JPS63225669A - Synthetic resin emulsion for lye-preventive coating agent - Google Patents

Abstract

PURPOSE:To obtain the title emulsion which has an excellent effect of preventing lye and excellent workability in coating, adhesiveness, and waterproofness, and is safe and free from pollution, by incorporating one or more specified surface active agents. CONSTITUTION:A monomer, such as a (meth)acrylate monomer or an aromatic vinyl monomer, and if necessary, an unsaturated monomer of formula I (wherein R7 is H, CH3 or C2H5; R8-10 are each 1-4C alkyl, cyclohexyl or pheny; X is halogen) are made to execute emulsion polymerization at 40-90 deg.C in an aqueous medium in the presence of a polymerization catalyst, such as 2,2'-azobis(2-amidinopropane) hydrochloride of formula II, using at least 70wt.% of one or more surface active agents selected from cationic surface active agents of formulas III and IV (wherein R1 and R6 are each 8-24C alkyl; R2 is having a 1-2C aralkyl in alkyl moiety, R1 or R3; R3-4 are each 1-4C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous cationic synthetic resin emulsion for use in a coating agent for clay.

When applying water-based paint to wooden boards such as natural flat boards and plywood,
When applying water-based paint on top of the coating on the wood base material,
Or a dirty room t im +: When applying water-based paint, the scum inside or on the surface of the wooden board, or the scum on the dirty wall surface oozes out onto the surface of the newly applied water-based paint, causing the paint surface to become dirty. The appearance of the product was often damaged.

Conventionally, to prevent discoloration of the paint surface due to such scum,
Prior to applying the water-based paint, an organic solvent-based primer was applied. However, organic solvent-based paint brushers have problems such as the dangers associated with the use of organic solvents, deterioration of the working environment, and extremely poor workability. The emergence of has long been anticipated.

As a result of intensive research aimed at solving such technical problems, the present inventors surprisingly discovered that a coating agent containing a cationic synthetic resin emulsion as a main component is extremely effective in preventing oxidation, thereby completing the present invention. This is what led to this.

Conventionally, cationic synthetic resin emulsions have been mainly used as additives for strengthening mortar, added to beaters as paper modifiers, and partially used as primers for cement bases. , it has also been proposed to be used as an undercoat material to improve the adhesion between wood cement boards and cement-based finishing paints (Japanese Patent Laid-Open No. 1983-1999).
-92184), cationic synthetic resin emulsions have extremely limited uses compared to anionic or nonionic synthetic resin emulsions.The present invention has developed a completely new use for cationic synthetic resin emulsions. It is expected that this will greatly contribute to technological innovation in the coating industry as a whole.

The coating agent for abrasive soil of the present invention is mainly composed of a cationic synthetic resin aqueous emulsion, and preferably the synthetic resin aqueous emulsion is represented by formula (I), where RI is an alkyl group having 8 to 24 carbon atoms. represents, R7 is aralkyl having 1 to 2 carbon atoms in the alkyl moiety, alkyl having 8 to 24 carbon atoms, or 1 to 2 carbon atoms in the alkyl moiety;
4 alkyl, R5 and R4 independently represent alkyl having 1 to 4 carbon atoms, and X represents chlorine, bromine, iodine or fluorine, a cationic surfactant of the formula (II), where: R5 represents alkyl having 8 to 24 carbon atoms,
m and n independently represent integers of 5 to 25, and a cationic surfactant of the formula (I[I)Ra N
H2・HA (Ill) In the formula, R6 represents an alkyl having 8 to 24 carbon atoms, and A represents 1 equivalent of an acid residue. One or more selected from the group consisting of cationic surfactants. This is a coating agent for aqueous soil containing a cationic surfactant. Among the above cationic surfactants, formula (I
) and formula (n) are preferred, and cationic surfactants of the formula (n) are particularly preferred.

Since the paint agent for scum soil of the present invention is water-based, it is free from danger and problems in the working environment compared to conventionally used organic solvent-based primers. It also exhibits excellent effects in terms of adhesiveness, adhesive strength, and waterproofness.

As used herein, "scum" refers to a substance that oozes out onto the paint film from the base material when a water-based paint is applied to the base material and causes discoloration of the paint film surface during or after drying. Typical examples of such substances include scum on wood and cigarette tar on indoor walls that have been used for a long time.

In an embodiment in which the paint for dirt of the present invention is used, for example, the paint for dirt of the present invention is applied onto a base material such as plywood, fiberboard, particle board, etc., and then water-based fibers are further applied on top of the paint. Wall materials, general-purpose indoor and outdoor paints, and other spraying materials may be applied to indoor wall surfaces (base materials) that have become dirty with cigarette tar or scum from the base materials due to long-term use. After applying the stain coating agent of the present invention on top, a water-based finishing agent as described above may be applied.

Furthermore, after applying the coating agent for gray soil of the present invention to the plywood base material,
Apply putty on top of this to improve the smoothness of the plywood surface,
If necessary, decorations are done by printing patterns or pasting wallpaper.

Preferably, the base material to which the paint for dirt of the present invention is applied is a wood material such as plywood, fiberboard, or particle board (mainly refers to a material containing wood material, preferably 50% by weight of wood). (referring to the base material occupying the surface area) and the wall surface whose surface is soiled by use (referring to the surface coated with paint or the surface pasted with wallpaper, etc.), and among these, the wall surface whose surface is soiled by use is particularly suitable.

Conventional water-based paint coating methods are suitably adopted as the coating method for the paint for scorch soil of the present invention, but coating methods such as brush, roller, spray, roll, and curtain flow coating are preferred, and the coating film thickness is Approximately 0.0 as a dry coating film.
005-0.45mm, preferably 0.01-0.45
mm, particularly preferably 0.02 to 0.40 mm, * also preferably 0.02 to 0.2 mm, and 0.005 mm
If it is too thin (less than 0.45 mm), the anti-snap effect will be insufficient, which is undesirable, and if it is too thick (more than 0.45 mm), there will be no particular advantage.

The synthetic resin constituting the cationic synthetic resin aqueous emulsion, which is the main component of the Aku-Osaka coating agent of the present invention, is a homopolymer or copolymer of one or more monomers having polymerizable double bonds. Examples of such monomers include (meth)acrylic acid ester monomers, aromatic vinyl monomers, vinyl ester monomers, and acrylonitrile monomers, among which (meth) Acrylic acid ester monomers and aromatic monomers are preferred.

Examples of (meth)acrylic acid ester monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, Examples include butyl methacrylate, 2-ethylhexyl methacrylate, tert, butylaminoethyl methacrylate, aminoethyl acrylate, aminoethyl methacrylate, dimethylaminoethyl methacrylate, and the like. Among these, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate are preferred.

Examples of the aromatic vinyl monomer include styrene, methylstyrene, dimethylstyrene, ethylstyrene, butylstyrene, benzylstyrene, and chlorostyrene, with styrene and methylstyrene being preferred.

As the vinyl ester spinning wheel cover, for example, vinyl acetate,
Examples include vinyl propionate, vinyl acetate, and vinyl vasatate, among which vinyl acetate and vinyl vasatate are preferred. Examples of the acrylonitrile monomer include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.

Preferred examples of the polymer constituting the aqueous emulsion of the coating agent for paint according to the present invention are: - one or two of the above monomers;
or more, and formula (■) 8゜o R111 (■) In the formula, R6 represents H, methyl or ethyl, and R8, R9 and Rlo independently represent alkyl having 1 to 4 carbon atoms, cyclohexyl or phenyl. Examples of monomers of formula (IV) are 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 2-hydroxy-3-methacryloxypropyl trimethylammonium chloride, Hydroxy-3-acryloxypropyl trimethylammonium chloride, 2-hydroxy-3-methacryloxypropyl triethylammonium bromide,
2-hydroxy-3-methacryloxypropyltributylammonium chloride, 2-hydroxy-3-
Methacryloxypropylmethylethylbutylammonium chloride, 2-hydroxy-3-methacryloxypropyldimethylphenylammonium chloride, 2-hydroxy-3-methacryloxypropyldimethylcyclohexylammonium chloride, etc. Among them, 2-hydroxy-3- Methacryloxypropyltrimethylammonium chloride is preferred.

In addition, ethylenically unsaturated monomers having carboxyl groups, crosslinkable monomers, (meth)acrylic acid amide monomers,
Ethylenically unsaturated monomers having carboxyl groups, which may be copolymerized with vinyl halide monomers and olefin monomers as necessary, include maleic acid, fumaric acid, maleic anhydride, etc. , crotonic acid, acrylic acid, methacrylic acid, itaconic acid, etc., among which acrylic acid, methacrylic acid, and itaconic acid are preferred.

Examples of crosslinkable monomers include divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, hexylene glycol dimethacrylate, ethylene glycol diacrylate, hexylene glycol diacrylate, and glycidyl. Examples include acrylate, glycidyl methacrylate, and the like.

(Meth)acrylic acid amide monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide,
Examples include N,N'-dimethylacrylamide and hydroxyethyl acrylamide, and examples of halogenated vinyl monomers include vinyl chloride, vinylidene chloride, and vinyl fluoride.

Further, examples of the olefinic monomer include ethylene, propylene, butadiene, etc., and vinylpyrrolidine and the like can also be used.

A particularly preferable example of the polymer constituting the aqueous synthetic resin emulsion of the acrylic coating agent of the present invention is methyl methacrylate or styrene in an amount of 0 to 200 parts by weight, preferably 30 to 150 fE per 100 parts by weight of butyl acrylate. Department,
Most preferably 50 to 120 parts by weight and 0 to 60 parts by weight of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, preferably 2 to 30 parts by weight, most preferably 5 to 15 parts by weight. It is a polymer.

The cationic synthetic resin aqueous emulsion of the present invention can be any resin as long as it is a cationic aqueous emulsion obtained from the above-mentioned monomers, but generally the above-mentioned monomers are homopolymerized or copolymerized under emulsion polymerization conditions. obtained by doing.

In addition, a cationic aqueous emulsion obtained by solution polymerizing the monomer and post-emulsifying it can be used,
Although a cationic aqueous emulsion or a cationic aqueous emulsion obtained by post-adding a cationic surfactant to a nonionic synthetic resin aqueous emulsion can be used, emulsion polymerization is preferred.

Emulsion polymerization, which is a preferred polymerization means for the cationic aqueous synthetic resin emulsion used in the present invention, is carried out by a method known per se using a surfactant and/or protective colloid in the presence of a polymerization catalyst in an aqueous medium. It is done. The surfactant used is a cationic surfactant, and a nonionic surfactant can also be used in combination with the cationic surfactant. The cationic surfactant and the nonionic surfactant that can be used in combination may be used alone or in combination of two or more types.

Preferred cationic surfactants are those of formula (I) in which R8
~R6 and X are a cationic surfactant having the above meanings, formula (II), wherein Rs, m and n are a cationic surfactant having the above meanings, and R, -NH , -HA where R1 and A are cationic surfactants having the above-mentioned meanings, and formula (CI) and formula (II)
The cationic surfactants of formula (I) are more preferred, and the cationic surfactants of formula (I) are particularly preferred.

Among the cationic surfactants of formula (I), formula (I') where R and t represent alkyl having 10 to 22 carbon atoms, and R2' represents R, /, benzyl, or alkyl having 1 to 22 carbon atoms; Preferred are cationic surfactants in which R4' represents alkyl (preferably methyl), and R and/or R4' independently represent alkyl having 1 to 4 carbon atoms (preferably methyl). Examples of the cationic surfactant of formula (I') include octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, didodecyldimethylammonium chloride, dodecylbenzyldimethylammonium chloride, Tetradecylbenzyldimethylammonium chloride, octadecylbenzyldimethylammonium chloride, tetradecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, hexadecylbenzyldimethylammonium chloride, balmityltrimethylammonium chloride, oleyltrimethylammonium chloride, Sibal Examples include mitylbenzyltrimethylammonium chloride and dioleylbenzyltrimethylammonium chloride.

Among the cationic surfactants of formula (n), formula (■') is used, where R5' represents an alkyl having 10 to 20 carbon atoms, and m/ and n' independently represent an integer of 5 to 25. The following cationic surfactants are preferred. As an example of a cationic surfactant of formula (■'), m / and n' are each 1
0 to 20 polyoxyethylene dodecylamine, polyoxyethylene hekidecylamine, polyoxyethylene octadecylamine, and the like.

Among the cationic surfactants of formula (III), those of formula (m
') R,'-NH,・HA (DI') In the formula, R6
A cationic surfactant in which ' represents an alkyl having 10 to 20 carbon atoms and A represents an acid residue is preferred. Examples of cationic surfactants of formula (■') include dodecylamine acetate, tetradodecylamine acetate, octadecylamine acetate, dodecylamine hydrochloride, tetradecylamine hydrochloride, octadecylamine hydrochloride, and hardened beef tallow. Examples include amine acetate.

In the cationic surfactants of formula (I'), formula (■') and formula (■'), "alkyl having 10 to 22 carbon atoms" is coconut oil, palm oil, safflower oil, cottonseed oil,
Alkyl groups (mixed alkyl groups) starting from natural vegetable oils such as rapeseed oil and linseed oil can be particularly preferably used.

Among the many cationic surfactants mentioned above, coconut oil alkylbenzyldimethylammonium chloride, dodecylbenzyldimethylammonium chloride, tetradecylbenzyldimethylammonium chloride and ammonium chloride are particularly most suitable.

In a preferred embodiment, the composition ratio of coconut oil alkyl groups is C1
．． Alkyl; 58%, CI4 alkyl: 35%, Cll
The alkyl content is 27%.

Examples of nonionic surfactants used in combination with cationic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether; polyoxyethylene nonylphenyl ether polyoxyethylene octylphenyl ether; polyoxyethylene alkyl phenyl ethers; polyoxyethylene alkyl esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; sorbitan esters such as sorbitan monolaurate and sorbitan monostearate; polyoxyethylene sorbitan monolaurate; Sorbitan ester ethers such as esters; polyoxyethylene oxypropylene block polymers, polyethylene glycols, etc.

Also, dimethylalkyl betaine, lauryl betaine,
Amphoteric surfactants such as stearyl betaine are also used in combination.

On the other hand, examples of protective colloids include partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose salts and their salts, and natural polysaccharides such as guar gum. , etc. These can be used alone or in combination.

As a polymerization catalyst, persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; 2,2'-azobis-(2-amidinopropane) hydrochloride-hydrogen peroxide, tert-butyl hydro Peroxides such as peroxide, cumene hydroperoxide, paramenthane hydroperoxide, and tert-butyl peroxymaleic acid are used, among which hydrogen peroxide, 2,2'-azobis-(2-amidinopropane) Hydrochloride is preferred, and 2,2'-azobis-(2-amidinopropane) hydrochloride of the above formula (V) is particularly preferred.

Further, during emulsion polymerization, a reducing agent may be used in combination, if desired. Examples include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, and glucose, sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite.

The polymerization temperature can be selected as appropriate, for example, from about 40 to about 90
An example is a temperature such as °C. During polymerization, the entire amount of a given surfactant can be added to the reaction system in advance, or a part can be added to the reaction system in advance to start the reaction, and the rest can be added continuously or at intervals during the polymerization. It can also be added in portions.

Further, each monomer can be added all at once, added in portions, or added continuously, but it is preferable to add them continuously from the viewpoint of reaction control.

In addition to the above-mentioned surfactant and catalyst, a pH regulator, a degree of polymerization regulator, an antifoaming agent, etc. can be added as appropriate during emulsion polymerization.

The viscosity, solid content concentration, pH 1 average particle diameter, glass transition point and degree of polymerization of the cationic aqueous synthetic resin emulsion, which is the main component of the ac-pressure coating agent of the present invention, are not particularly limited, but are as follows: Preferably, the range is .

Solid content concentration (JIS-6833) is 10 to 70% by weight
Preferably 15 to 60% by weight, particularly 30 to 55% by weight.

The viscosity was determined by measuring BH using a rotational viscometer, 2Q rpm, 10~ at 25°C.
l 0.000cps, preferably 10-5.000
cps5, especially 10 to 1.000 cps is preferred.

The pH is 1-8, preferably 1.5-7, particularly preferably 2-6.5.

The average particle diameter is 0. O1~0.6μ, preferably 0°O1
-0.5, particularly preferably 0.02-0.5.

The molecular weight of the polymer is to, 000 to 1.000.000,
Preferably 50,000 to 1. ooo, 000, particularly preferably 10.000 to 500.000.

The glass transition point (hereinafter referred to as Tg) of the polymer is 203~
3236, preferably 220-305', especially 2
60-300'K is preferred. However, the above Tg value (0K)
shall use the value determined by the following formula: Tgt Tgt Tg Snow
Tg in the above expression, T
gt represents the Tg value of the copolymer to be determined, Tgt, Tgt, ..., Tg is the constitutional unit of the copolymer, monomer 5, monomer 2, ..., monomer represents the Tg value of each homopolymer of the body, W l, W 2, ·
..., Wn represents the respective weight fractions of monomer 2, monomer 2, ..., monomer n in the monomer, and Tg of the homopolymer of each QLIL body Examples of values are shown in the table below: Table 1 Tg values of homopolymers of each monomer The above cationic aqueous synthetic resin emulsion may be used as is for the ac-pressure coating agent of the present invention, but if necessary Coloring agents such as pigments, freeze stabilizing aids, film forming aids,
Antifoaming agent, plasticizer, thickener, pH 111 moderator, anti-mold agent,
Additives such as surfactants and other synthetic resins are added.

The anti-soil coating agent of the present invention has a cationic water-based synthetic resin emulsion as its main component, and in this specification, "having it as a main component" means that the anti-soil coating agent contains the cationic water-based synthetic resin emulsion. The content per coating agent is 70% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight or more. The coating agent for sludge soil of the present invention can be further diluted to an appropriate concentration with water or an aqueous solvent before use.

The anti-acid coating agent of the present invention has a coating composition of 0.005-1 as described above.
Preferably 0.01-ring, most preferably 0.02mm
Even extremely thin dry paint films, such as dry paint films, exhibit good anti-acid effects, but in order to make it easier to distinguish between coated areas and uncoated areas during construction, colorants such as pigments are added to the anti-acid film. Examples of such colorants that are preferably added within a range that does not impair the inhibitory effect include titanium oxide,
Titanium yellow, carbon black, beige, dark blue,
Examples include yellow ocher, Hansa yellow, permanent orenno, rhodamine lake, thioindigoleft, 7-thalocyanine puru-, 7-thalocyanine green, and naphthol green. Among these, titanium oxide, carbon black, navy blue, and 7-talocyanine green are preferred. The blending amount thereof is about 0.1 to 10% by weight, preferably about 0.5 to 3% by weight.

In addition, since the paint agent for clay of the present invention is often used on wall surfaces, decorative materials and optical agents commonly used in wall paints, such as wood fibers, aggregates, clays, mica, granules, and fibers, may also be used as needed. Synthetic resins, etc., are added within the range that does not interfere with the anti-slip effect.

The details of the present invention will be explained below with reference to Examples: Example 1 412 g of water was placed in a 21 round bottom flask and heated to 80°C.
Adjust to. After sufficiently purging the inside of the flask with nitrogen, 228 g of butyl acrylate (BA) and 168 g of styrene (St) were added.
mixture of g, 4 g of 2-hydroxy-3-methacryloxypropyltrimethylammonium cloide (HM)
, (BA:St:HM polymerization [ratio 57:42:1)
Alkylbenzeldimethylammonium chloride 6g
132 g of aqueous solution mixed with 2% 2,2'-azobis (
2-amidenopropane) hydrochloride aqueous solution 60. was continuously added under stirring for 4 hours to polymerize and pH 2.8,
Viscosity 70eps, solids content 40.1%, Tg-9″F′,
A cationic emulsion having an average particle size of 0.23 μm was obtained, and this was used as the composition of the present invention.

The above composition was dried with a spatula and then applied to a thickness of about 100μ on top of the plywood. After drying at room temperature for one day, an indoor/outdoor paint (trade name: Neodelux A-20, Asia) was applied. Apply approximately 200g/2 of Kogyo Co., Ltd.) uniformly,
After drying in a drying room at a temperature of 20°C and humidity of 75% for 24 hours, the painted surface was observed and found that there were no yellowing or stains due to scum from the plywood or tar, and the color was white.
Mitsuya No. 4 (manufactured by Tokyo Fukuko Painting Co., Ltd.) was painted, and the appearance was observed after drying, but there was no yellowing or staining. In addition, yellowish brown nicotine obtained by immersing and extracting unused tobacco in water was applied to lauan plywood, applied to the surface of the dried white fiber wall, and after drying, the composition of the present invention was applied to about 100 μm (after drying) with a brush. ), and after drying at room temperature for one day, apply the above indoor/outdoor paint (trade name: Neo Deluxe A-20, manufactured by Asisara Kogyo Co., Ltd.) uniformly at a rate of approximately 200 g/m'' at a temperature of 20°C and a humidity of 75°C. After drying in a drying room for 24 hours, the coated surface was observed to be white with no yellowing or stains due to tobacco tar from the base.

In addition, both the plywood tested in the anti-stick test and the cigarette tar test had excellent adhesive strength and waterproof properties. The results of the locking test are shown in Table 2.

Example 2 Put 416 g of water into a 21 round bottom flask, warm it, and bring it to 80 g.
℃に'I! 4 Adjust. After sufficiently purging the inside of the flask with nitrogen, a mixture of 224 g of butyl acrylate (BA) and 16 g of methyl methacrylate (MMA) was added to 120 g of water.
-Hydroxy-3-7 tacryloxypropyltrimethylammonium chloride (HM) 8g, (BA:MM
A: HM mixing weight ratio 56:42:2) Mix and emulsify 132 g of an aqueous solution in which 4 g of alkyl pensilk methyl ammonium chloride was dissolved, and add 10 g of a 5% aqueous ascorbic acid solution and 5% t-7' methyl hydroperoxide.
Continuously added with 0g for 4 hours under stirring to react, pH 3 viscosity 50cps, solid content 40.2%
A cationic emulsion having a temperature of -3° C. and an average particle size of 0.26 μm was obtained, and this was used as the composition of the present invention. The resulting composition was subjected to a plywood stagnation test and a tobacco stagnation test in the same manner as in Example 1. The test results are shown in Table-2.

Example 3 Emulsion polymerization was carried out in the same manner as in Example 1, except that the monomer mixing ratio, emulsifier, and catalyst were described in Wave-2 below, to obtain a cationic emulsion.

The resulting emulsion was 100. Ethylene glycol 7-15
g1 butyl carbitate acetate 2g1 antifoaming agent 0.0
The composition of the present invention was prepared by adding and mixing 5 g. The resulting composition was subjected to a plywood stagnation test and a tobacco stagnation test in the same manner as in Example 1.

The test results are shown in Table-2.

Examples 4 to 12 Emulsion polymerization was carried out in the same manner as in Example 1, except that the monomer mixing ratio, emulsifier, and catalyst were described in Wave-2 below, respectively, to obtain a cationic emulsion, which was used in the present invention. The composition was

The obtained composition was subjected to a plywood stagnation test and a tobacco stagnation test in the same manner as in Example 1 using the coating thickness shown in Table 2. The test results are shown in Table-2.

Comparative Example 1 In Example 1, the cationic mo/mer (2-hydroxy-3-7 tacryloxyprobyl trimethylammonium chloride) was not used, and instead of the alkylbennordimethylammonium chloride as an emulsifier, polyester was used. 12g of oxyethylene nonylphenyl ether, 4g of sodium dodecylbenzenesulfonate, 2 as a catalyst
．． A 7-ion emulsion was obtained by using ammonium persulfate instead of 2'-azobis(2-amidinopropane) hydrochloride.

When a test was conducted on lauan plywood in the same manner as in Example 1, the fiber wall, which should be white, was clearly colored yellow due to the scum of the plywood, and the appearance was extremely poor. The same thing happened with tobacco scum, and the fiber walls were so contaminated by seeping tobacco scum that they were unbearable to look at.

The test results are shown in Table-2.

Comparative Examples 2 to 3 Emulsion polymerization was carried out in the same manner as in Comparative Example 1, except that the mixing weight ratio of monomers and the catalyst in Comparative Example 1 were respectively described in Wave-2 below, to obtain an anionic emulsion.

The resulting composition was subjected to a plywood anti-slip test and a tobacco anti-slip test in the same manner as in Comparative Example 1. The test results are written in 1 & -2.

Tobacco smoke test: Measure the dried white paint (Neo Deluxe A-20, manufactured by Ojia Kogyo Co., Ltd.) using a color difference meter ND-5041) E
Measure the color using the mold. Examples on plastic board and wood board,
Measure ΔE with respect to the comparative example. ΔE=0~0.2 as 10,
9 for ΔE=0.2-0.4, 8 for ΔE=0.4-0.6
, 7 for ΔE=0.6-0.8, 6 for ΔE=0.8-1.0, 5 for ΔE=1.0-1.2, 5 for ΔE=1.2-1.4
4, ΔE=1.4~1°6, 3, ΔE=1.6~1.
8 was set as 2, and ΔE=1.8 or more was set as 1. Evaluation: Up to α8, the pigment is almost indistinguishable to the naked eye, but the score is 3.
Below, you can see that the yellow color has a very drastic change.

Patent applicant: Nippon Carbide Industries Co., Ltd. (and one other person)

Claims (1)

[Claims] 1. Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) In the formula, R_1 represents an alkyl having 8 to 24 carbon atoms, and R_2 represents the number of carbon atoms in the alkyl moiety. represents aralkyl having 1 to 2 carbon atoms, alkyl having 8 to 24 carbon atoms, or alkyl having 1 to 4 carbon atoms, R_3 and R_4 independently represent alkyl having 1 to 4 carbon atoms, and X is Cationic surfactant representing chlorine, bromine, iodine or fluorine and formula (III) R_6-NH_2・HA(III) In the formula, R_6 represents alkyl having 8 to 24 carbon atoms, and A is 1 equivalent of A cationic synthetic resin aqueous emulsion for anti-acid coatings containing one or more cationic surfactants selected from the group consisting of cationic surfactants representing acid residues. 2. Synthetic resin has the formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) In the formula, R_7 represents H, methyl or ethyl, and R_8, R_9, and R_1_0 independently have a carbon number of 1 to
4. The aqueous cationic synthetic resin emulsion for coating agents according to claim 1, wherein X represents alkylcyclohexyl or phenyl, and X is a copolymer of unsaturated monomers having the above meaning. 3. The synthetic resin is a polymer containing residues of a polymerization catalyst of 2,2'-azobis(2-amidinopropane) hydrochloride of formula (V) ▲Mathematical formula, chemical formula, table, etc.▼(V) A cationic synthetic resin aqueous emulsion for coating agents according to claim 1 or 2.