JPH0757764B2 - Aqueous resin dispersion and its use - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an aqueous resin dispersion, more specifically, it shows good storage stability, and the polymerizable unsaturated group contained in the emulsifier during emulsion polymerization is emulsion polymerized. By reacting with the resin and grafting, the compatibility between the emulsifier and the emulsion-polymerized resin is greatly improved, and at least one of the polymerizable monomers used in the emulsion-polymerization is a functional group reactive with a carboxyl group. In the case of containing water, when the water is dispersed to form a film, the emulsifier and the emulsion-polymerized resin further undergo a crosslinking reaction to form a transparent film having particularly excellent water resistance. The present invention relates to a coating agent, a pressure-sensitive adhesive and a fiber processing agent using a dispersion liquid. (Problems to be solved by the prior art and the present invention) Aqueous resin dispersions have been conventionally produced by an emulsion polymerization method using various emulsifiers, and have no pollution, good workability, resource saving and Taking advantage of these advantages, it has a wide range of applications such as paints, adhesives, paper processing agents, fiber processing agents, and mortar modifiers. However, the hydrophilic emulsifier used for emulsion polymerization remains in the film even after the water is scattered to form a film, and since it is easily localized at the interface of the old particles, various properties such as water resistance of the film are adversely affected. It is a cause of this. In order to improve the essential drawbacks of such an aqueous resin dispersion, a soap-free emulsion polymerization method using a large amount of potassium persulfate and the like, an emulsion polymerization method using a high molecular emulsifier, etc. have been proposed. Regarding sex, it is still insufficient. The object of the present invention is to solve the above-mentioned problems that conventional aqueous resin dispersions have, less foaming, good film-forming properties, good stability in a water-dispersed state, and water scattering. Another object of the present invention is to provide an aqueous resin dispersion which gives a transparent and excellent water-resistant coating, and a coating agent, pressure-sensitive adhesive and fiber processing agent using the aqueous resin dispersion. (Means and Actions for Solving Problems) The present inventors emulsify a polymerizable unsaturated group-containing compound having a long-chain thioalkyl group at the terminal and having a carboxyl group and / or its salt in the molecule. When used as an emulsifier at the time of polymerization, in addition to the polymerizable unsaturated group contained in the compound reacts with the polymer formed by emulsion polymerization to be grafted, further, for example, with a carboxyl group such as an epoxy compound. The present invention has been accomplished by discovering that the compound having a reactivity is mixed with the carboxyl group and / or its salt contained in the compound and the epoxy group efficiently during the film formation. That is, the present invention has the general formula (In the formula, R ₁ represents an alkyl group having 6 to 18 carbon atoms, R ₂ ,
R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt of a carboxyl group or a carboxymethyl group, and X
Represents hydrogen, an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group having a polymerizable unsaturated group and an ether bond, an ester group, an amide group or an amino group, and Z Represents a nitrile group or a phenyl group which may have a substituent, an amide group or a carboxylic acid alkyl ester group, and a represents 1 to 50
0 and b are integers of 1 to 100, and c is 0 or an integer of 1 to 250. And an aqueous resin dispersion obtained by emulsion-polymerizing one or more polymerizable monomers in an aqueous medium using a reactive surfactant composed of a polymerizable unsaturated group-containing compound represented by The present invention relates to a coating agent, a pressure-sensitive adhesive and a fiber processing agent using the aqueous resin dispersion liquid. In the present invention, the reactive surfactant comprising a polymerizable unsaturated group-containing compound used as an emulsifier is a polymerizable monomer (A) having a carboxyl group and optionally other polymerizable monomer (B) in the presence of an alkyl mercaptan. It is composed of a reaction product of a polymer obtained by lower radical polymerization and a polymerizable monomer (C) having a group having reactivity with a carboxyl group and / or a salt thereof. Examples of the polymerizable monomer (A) having a carboxyl group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid or maleic acid or fumaric acid monoesters. 1
One kind or a mixture of two or more kinds can be used. In addition, styrene as the other polymerizable monomer (B),
Styrene derivatives such as α-methylstyrene, chlorostyrene, methylstyrene, chloromethylstyrene, styrenesulfonic acid or salts thereof; (meth) acrylamide, methylolated (meth) acrylamide, carbon number 1 to
Amide group-containing polymerizable monomers such as four alkoxymethylolated (meth) acrylamides, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide; 18
(Meth) acrylic acid ester having one alkyl chain,
2-hydroxyethyl methacrylate, hydroxypropyl (meth) acrylate, 2-methacrylic acid-2-N,
(Meth) acrylic acid ester derivatives such as N-dimethylaminoethyl and N, N-dimethylaminopropyl (meth) acrylate; nitrile group-containing polymerizable monomers such as (meth) acrylonitrile. Can be used in one kind or a mixture of two or more kinds. Further, as the polymerizable monomer (C) containing a group having reactivity with a carboxyl group used for introducing a polymerizable unsaturated group into the reactive surfactant, glycidyl (meth) acrylate, Epoxy group-containing polymerizable monomers such as allylglycidyl ether; 2-isopropenyl-2-
Oxazoline group-containing polymerizable monomers such as oxazoline and 2-vinyl-2-oxazoline; methacrylic acid 2
-Aziridinylethyl, aziridine group-containing polymerizable monomers such as (meth) acryloylaziridine; (meth)
2-hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, (meth) allyl alcohol, hydroxyl group-containing polymerizable monomers such as monoester products of (meth) acrylic acid and polypropylene glycol or polyethylene glycol Can be mentioned. These can be used in one kind or in a mixture of two or more kinds, whereby as the Y in the above general formula, a hydrocarbon group having an ether bond, an ester group, an amide group or an amino group together with a polymerizable unsaturated group can be used. be introduced. The amount of the polymerizable monomer (C) used is in the range of 1 to 100 molecules, and preferably 1 to 10 molecules, per 1 molecule of the reactive surfactant. However, when a hydroxyl group-containing polymerizable monomer is used as the polymerizable monomer (B), the hydroxyl group-containing polymerizable monomer cannot be used as the polymerizable monomer (C). Examples of the alkyl mercaptan having 6 to 18 carbon atoms used in the polymerization include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, cetyl mercaptan, stearyl mercaptan and the like. Seed or 2
It can be used in a mixture of more than one species. The reaction conditions for obtaining the reactive surfactant are not particularly limited. For example, the alkyl mercaptan, the polymerizable monomer (A) and the polymerizable monomer (B) are used as they are by using a general radical polymerization initiator. Alternatively, if necessary, the resultant is diluted with a solvent and polymerized, and the resulting polymerizable monomer (C) containing a group having reactivity with a carboxyl group is diluted as it is or with a solvent if necessary. Therefore, the reaction can be carried out under the temperature condition of preferably room temperature to 200 ° C, more preferably 50 to 150 ° C. At this time, the radical polymerization initiator used is preferably not more than 1/10 mol of the alkyl mercaptan, and if necessary, the solvent used is the polymerizable monomers (A), (B), (C) and alkyl. It must be able to dissolve mercaptans and be inert to them. In addition, it is free to use a catalyst for promoting the reaction during the reaction. The molecular weight of the reactive surfactant synthesized under such conditions is preferably 400 to 10,000, more preferably 400 to 5,000. The reactive surfactant thus obtained can be mixed with a base to form a salt. The use of a salt is preferable because the solubility in water is improved. Examples of the base that can be blended include inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; organic bases such as trimethylamine and triethylamine, and one or a mixture of two or more of them can be used. . The polymerizable monomer used in the emulsion polymerization of the present invention is not particularly limited as long as it is a polymerizable monomer, and one kind or a combination of two or more kinds thereof can be used depending on the purpose and application. Examples of these polymerizable monomers include styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, styrenesulfonic acid and salts thereof; (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth)
(Meth) acrylamide derivatives such as acrylamide and N, N-dimethyl (meth) acrylamide; methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
(Meth) acrylic acid such as butyl acrylate and C _{1 to} C ₁₈
(Meth) acrylic acid esters synthesized by esterification of the alcohol of (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid and polypropylene glycol or polyethylene glycol Hydroxyl group-containing (meth) acrylic acid esters such as monoesters;
Ethyl 2-methacrylate (meth) acrylate and salts thereof,
Vinyl sulfonic acid and its salts, vinyl acetate, (meth) acrylonitrile, etc., dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, vinylpyridine, vinylimidazole, vinylpyrrolidone Basic polymerizable monomers such as; (meth) acrylic acid and ethylene glycol, 1,3-butylene glycol,
Two polymerizable unsaturated groups in the molecule such as diethylene glycol, 1,6-hexane glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and other polyhydric alcohol esters. Polyfunctional (meth) acrylic acid esters having the above; (meth) acrylamides such as N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide; vinyltrimethoxysilane, γ- (meth)
Organosilicon group-containing polymerizable monomers such as acryloxypropyltrimethoxysilane, allyltriethoxysilane, and trimethoxysilylpropylallylamine; and vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, divinylbenzene, diallyl phthalate And so on. Further, as the polymerizable monomer having a functional group capable of reacting with a carboxyl group used for further improving the water resistance of the film obtained by scattering water from the aqueous resin dispersion, the polymerizable unsaturated Among the polymerizable monomers (C) used when synthesizing the reactive surfactant composed of the group-containing compound, those excluding the hydroxyl group-containing polymerizable monomers can be mentioned as they are. The present invention also employs a reactive surfactant comprising the above-mentioned polymerizable unsaturated group-containing compound as an emulsifier, and emulsion-polymerizes one or more of the above-mentioned polymerizable monomers in an aqueous medium. The present invention relates to the resulting aqueous resin dispersion liquid, and as the polymerization method, any conventionally known emulsion polymerization method can be applied. For example, a polymerization catalyst, water, a reactive surfactant composed of the polymerizable unsaturated group-containing compound and / or a salt thereof, a method of actively mixing and mixing a polymerizable monomer, or a so-called monomer dropping method, The aqueous resin dispersion liquid of the present invention can be synthesized by a method such as an emulsion method. The polymerization temperature is 0 to 100 ° C, preferably 50 to 80 ° C, and the polymerization time is 1 to 10 hours. At the time of emulsion polymerization, addition of a hydrophilic solvent and addition of other known emulsifiers and additives are possible within a range that does not adversely affect the physical properties of the film. The amount of the reactive surfactant and / or salt thereof composed of the polymerizable unsaturated group-containing compound is not particularly limited,
Preferably 0.5 to 20 with respect to 100 parts by weight of the polymerizable monomer component
It is 0 part by weight, more preferably 1 to 15 parts by weight. As the polymerization catalyst, any conventionally known catalyst can be used. However, in order to obtain an aqueous resin dispersion which gives a film having further excellent water resistance, hydrogen peroxide and di-
One type of polymerization catalyst that does not leave sulfate radicals, such as t-butyl peroxide, peracetic acid, 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid) Alternatively, it is preferable to use a mixture of two or more kinds. In addition, when at least one of the polymerizable monomers has a functional group capable of reacting with a carboxyl group, it contains an amidino group, a carboxyl group, or the like having high reactivity with the reactive group in the molecule. It is more preferable to use 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid) or the like. The amount of the polymerization catalyst used is usually in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymerizable monomer component. When at least one of the polymerizable monomers has a functional group capable of reacting with a carboxyl group, the polymerizable monomer contains a polymerizable monomer having a functional group capable of reacting with a carboxyl group. By dividing into those which do not contain and polymerizing these in multiple stages, the water resistance, solvent resistance, strength and the like of the film of the obtained aqueous resin dispersion are remarkably improved. At that time, each of the polymerizable monomer components may be emulsion-polymerized in any number of stages, and the order of polymerization is not limited. Multi-stage polymerization
It is intended to remarkably improve the water resistance of the obtained film, but especially when the final polymerizable component does not contain a polymerizable monomer having a functional group capable of reacting with a carboxyl group, It is preferable because not only the above physical properties are further improved but also storage stability is dramatically improved. (Effect of the Invention) The aqueous resin dispersion of the present invention contains a polymerizable unsaturated group obtained by reacting a compound having a carboxyl group in the molecule with a polymerizable monomer (C) having a polymerizable unsaturated group. It is obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a reactive surfactant composed of a compound as an emulsifier, and is included in the reactive surfactant during emulsion polymerization. Since the polymerizable unsaturated group reacts with the polymer produced by emulsion polymerization and is grafted, the compatibility between the emulsifier and the polymer particles is improved. Therefore, the property of the conventionally known anionic emulsifier, which tends to be localized on the film-fused surface of the film after coating or the coating film, is eliminated, and a large film strength and excellent water resistance are provided. Furthermore, since the reactive surfactant has a carboxyl group in the molecule,
When at least one polymerizable monomer having a functional group capable of reacting with a carboxyl group is used in the polymerizable monomer component, it is used as an emulsifier when water is scattered from the aqueous resin dispersion. The reactive surfactant diffuses in the emulsion-polymerized resin, and the carboxyl group contained in the reactive surfactant reacts with the functional group in the emulsion-polymerized resin to form a crosslinked structure, so that film strength and water resistance are improved. It is possible to further improve and obtain a film having excellent solvent resistance. Therefore, when the aqueous resin dispersion is used as a coating agent for inorganic building materials, metals, wood, plastics, etc., it is very excellent in adhesion to base materials, water resistance, frost damage resistance and weather resistance. There is. Also, non-woven interlining binder,
When used as an aqueous resin dispersion for various fiber processing such as printing binders, flocking binders, fabric bonding agents, and texture processing agents, it is extremely useful as water resistance, washing resistance, weather resistance, and adhesives for substrates. Shows excellent characteristics. In addition, when used as an adhesive for packaging tapes, double-sided tapes, paper labels, etc., it not only excels in tackiness and retention on various substrates, but also when the tape is applied to the substrate and it is whitened even when immersed in water. It shows excellent water resistance and humidity resistance, in which the adhesive property is not deteriorated even under high temperature and high humidity. (Examples) Examples of the present invention will be shown below, but these are given for the purpose of illustration and do not limit the scope of the present invention. In the following, parts and% represent parts by weight and% by weight, respectively. Reference Example 1 180 parts of isopropyl alcohol was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser, and heated to 80 ° C. while gently blowing nitrogen gas. Then, a polymerizable mixture consisting of 174 parts of acrylic acid, 36 parts of n-dodecyl mercaptan and 0.42 part of 2,2'-azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added dropwise over 1.5 hours. Keep the temperature at 80-85 ℃ during dripping,
Further, after completion of dropping, the mixture was stirred at the same temperature for 1 hour to complete the polymerization. Further, 57 parts of allyl glycidyl ether and 21 parts of triethylenebenzylammonium chloride were added to the polymer mixture thus obtained, and the mixture was heated to 85 ° C. and reacted at the same temperature for 6 hours to prepare a reactive surfactant (1 ) Got. It was confirmed by the acid value measurement that the reaction was completed. The number average molecular weight of the reactive surfactant (1) was 1,300. Reference Example 2 Isopropyl alcohol was placed in the same flask as in Reference Example 1.
180 parts were charged and heated to 80 ° C. while blowing nitrogen. A polymerizable monomer mixture consisting of 148 parts of acrylic acid, 31 parts of itaconic acid, 18 parts of 2-ethylhexyl acrylate, 24 parts of n-octyl mercaptan and 0.41 part of AIBN was added thereto.
It was added dropwise over 0 hours. After completion of the dropping, the mixture was stirred under reflux for 1 hour to complete the polymerization. Further, 77 parts of 2-aziridinylethyl methacrylate was added to the polymer mixture thus obtained, and the mixture was reacted under reflux for 4 hours to obtain a reactive surfactant (2). The number average molecular weight of the reactive surfactant (2) was 1500. Reference Example 3 In the same flask as in Reference Example 1, add isopropyl alcohol.
180 parts were charged and heated to 80 ° C. while blowing nitrogen. Then, 86 parts of acrylic acid, 139 parts of 2-hydroxyethyl acrylate, 36 parts of n-dodecyl mercaptan, 30 parts of isopropyl alcohol and 2,2'-, which had been previously prepared.
A polymerizable monomer mixture consisting of 0.30 parts of azobisisobutyronitrile was dropped and polymerized for 1 hour. After the dropping is completed,
Polymerization was completed by aging for 1 hour under reflux. Further, 56 parts of isopropenyloxazoline was added to the polymer mixture thus obtained, and the mixture was reacted under reflux for 6 hours to obtain a reactive surfactant (3). The number average molecular weight of the reactive surfactant (3) was 1600. Reference Example 4 A flask similar to that of Reference Example 1 was charged with 180 parts of 1,4-dioxane and heated to 80 ° C. while blowing nitrogen. Subsequently, a previously prepared polymerizable monomer mixture consisting of 116 parts of acrylic acid, 43 parts of acrylonitrile, 51 parts of stearyl mercaptan and 0.32 part of AIBN was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred under reflux for 1 hour to complete the polymerization.
Further, 65 parts of 2-hydroxyethyl methacrylate, 3.4 parts of p-toluenesulfonic acid and 0.13 part of p-methoxyphenol were added to this polymer mixture, and the mixture was reacted at 90 ° C. for 12 hours to give a reactive surfactant (4). Obtained. The number average molecular weight of the reactive surfactant (4) was 1,300. Comparative Reference Example 1 A surfactant (1 ′) was obtained by the same procedure as in Reference Example 1 except that 14 parts of mercaptoethanol was used instead of n-dodecyl mercaptan. The number average molecular weight of the surfactant (1 ′) was 1100. Comparative Reference Example 2 In Reference Example 1, the same amount of 2-hydroxyethyl acrylate was used instead of acrylic acid as the polymerizable monomer during polymerization, and the polymerizable monomer, the alkyl mercaptan, and the AIBN mixture were separately added dropwise. The same polymerization was carried out except that the reaction was carried out to obtain a surfactant (2 '). The number average molecular weight of the surfactant (2 ′) was 1200. Comparative Reference Example 3 In Reference Example 1, the reaction was terminated only by polymerization to obtain a surfactant (3 ′). The number average molecular weight of the surfactant (3 ') was 1,000. Example 1 A flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser was charged with 193.5 parts of pure water and 4.9 parts of the solution of the reactive surfactant (1) obtained in Reference Example 1, 28%
1.6 parts of ammonia water was added for neutralization to obtain an emulsifier. The mixture was heated to 65 ° C while gently blowing nitrogen gas. Add 56.7 parts of butyl acrylate and methyl methacrylate to the dropping funnel.
A polymerizable monomer mixture consisting of 43.3 parts was prepared and
A 10% volume was added dropwise to the flask. Subsequently, 4 parts of a 5% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride was injected. After 20 minutes, the dropping of the remaining polymerizable monomer mixture was started, and the dropping was completed in 2 hours. Change the temperature during dropping
The temperature was maintained at 65 to 70 ° C., and after completion of dropping, the polymerization was completed by stirring at the same temperature for 1 hour to obtain an aqueous resin dispersion [1] having a nonvolatile content of 33.8% and pH = 7.1. Examples 2 to 3 In Example 1, except that the amount and kind of the solution of the reactive surfactant, the amount and kind of the neutralizing agent, and the kind of the polymerizable monomer mixture are as shown in Table 1. The same operation as in Example 1 was repeated to obtain aqueous resin dispersions [2] to [3]. The results are summarized in Table 1. Example 4 90 parts of pure water was charged into the same flask as in Example 1 and heated to 65 ° C. while gently blowing nitrogen gas. 190 parts of 2-ethylhexyl acrylate, 10 parts of vinyl acetate, 9.8 parts of a solution of the reactive surfactant (4) obtained in Reference Example 4, 10
% Aqueous potassium hydroxide solution (12.0 parts) and pure water (89.1 parts) were thoroughly stirred in advance, and the completely emulsified pre-emulsion was charged into a dropping funnel, and 10% of the amount was added dropwise to the flask. Then 2,2'-azobis (2-amidinopropane)
8 parts of a 5% aqueous solution of dihydrochloride were injected. After 20 minutes, the dropping of the remaining pre-emulsion was started, and the dropping was completed in 4 hours. After the dropping was completed, the dropping funnel was washed with 10 parts of pure water so that the pre-emulsion did not remain, and the washing solution was added into the flask. During the dropping, the temperature was kept at 65 to 70 ° C., and after the dropping was completed, the mixture was stirred at the same temperature for 2 hours to terminate the polymerization to obtain an aqueous resin dispersion [4] having a nonvolatile content of 49.8% and pH = 7.2. Examples 5 to 8 Examples were carried out except that in Examples 1 to 4, the polymerizable monomer mixture containing a group having a group and a group reactive with a carboxyl group shown in Table 1 was used in the polymerizable monomer mixture. The same operations as in Examples 1 to 4 were repeated to obtain aqueous resin dispersions [5] to [8]. Detailed results are summarized in Table 1. Comparative Examples 1-2 In Example 1, the surfactant (1 ′) obtained in Comparative Reference Examples 1-2 as an emulsifier in the amount shown in Table 1,
Polymerization was repeated by repeating the same procedure as in Example 1 except that the solution of (2 ') and the neutralizing agent of the type and amount shown in Table 1 were used. However, these surfactants had insufficient emulsifying power. It was sufficient, and the polymerization could not be carried out to the end because the polymerization was unstable and agglomerated. Comparative Example 3 In Example 1, as an emulsifier, the solution of the surfactant (3 ′) obtained in Comparative Reference Example 3 in the amount shown in Table 1 and the neutralizing agent in the type and amount shown in Table 1 were used. Example 1 other than use
The same operation as above was repeated to obtain an aqueous resin dispersion liquid [3 ′]. Detailed results are summarized in Table 1. Comparative Examples 4 to 6 Hytenol N-as an emulsifier in Examples 2 to 4
The same procedure as in Examples 2 to 4 was repeated except that 2 parts of 08 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used and no neutralizing agent was used. ] Detailed results are summarized in Table 1. Example 9 A flask similar to that of Example 1 was charged with 196.7 parts of pure water and 4.9 parts of the solution of the reactive surfactant (1) obtained in Reference Example 1, and neutralized by adding 1.6 parts of 28% aqueous ammonia. . The mixture was heated to 65 ° C while gently blowing nitrogen gas. A polymerizable monomer mixture consisting of 22.4 parts of butyl acrylate, 6.6 parts of glycidyl methacrylate, and 1 part of trimethylolpropane trimethacrylate was prepared in the dropping funnel, and 10 of them were prepared.
Parts were dropped into the flask. Then 2,2'-azobis (2
4 parts of a 5% aqueous solution of amidinopropane) dihydrochloride were injected. After 10 minutes, the rest of the polymerizable monomer mixture was added dropwise, and the addition was completed in 20 minutes. After continuing stirring for 30 minutes, a polymerizable monomer mixture consisting of 39.7 parts of butyl acrylate and 30.3 parts of methyl methacrylate was prepared in a dropping funnel as the second stage polymerization and added dropwise over 1 hour. During the polymerization, the temperature was maintained at 65 to 70 ° C, and after the second stage dropping was completed, the mixture was stirred at the same temperature for 1 hour to complete the polymerization, and the non-volatile content of 33.7
%, PH = 8.4 aqueous resin dispersion

[9] was obtained. Example 10 Similar to Example 1 except that the same amount of 5% aqueous solution of potassium persulfate was used instead of the 5% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride. The operation was repeated to obtain an aqueous resin dispersion liquid [10]. Detailed results are summarized in Table 1. Example 11 The aqueous resin dispersions [1] to [10] and [1 '] to [6'] obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were dried on a Teflon plate to give a film thickness when dried. It was cast to a thickness of 0.2 to 0.3 mm, dried at 20 ° C. for 1 day to form a film, and then heated at 130 ° C. for 3 minutes to prepare a test film. The following tests were performed on the water resistance and appearance of the obtained film to evaluate the performance of each aqueous resin dispersion. As a result, in a system using the reactive surfactant composed of a polymerizable unsaturated group-containing compound as an emulsifier, a significant improvement in water resistance is obtained as compared with a system using other high molecular weight or low molecular surfactant as an emulsifier. I was seen. Further, when at least one of the polymerizable monomers has a functional group capable of reacting with a carboxyl group, water resistance is further improved, and a polymerizable monomer containing a functional group capable of reacting with a carboxyl group is contained. The water resistance was further improved in a system in which the polymerizable monomer mixture was not emulsion-polymerized as a second stage after emulsion-polymerizing the polymerizable monomer mixture. Detailed results are shown in Table 2. Test method Water resistance: The test film was cut into about 20 mm square and weighed (W ₀ ). The film was immersed in deionized water for 3 days, pulled up to gently wipe off water on the film surface, and then weighed (W ₁ ). Further, the film is dried at 100 ° C for 1 hour,
After cooling, it was weighed (W ₂ ). The water absorption rate and the elution rate were calculated by the following formulas to evaluate the water resistance of the test film. Film appearance: The transparency of the film immersed in deionized water for 3 days was evaluated. ○: Transparent and no change △: Pale white ×: Whitening Example 12 Aqueous resin dispersions [2] obtained in Examples 2 and 6,
[6] and the aqueous resin dispersion liquid [4 ′] obtained in Comparative Example 4
20 g / m ² on each of the calcium silicate plates and 120 ° C
After drying in a hot air drier for 10 minutes, the adhesion of the coating film to the substrate, the hot water resistance and the frost damage resistance were examined. As for the aqueous resin dispersions [2] and [6], the primary adhesion, Very good results were obtained for both hot water resistance and frost damage resistance, but satisfactory results were not obtained for water resistance and frost damage resistance with the aqueous resin dispersion [4 ′]. Detailed results are shown in Table 3. Test Method Primary Adhesion: The coating film was cut into 5 × 5 grids with a cutter knife at 3 mm intervals, a polyester adhesive tape was pressure-bonded, and then peeled off to examine the remaining state of the coating film. ○: The coating film is not peeled at all Δ: The coating film is partially peeled ×: The coating film is completely peeled Warm water resistance: The test piece coated with the coating film is immersed in warm water at 60 ° C for 5 days and then for 2 days After drying at room temperature, the adhesion was examined by the same method as above. Freezing damage resistance: 10 ° C water immersion for 2 hours → -20 ° C freezing in air 2
One cycle of time was repeated 200 times, and after drying at room temperature for 2 days, the adhesion was examined by the same method as above. Example 13 Aqueous resin dispersions [3] obtained in Examples 3 and 7,
[7] and the aqueous resin dispersion liquid [5 ′] obtained in Comparative Example 5.
As a binder for nonwoven fabric interlining, the following performance tests were conducted. As shown in Table 4, the aqueous resin dispersion liquids [3] and [6] showed excellent washing resistance and excellent adhesiveness. However, the aqueous resin dispersion [5 '] was considerably inferior in washing resistance. Performance test for non-woven fabric interlining Processing conditions Aqueous resin dispersion liquids [3], [7] and [5 '] were diluted with water to adjust the nonvolatile content concentration to 20%. Polyester non-woven fabric interlining (basis weight of 160 g / m ² ) was dipped in this solution, squeezed with a squeezing ratio of 80%, and dried by heating at 100 ° C. for 5 minutes. Washing resistance test The texture was measured according to JIS L-1085 "Nonwoven fabric interlining test method" 45 ° cantilever method. The wash resistance was evaluated based on the percentage of the texture after 5 times of washing retained against the texture before washing. The washing test was also performed according to JIS L-1085. Example 14 Aqueous resin dispersions [4] obtained in Examples 4 and 8,
[8] and the aqueous resin dispersion obtained in Comparative Example 6 [6 ']
Tested by applying to the release paper so that the thickness after drying becomes 15 to 20μ, drying at 100 ° C for 2 minutes, and then sticking the coated paper on it and transferring the adhesive phase from the release paper to the coated paper. I made a paper label to do this. Then, the physical properties of these test paper labels were evaluated by the test methods shown below. As a result, the aqueous resin dispersions [4] and [8]
It was found that the initial properties such as ball tack, adhesive strength and holding power were very excellent, and those physical properties did not drop easily even after storage under high temperature and high humidity, and showed excellent moisture resistance. However, in the aqueous resin dispersion [6 '], the physical properties such as ball tack, adhesive strength and holding power after storage at high temperature and high humidity remarkably deteriorated, and the moisture resistance was very poor. Detailed results are shown in Table 5. Test method tack: The tack was measured by the ball rolling method defined in JIS Z-0237. Adhesive strength: 180 ° peeling adhesive strength determined by JIS Z-0237 (adherend: stainless steel plate g / 25 mm) was measured. Also, the adhesive force when a polyethylene plate was used as an adherend was measured by the same method. Holding power: According to the method specified in JIS Z-0237, a load of 1 kg at 40 ° C on a pasting surface of 20 mm x 20 mm was applied and a holding time or a deviation width after a certain time was measured.

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Claims (8)

[Claims] 1. A general formula (In the formula, R ₁ represents an alkyl group having 6 to 18 carbon atoms, R ₂ ,
R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt of a carboxyl group or a carboxymethyl group, and X
Represents hydrogen, an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group having a polymerizable unsaturated group and an ether bond, an ester group, an amide group or an amino group, and Z represents Nitrile group or a phenyl group which may have a substituent, an amide group or a carboxylic acid alkyl ester group, wherein a is 1 to 500,
b is an integer of 1 to 100, and c is 0 or an integer of 1 to 250. ) Is obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a reactive surfactant composed of a polymerizable unsaturated group-containing compound represented by Characteristic aqueous resin dispersion. 2. The aqueous resin dispersion according to claim 1, wherein at least one of the polymerizable monomers has a functional group capable of reacting with a carboxyl group. 3. General formula (In the formula, R ₁ represents an alkyl group having 6 to 18 carbon atoms, R ₂ ,
R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt of a carboxyl group or a carboxymethyl group, and X
Represents hydrogen, an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group having a polymerizable unsaturated group and an ether bond, an ester group, an amide group or an amino group, and Z represents Nitrile group or a phenyl group which may have a substituent, an amide group or a carboxylic acid alkyl ester group, wherein a is 1 to 500,
b is an integer of 1 to 100, and c is 0 or an integer of 1 to 250. ) An aqueous resin dispersion obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a reactive surfactant composed of a polymerizable unsaturated group-containing compound represented by The coating agent used. 4. The coating agent according to claim 3, wherein at least one of the polymerizable monomers has a functional group capable of reacting with a carboxyl group. 5. A general formula (In the formula, R ₁ represents an alkyl group having 6 to 18 carbon atoms, R ₂ ,
R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt of a carboxyl group or a carboxymethyl group, and X
Represents hydrogen, an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group having a polymerizable unsaturated group and an ether bond, an ester group, an amide group or an amino group, and Z represents Nitrile group or a phenyl group which may have a substituent, an amide group or a carboxylic acid alkyl ester group, wherein a is 1 to 500,
b is an integer of 1 to 100, and c is 0 or an integer of 1 to 250. ) An aqueous resin dispersion obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a reactive surfactant composed of a polymerizable unsaturated group-containing compound represented by Adhesive used. 6. The pressure-sensitive adhesive according to claim 5, wherein at least one of the polymerizable monomers has a functional group capable of reacting with a carboxyl group. 7. General formula (In the formula, R ₁ represents an alkyl group having 6 to 18 carbon atoms, R ₂ ,
R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, a methyl group, a carboxyl group, a carboxymethyl group, or a salt of a carboxyl group or a carboxymethyl group, and X
Represents hydrogen, an ammonium group, an amine base, an alkali metal or an alkaline earth metal, Y represents a hydrocarbon group having a polymerizable unsaturated group and an ether bond, an ester group, an amide group or an amino group, and Z represents Nitrile group or a phenyl group which may have a substituent, an amide group or a carboxylic acid alkyl ester group, wherein a is 1 to 500,
b is an integer of 1 to 100, and c is 0 or an integer of 1 to 250. ) An aqueous resin dispersion obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a reactive surfactant composed of a polymerizable unsaturated group-containing compound represented by Fiber processing agent used. 8. The textile finishing agent according to claim 7, wherein at least one of the polymerizable monomers has a functional group capable of reacting with a carboxyl group.