JPH0745529B2 - Cationic aqueous resin dispersion - Google Patents

Description

Detailed Description of the Invention

(Field of Industrial Application) The present invention relates to a novel cationic aqueous resin dispersion. More specifically, it relates to a cationic aqueous resin dispersion liquid having excellent emulsifying power and capable of forming a film excellent in various properties including water resistance obtained by using a cationic emulsifier having cross-linking reactivity. is there. The cationic aqueous resin dispersion of the present invention has excellent adsorptivity and adhesiveness to various substances because it has a cationic particle charge, and foams as compared with a known emulsifier generally used in the art. Since it can form a high-strength film with less water resistance and good strength, it can be used for fiber processing, glass fiber processing, leather processing, and coating and adhesion to various inorganic and organic materials such as glass, metal, cement, plastics, etc. It is useful in a wide range of fields such as. (Prior Art) Cationic emulsifiers such as dodecyltrimethylammonium chloride, stearyltrimethylammonium chloride, etc. and cationic emulsions obtained by emulsion polymerization of vinyl compounds in the presence of them have hitherto been known and are cationic. Although it is used for various purposes by taking advantage of this fact, it has a drawback that the water resistance and strength of the film are poor. (Problems to be Solved by the Invention) The present invention solves the above-mentioned problems that conventional cationic emulsions have, and therefore, the object thereof is to provide a film with excellent water resistance and strength. It is intended to provide a cationic aqueous resin dispersion which is excellent in stability during emulsion polymerization and stability during storage. (Means and Actions for Solving Problems) The present inventors have found that a polyamine having a hydrophilic primary amino group and / or a secondary amino group and / or a derivative thereof has a hydrophobic group or a hydrophobic group. A cationic modified polyamine obtained by introducing a hydrophilic group and a hydrophilic group through a reactive group such as an epoxy group, a carboxyl group, or an isocyanate group exhibits excellent emulsifying power, and the modified polyamine has a specific functional group. It was found that the compound has a crosslinkability with a compound having Further, when the modified polyamine is used as an emulsifier for emulsion polymerization of a polymerizable monomer, an aqueous resin dispersion having good stability during polymerization can be produced, and the obtained aqueous resin dispersion is
The present invention was found to form a film having excellent stability during storage, excellent water resistance, and high strength, and further, a film having good adhesion to various materials due to its cationic property, and reached the present invention. did. That is, the present invention is to polyamine and / or derivatives thereof having a primary amino group and / or secondary amino group, the general formula ROA _n X (wherein, R a hydrocarbon group having 4 to 28 carbon atoms Where A represents an alkylene group having 2 to 4 carbon atoms, X represents an atomic group having an epoxy group, a carboxyl group, a vinyl group or an isocyanate group or a halogen atom, and n is 0 or 1 to
Indicates an integer of 30. ) A cationic aqueous resin dispersion obtained by emulsion-polymerizing one or more polymerizable monomers in an aqueous medium using a modified polyamine obtained by reacting a chemical represented by is there. The polyamine and / or its derivative used in the present invention is one having at least two nitrogen atoms in the molecule and at least two primary and / or secondary amino groups. The molecule may have a tertiary amino group. Examples of polyamines include polyalkyleneimines obtained by polymerizing or copolymerizing alkyleneimines such as polyethyleneimine obtained by polymerizing ethyleneimine; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, (Poly) alkylenepolyamines such as pentaethylenehexamine; polyamidepolyamines obtained by condensation of polyalkyleneimines and / or (poly) alkylenepolyamines with polybasic acids such as adipic acid; polyalkyleneimines and / or ( Poly) alkylene polyamines and / or polyurea polyamines obtained by reaction of alkylene imines with urea; polyamide poly obtained by copolymerization of alkylene imines with acid anhydrides such as phthalic acid Or the like can be mentioned ester polyamine. Examples of the polyamine derivative include those obtained by addition-reacting the polyamine with an alkylene oxide such as ethylene oxide or propylene oxide, or an α, β-unsaturated acid amide compound such as acrylamide. In the compound represented by the general formula ROA _n X (wherein R, A, X and n are the same as described above) used in the present invention (hereinafter referred to as compound (I)),
Examples of the hydrocarbon group having 4 to 28 carbon atoms corresponding to R in the formula include linear or branched alkyl groups having 4 to 28 carbon atoms, (alkyl) aryl groups, (alkyl) hydrogenated aryl groups, (Alkyl) aralkyl group etc. can be mentioned. Examples of the compound (I) include n having an addition mole number of alkylene oxide such as ethylene oxide, propylene oxide and isobutylene oxide of 1 to 30.
-Octyl polyoxyalkylene glycidyl ether,
n-nonyl polyoxyalkylene glycidyl ether,
Lauryl polyoxyalkylene glycidyl ether, stearyl polyoxyalkylene glycidyl ether, 2
-Primary alkyl polyoxyalkylene glycidyl ethers such as ethylhexyl polyoxyalkylene glycidyl ether; 1 to 30 mol of alkylene oxide is added to a compound of a secondary alcohol having 12 to 14 carbon atoms, and further glycidyl etherified. Thing, carbon number 10
1 to 30 moles of alkylene oxide added to a mixture of 1 to 12 secondary alcohols and further glycidyl etherified secondary alkyl polyoxyalkylene glycidyl ethers; 30 alkyl phenyl polyoxyalkylene glycidyl ethers such as octyl phenyl polyoxy alkylene glycidyl ether, nonyl phenyl polyoxy alkylene glycidyl ether, lauryl phenyl polyoxy alkylene glycidyl ether, stearyl phenyl polyoxy alkylene glycidyl ether, etc. The number of moles of alkylene oxide added is from 1
30 octyl cyclopentyl polyoxyalkylene glycidyl ether, octyl cyclohexyl polyoxyalkylene glycidyl ether, nonyl cyclopentyl polyoxyalkylene glycidyl ether, nonyl cyclohexyl polyoxyalkylene glycidyl ether, lauryl cyclopentyl polyoxyalkylene glycidyl ether, lauryl cyclohexyl polyoxyalkylene glycidyl ether, Alkylcycloalkyl polyoxyalkylene glycidyl ethers such as stearyl cyclopentyl polyoxyalkylene glycidyl ether and stearyl cyclohexyl polyoxyalkylene glycidyl ether; Octylbenzyl polyoxyalkylene glycidyl ether having 1 to 30 added moles of alkylene oxide Alkylbenzyl polyoxyethylene glycidyl ethers such as benzyl, nonylbenzyl polyoxyalkylene glycidyl ether, lauryl benzyl polyoxyalkylene glycidyl ether, stearyl benzyl polyoxyalkylene glycidyl ether; octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, Glycidyl ethers of higher alcohols such as 2-ethylhexyl glycidyl ether; glycidyl ethers of alkylphenols such as octylphenyl glycidyl ether, nonylphenyl glycidyl ether, lauryl phenyl glycidyl ether, stearyl phenyl glycidyl ether; Octyl cyclopentyl glycidyl ether, octyl cyclohexyl Glycidyl ethers of alkylcycloalkanols such as ruglycidyl ether, nonylcyclopentyl glycidyl ether, nonylcyclohexyl glycidyl ether, lauryl cyclopentyl glycidyl ether, lauryl cyclohexyl glycidyl ether, stearyl cyclopentyl glycidyl ether, stearyl cyclohexyl glycidyl ether; octylbenzyl glycidyl ether, Glycidyl ethers of alkylbenzyl alcohols such as nonylbenzyl glycidyl ether, lauryl benzyl glycidyl ether, stearyl benzyl glycidyl ether, etc .; such as C 12 or 14 α-olefin epoxides, C 16 or α olefin epoxides, etc. 1,2-epoxyalkanes; octyliso Alkyl isocyanates such as anate, decyl isocyanate, octadecyl isocyanate, etc .; Reaction of alcohols such as octanol, lauryl alcohol, stearyl alcohol etc. or alkylene oxide adducts of these alcohols with diisocyanates such as tolylene diisocyanate Monoisocyanate compounds obtained by: octanol,
Alcohols such as lauryl alcohol, stearyl alcohol, etc. or alkylene oxide adducts of these alcohols, wherein the unterminated hydroxyl group is substituted with a halogen atom such as chlorine, bromine, iodine; lauric acid,
Saturated fatty acids such as myristic acid, palmitic acid, stearic acid; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, eleostearic acid;
2-ethylhexyl acrylate, lauryl acrylate,
Examples thereof include acrylic acid alkyl esters such as stearyl acrylate, acrylamide, methacrylamide, etc., and one or two selected from these groups.
More than one species can be used. The amount of the above-mentioned compound (I) used to obtain the modified polyamine used in the present invention is not particularly limited, but in order to reproduce sufficient surface activity, it is 0.01 per amine hydrogen in the polyamine and / or its derivative. It is preferred to use from 1 molecule of compound (I). The reaction conditions for obtaining the modified polyamine used in the present invention are not particularly limited and may be appropriately selected depending on the properties and reactivity of the polyamine and / or its derivative and the compound (I), and are appropriately selected if necessary. A catalyst may be used. It is also possible to adjust the pH by adding an acid to the obtained modified polyamine. As the acid, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or the like, or an organic acid such as formic acid, acetic acid, acrylic acid, methacrylic acid or the like can be used. The thus obtained modified polyamine emulsifier has excellent emulsifying power and can stably carry out emulsion polymerization of a wide variety of polymerizable monomers, and thus a cation having excellent performance of the present invention. A water-based resin dispersion liquid is provided. The polymerizable monomer used in the present invention is not particularly limited as long as it contains a polymerizable unsaturated group, but, for example, methyl or ethyl of acrylic acid or methacrylic acid, propyl, isopropyl, butyl, Of linear or branched aliphatic alkyl alcohols or alicyclic alkyl alcohols having 1 to 18 carbon atoms such as isobutyl, octyl, 2-ethylhexyl, lauryl, stearyl or cyclohexyl ester with acrylic acid or methacrylic acid (Meth) acrylic acid esters which are ester compounds; polymerizable unsaturated such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid or maleic acid or fumaric acid monoester Carboxylic acids and salts thereof; vinyl sulfonic acid, styrene Nsuruhon acid, (meth) polymerizable unsaturated sulfonic acids and salts thereof such as sulfoethyl acrylate; (meth) aminoethyl acrylate,
Dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine,
Basic unsaturated monomers such as vinylimidazole and vinylpyrrolidone; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, monoesters of acrylic acid or methacrylic acid with polypropylene glycol or polyethylene glycol, etc. Hydroxyl group-containing unsaturated monomers such as: (meth)
Epoxy group-containing unsaturated monomers such as glycidyl acrylate; (meth) acrylic acid 2-hydroxy-3-
Halohydrin group-containing unsaturated monomers such as chloropropyl; Blocked isocyanate group-containing unsaturated monomers such as phenol adduct of (meth) isocyanatoethyl acrylate; (Meth) acryloylaziridine; Aziridinyl group-containing unsaturated monomers such as (meth) acryloyloxyethylaziridine; Oxazoline group-containing unsaturated monomers such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline A diester of acrylic acid or methacrylic acid with a dihydric alcohol such as ethylene glycol, 1,3-butylene glycol, 1,6-hexane glycol, neopentyl glycol, polyethylene glycol or polypropylene glycol, acrylic acid or methacrylic acid and trimethylol propane Polyfunctional (meth) acrylic acid esters containing two or more polymerizable unsaturated groups in the molecule such as triester with any trihydric alcohol; (meth) acrylamide, methylolated (meth) acrylamide, carbon (Meth) acrylamides such as alkoxymethylolated (meth) acrylamides of 1 to 4 number; vinyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, allyltriethoxysilane, trimethoxysilylpropylallylamine Organic silicon monomers such as; and styrene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, ethylene, propylene, butadiene, Isoprene, dicyclo Ntajien, divinylbenzene, there may be mentioned diallyl phthalate, can be used one or a mixture of two or more selected from these groups. The cationic aqueous resin dispersion of the present invention is obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using the modified polyamine as an emulsifier. The emulsion polymerization can be carried out according to a known method using a known polymerization initiator and other various additives if necessary. The amount of the modified polyamine used as an emulsifier during emulsion polymerization is not particularly limited, but it is preferably used in the range of 0.5 to 200 parts by weight with respect to 100 parts by weight of the polymerizable monomer.
Further, it is preferable to use an emulsifier composed of the modified polyamine alone, but it is free to use together a conventionally known emulsifier so long as the characteristics of the present invention are not impaired. After emulsion polymerization, if necessary, a pH adjusting agent, a curing catalyst, a diluent and the like can be added. The cationic aqueous resin dispersion of the present invention thus obtained has characteristics such as excellent adsorbability to various substances and adhesiveness, little foaming, and excellent long-term emulsion stability. However, if at least one of the polymerizable monomers used for preparing the cationic aqueous resin dispersion is a compound having a functional group capable of reacting with the modified polyamine used in the present invention, it can be obtained. It is preferable because the performance of the cationic aqueous resin dispersion can be further improved. Examples of the functional group capable of reacting with the modified polyamine include a carboxyl group, a sulfonic acid group, an aziridinyl group, an oxazoline group, a hydroxyl group, an epoxy group, a halohydrin group, a blocked isocyanate group, and an alkoxysilyl group. Examples of the compound having a functional group include a polymerizable unsaturated carboxylic acid among the above-mentioned polymerizable monomers, an aziridinyl group-containing unsaturated monomer, an oxazoline group-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer. Examples thereof include monomers, halohydrin group-containing unsaturated monomers, blocked isocyanate group-containing unsaturated monomers, epoxy group-containing unsaturated monomers and organosilicon monomers. (Effect of the invention) The cationic aqueous resin dispersion of the present invention is excellent in stability during storage and uses a crosslinkable emulsifier, so that it forms a film having excellent water resistance and high strength. Since it has excellent properties, it forms a film having excellent adhesion to various inorganic and organic materials such as metal, glass, cement, plastics and various fiber products. Since it has such characteristics, the cationic aqueous resin dispersion of the present invention is used for paper processing, fibers, glass fibers, leather, civil engineering,
It is useful in a wide range of fields such as adhesives and paints. (Examples) Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited to these Examples.
Unless otherwise specified,% means% by weight and part means part by weight. Reference Example 1 45 parts of polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., average molecular weight about 600) in a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer and a reflux condenser. A mixture of α-olefin epoxides having 12 and 14 carbon atoms (AOE-X24, manufactured by Daicel Chemical Industries, Ltd.) 14.7
80 ° C while charging the part and blowing nitrogen gas gently
The mixture was heated to 1, and reacted for 2 hours to obtain an emulsifier (1). Reference Examples 2 to 6 The same procedure as in Reference Example 1 was repeated except that the polyamine and the compound (I) were as shown in Table 1, and the emulsifier (2) was used.
~ (6) was obtained. Reference Example 7 Polyethyleneimine (Epomin SP-012, Nippon Shokubai Chemical Co., Ltd.) was placed in the same flask as used in Reference Example 1.
100 parts of an average molecular weight of about 1200), 50 parts of stearic acid and 70 parts of xylene were charged, and the mixture was heated to 140 ° C. while gently blowing nitrogen gas to carry out dehydration condensation for 4 hours.
After completion of the reaction, xylene was distilled off to obtain an emulsifier (7). Reference Example 8 In the same flask used in Reference Example 1, adipic acid 14
6.1 parts, 112.5 parts of diethylenetriamine and 50 parts of water were charged, and the mixture was heated to 200 ° C. while gently blowing nitrogen gas, and dehydration condensation was performed for 4 hours. After cooling, 39.2 parts of α-olefin epoxide (AOE-X24) was added dropwise from the dropping funnel and reacted at 120 ° C for 3 hours to obtain an emulsifier (8). Reference Example 9 To the same flask as used in Reference Example 1, 60 parts of polyethyleneimine (Epomin SP-006) and 19.6 parts of α-olefin epoxide (AOE-X24) were charged and reacted in the same manner as in Reference Example 1. After cooling, add 179.2 parts of water and stir to form a uniform aqueous solution. Then add an acrylamide aqueous solution consisting of 49.8 parts of acrylamide and 112.1 parts of water prepared in advance from a dropping funnel, and react at 50 ° C for 4 hours. An aqueous solution of emulsifier (9) having a nonvolatile content of 30.7% was obtained. Example 1 A flask equipped with a dropping funnel, a stirrer, an inert gas introducing tube, a thermometer and a reflux condenser was charged with 5 parts of the emulsifier (1) obtained in Reference Example 1 and 100 parts of water to obtain a uniform aqueous solution. The pH was adjusted with acetic acid so that the pH became 4.5, and then diluted with water so that the total amount became 167 parts. 2, as a polymerization catalyst
Charge 3 parts of a 10% aqueous solution of 2'-azobis (2-methylpropanediamine) dihydrochloride, heat to 55 ° C while gently blowing nitrogen gas, stir to form a uniform aqueous solution, and then add it from the dropping funnel. A previously prepared monomer mixture consisting of 50 parts of methyl methacrylate and 50 parts of butyl acrylate was added dropwise at 55 to 60 ° C. over 2 hours. Then, the temperature was maintained at 55 to 60 ° C., and the mixture was further stirred for 1 hour to obtain a cationic aqueous resin dispersion [1] having a nonvolatile content of 39.8% and a pH of 5.3. Examples 2 to 9 The same procedure as in Example 1 was repeated except that the composition of the monomer mixture, the emulsifier and the pH adjuster of the emulsifier were as shown in Table 2, and the cationic aqueous resin dispersion liquid [ 2] ~

[9] was obtained. Example 10 Into the same flask as used in Example 1, 16.3 parts of an aqueous solution of the emulsifier (9) obtained in Reference Example 9 and 90 parts of water were charged and stirred to form a uniform aqueous solution so that the pH was 4.5. P with acetic acid
After adjusting H, the mixture was diluted with water so that the total amount was 167 parts.
Charge 3 parts of a 10% aqueous solution of 2,2'-azobis (2-methylpropanediamine) dihydrochloride as a polymerization catalyst, heat to 55 ° C while gently blowing nitrogen gas, and stir to make it uniform water-soluble. Then, a monomer mixture consisting of 10 parts of glycidyl methacrylate, 45 parts of methyl methacrylate and 45 parts of butyl acrylate, which had been prepared in advance from a dropping funnel, was added dropwise at 55 to 60 ° C. over 2 hours. Then, keep the temperature at 55-60 ° C and stir for an additional 1 hour to remove non-volatile components.
A cationic aqueous resin dispersion [10] having a pH of 5.2 and 39.9% was obtained. Examples 11 to 13 A cationic aqueous resin dispersion liquid was prepared by repeating the same procedure as in Example 1 except that the composition of the monomer mixture, the emulsifier and the type of pH adjuster for the emulsifier were as shown in Table 2. 11] ~ [1
3] was obtained. Comparative Example 1 The same operation as in Example 1 except that an emulsifier aqueous solution obtained by dissolving 5 parts of dodecyltrimethylammonium chloride in 162 parts of water was used instead of the pH-adjusted product of the emulsifier (1) aqueous solution in Example 1. Repeat non-volatile content 39.9%, pH
A comparative aqueous resin dispersion [1] of 5.5 was obtained. Comparative Example 2 As in Comparative Example 1, polyoxyethylene nonylphenyl ether (Nonipol 200, manufactured by Sanyo Chemical Industry Co., Ltd.) 5
Except that the emulsifier aqueous solution obtained by dissolving 162 parts of water in 162 parts is used, the same procedure as in Example 1 is repeated to obtain a nonvolatile content of 40.0%.
%, PH 6.3 comparative aqueous resin dispersion [2] was obtained. Example 14 The cationic aqueous resin dispersions [1] to [13] and the comparative aqueous resin dispersions [1] to [2] obtained in Examples 1 to 13 and Comparative Examples 1 and 2 were placed on a Teflon plate. The dry film thickness is 0.2
The film was cast to a thickness of 0.3 mm, heated and dried at 80 ° C. for 15 minutes to form a film, and then heated at 120 ° C. for 10 minutes to prepare a test film. The obtained film was subjected to the following performance tests to evaluate the performance of each aqueous resin dispersion. The evaluation results are shown in Table 3. 1. Water resistance: The test film was cut into about 2 cm 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 was dried at 100 ° C. for 1 hour, allowed to cool, and then 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. 2. Film strength: The elongation and tensile strength of the film were measured based on the test method described in JIS K-6732. Example 15 The cationic aqueous resin dispersions [1] to [13] and the comparative aqueous resin dispersions [1] to [2] obtained in Examples 1 to 13 and Comparative Examples 1 and 2 were mixed with a glass plate, An aluminum plate and a polycarbonate plate were coated with a No. 16 bar coater and then dried by heating at 80 ° C. for 10 minutes to prepare a coated test plate. The obtained test plate was subjected to the following performance tests to evaluate the performance of each aqueous resin dispersion. The evaluation results are shown in Table 4. 1. Normal adhesion: 1mm on the coating film using a cutter knife
10 mm × 10 mm goggles were cut at intervals, cellophane tape was pressure-bonded and then peeled off vigorously, and the peeled state of the gougins was scored as ⊚, ○, Δ and ×. ⊚: 90 to 100% of non-peelable part ○ ○: 70 to 90% of non-peelable part △: 40 to 70% of non-peelable part × × of non-peelable part Percentage 0-40% 2. Water resistant adhesion: dip the test plate in deionized water for 1 day,
After wiping off the water on the surface of the coating film within 1 minute after pulling it up, an adhesion test was conducted in the same manner as the above-mentioned normal state adhesion.

Claims (2)

[Claims] To 1. A polyamine and / or derivatives thereof having a primary amino group and / or secondary amino group, the general formula ROA _n X (wherein, R represents a hydrocarbon group having 4 to 28 carbon atoms , A represents an alkylene group having 2 to 4 carbon atoms, X represents an atomic group having an epoxy group, a carboxyl group, a vinyl group or an isocyanate group or a halogen atom, and n is 0 or 1
Indicates an integer of 30. ) A cationic aqueous resin dispersion obtained by emulsion-polymerizing one or more polymerizable monomers in an aqueous medium using a modified polyamine obtained by reacting the compound represented by the formula as an emulsifier. 2. The cationic aqueous resin dispersion according to claim 1, wherein at least one of the polymerizable monomers is a compound having a functional group capable of reacting with the modified polyamine.