polymerization, and gas polymerization in the presence of heat, light, electron beams, or a catalyst such as peroxide. A copolymer is produced by phase polymerization or emulsion polymerization, and then 20% by weight or less, preferably 0.1 to 10% by weight, of the copolymer is added to the copolymer.
A corresponding amount of silane coupling agent is added, and the mixture thus obtained is dissolved in an appropriate organic solvent to form a solution with an appropriate viscosity. Addition of the above-mentioned silane coupling agent is effective in improving the adhesion, cold resistance, and hot water resistance of the target object, but if the amount added is too large, it becomes soft and the adhesion decreases. Examples of the silane coupling agent include mercaptosilane, aminosilane, and epoxysilane. Solution polymerization is most advantageous for monomer polymerization, and the organic solvent used during polymerization can remain in the final product without being removed. For solution polymerization, for example, benzoyl peroxide, t-butyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide,
A commonly used polymerization initiator such as cumene peroxide, dicumene peroxide, dicumene hydroperoxide, azobisisobutyronitrile, etc. may be used in a proportion of 0.05 to 5 parts by weight per 100 parts by weight of the monomer. At that time, a chain transfer agent such as butyl mercaptan, dodecyl mercaptan, acetic acid trichloride, carbon tetrachloride, etc. is added to the monomer.
It can be used in a proportion of 0.05 to 10 parts by weight per 100 parts by weight. The solvent used in solution polymerization may be any solvent as long as it dissolves the copolymer, but alcohols, amines, and the like containing active hydrogen should preferably be avoided. The thus obtained copolymer was heated in DMF at 30°C.
Intrinsic viscosity in solution [η] is 0.07 to 0.50 dl/
g, especially those exhibiting 0.1 to 0.3 dl/g are good; the smaller the intrinsic viscosity, the lower the adhesiveness and heat resistance; conversely, if it becomes too large, the adhesiveness will decrease and the workability will also decrease. Deteriorate. Finally, the sealant primer of the present invention is
The copolymer and silane coupling agent are dissolved in an appropriate solvent so that the solution viscosity in the environment of use is 200 cps or less, preferably 100 cps or less. The same solvent may be used. The sealant primer can also contain commonly used additives such as colorants, viscosity modifiers, and storage stability improvers. As is clear from the above, the present invention provides a primer composition that can be applied to an acrylic modified urethane sealant without incorporating a urethane resin, and is intended for cement mortar where adhesion is most likely to be a problem. When used as a raw material, it exhibits good performance over a relatively wide composition range, as shown in the Examples and Test Examples described below. Hereinafter, the present invention will be explained in more detail with reference to copolymer production examples, examples, test examples, etc. Production example of copolymer 1 20 parts of acrylonitrile, 45 parts of butyl methacrylate, 10 parts of styrene, 25 parts of 2-hydroxyethyl methacrylate, 75 parts of toluene, and 25 parts of acetone were mixed uniformly, and azobisisobutylene was added to the mixture. Add 3 parts of lonitrile and heat for 15 hours while stirring and refluxing while keeping the liquid temperature at 85°C, and the non-volatile content is 49.5
% of a colorless and transparent copolymerization liquid was obtained. This copolymer was precipitated with petroleum benzine, separated and dried under reduced pressure at room temperature.The intrinsic viscosity at 30°C was determined using dimethyl formaldehyde and was found to be 0.258. Copolymer production example 17 Uniformly mix 20 parts of acrylonitrile, 45 parts of butyl methacrylate, 10 parts of styrene, 25 parts of 2-hydroxyethyl methacrylate, 10 parts of triallylisocyanuric acid, 80 parts of toluene, and 30 parts of acetone. Then, 3 parts of azobisisobutyronitrile was added thereto, and the mixture was heated under stirring and reflux for 18 hours while maintaining the liquid temperature at 80°C to obtain a colorless and transparent copolymer solution with a non-volatile content of 49.0%. The intrinsic viscosity of this copolymer was measured in the same manner as in Production Example 1 and was found to be 0.289. Copolymer production example 18 25 parts of acrylonitrile, 50 parts of butyl methacrylate, 10 parts of styrene, 15 parts of 2-hydroxyethyl methacrylate, 25 parts of triallylisocyanuric acid, 20 parts of γ-methacryloxypropyltrimethoxysilane, toluene 100 parts, and acetone
45 parts were mixed uniformly, 3.5 parts of azobisisobutyronitrile was added thereto, and heated under stirring and reflux for 18 hours while maintaining the liquid temperature at 80°C, resulting in a non-volatile content of 48.5%.
A colorless and transparent copolymerization solution was obtained. This copolymer was precipitated with petroleum benzine, diluted with a small amount of acetone, precipitated again with petroleum benzine, and the separated product was dried under reduced pressure at room temperature, and its intrinsic viscosity at 30°C was determined with dimethylformamide, which was 0.261. It was hot. Production Examples of Copolymers 2 to 16, 19 to 32 Copolymers of the present invention and copolymers for comparison were obtained in the same manner as in the production examples above except that the type and amount of monomers were changed. The types and amounts of monomers and the intrinsic viscosity [η] of the produced copolymers in these production examples are shown in Table 1 together with Production Examples 1, 17, and 18.

【table】

【table】

【table】

[Table] Examples and Comparative Examples Toluene was added to the toluene-acetone solution of the copolymer obtained in the above production example so that the concentration of the copolymer was 30%, and then silane was added to the 30% solution of the copolymer. A coupling agent was added and mixed uniformly to obtain a primer composition of the present invention and a primer composition for comparison. The above is shown in Table 2. In Table 2, trimethoxymercaptopropylsilane is a product "SH6062" manufactured by Toray Silicone Co., Ltd., and trimethoxyglycidoxyethylsilane is a product "SH6040" manufactured by the same company.

【table】

[Table] Test Examples The following tests were conducted using the sealant primer compositions obtained in the Examples and Comparative Examples. The results were as shown in Table 3. <Adhesion test> 50mm× prepared in accordance with JISA5758 Section 5.12.2
Apply the primer composition to one side of each of two 50mm x 25mm cement mortar blocks, leave it at room temperature for 30 minutes, and then apply the primer composition in accordance with JISA5758 Section 5.12.3.
Center top sealer Au using spacer
(Manufactured by Yamauchi Rubber Industries Co., Ltd., trade name, acrylic modified sealing material) was extruded into a column of 50 mm x 12 mm x 12 mm, adhered to the cement mortar, and cured for 7 days at room temperature and then at 50°C for 7 days. A test piece for a tensile adhesion test was prepared. Using three test pieces thus obtained, the cohesive failure rate and tensile adhesive strength were measured using a tensile tester. <Hot Water Resistance Test> Three test pieces prepared in the same manner as in the adhesion test were immersed in warm water at 50°C for 2 days, and then a tensile test was conducted in the same manner as in the adhesion test. <Heat resistance test> Using three test pieces prepared in the same way as the adhesion test,
14 at 80℃ or 90℃ in accordance with JISA5758 Section 5.12.3
After heating for several days, a tensile test similar to the adhesion test was conducted. <Durability test> Using three test pieces prepared in the same way as the adhesion test,
A durability test (durability classification 8020 and 9030) was conducted according to JISA5758 Section 5.12.3.

【table】

【table】

[Table] In Table 3, CF is cohesive failure (failure at the sealant part), TL is thin layer failure (failure at the boundary between the sealant and primer), and AF is interfacial failure (failure between the primer and the target material). destruction) respectively, CF,
The numbers after TL and AF mean the area ratio.

Claims (1)

[Scope of Claims] 1 (a) Acrylonitrile or methacrylonitrile, (b) A methacrylate compound represented by the general formula [Formula] (wherein R ¹ means an alkyl group having 1 to 4 carbon atoms), (iii) Styrene or a styrene derivative represented by the general formula [Formula] (wherein n is an integer of 1 to 3 meaning the number of methyl groups substituted on the benzene nucleus), and (iv) General Formula [Formula] [In the formula, R ² is H or a methyl group, X is COOH, [Formula] [Formula] (m is an integer from 2 to 4) or CO-Y {Y is NH ₂ ,
NHCH ₂ OR ³ (R ³ is H or an alkyl group having 1 to 4 carbon atoms) or (CH ₂ ) _l -N(R ⁴ ) ₂ (l is 1 to 4
^R4 is an alkyl group having 1 to 4 carbon atoms). ] A monomer mixture containing 70% by weight or more of the compound represented by the following, wherein the proportion of the components (a), (b), (c), and (d) in the total monomers is 70% by weight or more. In order of percentage, 10~
40% by weight, 20-70% by weight, 2-30% by weight, 3-40
A primer composition for an acrylic-modified urethane sealant, the main component of which is a mixture of a copolymer obtained by copolymerizing a monomer mixture in a range of 20% by weight or less and a silane coupling agent in an amount corresponding to 20% by weight or less. . 2 (a) Acrylonitrile or methacrylonitrile, (b) A methacrylate compound represented by the general formula [Formula] (wherein R ¹ means an alkyl group having 1 to 4 carbon atoms), (c) Styrene or a general formula A styrene derivative represented by the formula [Formula] (where n is an integer from 1 to 3 indicating the number of methyl groups substituted on the benzene nucleus), (d) General formula [Formula] [In the formula R ² is H or methyl group, X is COOH, [Formula] [Formula] (m is an integer from 2 to 4) or CO-Y {Y is NH ₂ ,
NHCH ₂ OR ³ (R ³ is H or an alkyl group having 1 to 4 carbon atoms) or (CH ₂ ) _l -N(R ⁴ ) ₂ (l is 1 to 4
^R4 is an alkyl group having 1 to 4 carbon atoms). ] and (e) triallylisocyanuric acid, a monomer mixture containing 70% by weight or more of the compound represented by The proportions of component ) and component (d) are 10 to 10, respectively.
40% by weight, 20-70% by weight, 2-30% by weight, 3-40
A copolymer obtained by copolymerizing a monomer mixture in which the weight of the component (e) does not exceed the total weight of the components (a) to (d); A primer composition for an acrylic-modified urethane sealant, the main component of which is a mixture with a silane coupling agent in an amount equivalent to 20% by weight or less. 3 (a) Acrylonitrile or methacrylonitrile, (b) A methacrylate compound represented by the general formula [Formula] (wherein R ¹ means an alkyl group having 1 to 4 carbon atoms), (c) Styrene or a general formula A styrene derivative represented by the formula [Formula] (where n is an integer from 1 to 3 indicating the number of methyl groups substituted on the benzene nucleus), (d) General formula [Formula] [In the formula R ² is H or methyl group, X is COOH, [Formula] [Formula] (m is an integer from 2 to 4) or CO-Y {Y is NH ₂ ,
NHCH ₂ OR ³ (R ³ is H or an alkyl group having 1 to 4 carbon atoms) or (CH ₂ ) _l -N(R ⁴ ) ₂ (l is 1 to 4
^R4 is an alkyl group having 1 to 4 carbon atoms). ], (e) triallylisocyanuric acid, and (f) general formula [formula] [wherein Z is (CH ₂ ) _p or [formula] (p is an integer of 1 to 4, q is integer from 1 to 10), R ⁵
represents H or a methyl group, and R ⁶ represents an alkyl group having 1 to 10 carbon atoms. ] A monomer mixture containing 70% by weight or more of a silane compound represented by the following, in which the components (a), (b), (c), and (d) account for 70% by weight or more of the total monomers. The percentage of each in order is 10~
40% by weight, 20-70% by weight, 2-30% by weight, 3-40
% by weight, and the weight of the components (e) and (f) does not exceed the total weight of the components (a) to (d). A primer composition for an acrylic-modified urethane sealant, the main component of which is a mixture of a copolymer obtained by polymerization and a silane coupling agent in an amount corresponding to 20% by weight or less of the copolymer.