JPS6240464B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aerosol-type hardener composition used as a spray, and more specifically, by using a specific acrylic or styrene synthetic resin aqueous dispersion, the composition has excellent storage stability and corrosion resistance of the container. , and the valve button does not get stuck, and when used as an aerosol to harden the creases of pants, the pleats of skirts, etc., the spray properties are uniform when sprayed onto fabrics, making it easy to work with and can be used on processed fabrics. To obtain a hardener composition whose finish is not affected by the type of fabric, has a uniform and appropriate texture, whose texture does not always change, and which does not exhibit any finishing fabric mechanism. The present invention relates to an aerosol type hardener composition characterized by: Conventionally, various polymer solutions or dispersions such as vinyl acetate resin, urethane resin, methyl cellulose, carboxymethyl, cellulose soda, and hydroxyethyl cellulose have been studied as hardener compositions, but these resins It has various drawbacks. In other words, vinyl acetate resins turn yellow or become aged over time after being applied to woven fabrics, and especially in aerosol formulations, corrosion of the container, clogging of the valve, and even the stability of the contents may occur. It's bad and I can't get anything satisfactory. Furthermore, even with urethane resin, the stability of the contents
Corrosion of the container is bad, and if you iron the resin after applying it to the fibers, the resin will stick to the iron so much that you won't be able to get a satisfactory hardness.Furthermore, it will easily stain the colored fibers. The disadvantage is that it has a bad texture. In addition, the stability of the contents of cellulose-based resins is very poor, and the viscosity in particular has a large temperature dependence.
There are many shortcomings. Furthermore, various proposals have been made regarding the above technology. For example, Japanese Patent Publication No. 41-20436 proposes a sizing agent containing a copolymer of acrylic acid or methacrylic acid, an alcohol ester of methacrylic acid having 3 or less carbon atoms, and vinyl acetate, or a water-soluble salt thereof. However, when these glues are used in aerosol form, they contain vinyl acetate as an essential ingredient, which can lead to corrosion of the container, poor stability of the glue, coloring, emitting strange odors, and inability to spray uniformly. It has drawbacks such as sagging, so it cannot be used in an aerosol type. In addition, JP-A-49-117795 proposes a laundry paste made of an aqueous emulsion of ethylene-vinyl acetate copolymer, but ethylene-vinyl acetate copolymer generally cannot be sprayed uniformly, and modifiers Even if the spray can be uniformly sprayed using ironing methods, it has disadvantages such as thermal decomposition on the ironing surface and producing a pungent odor when ironing, so it is not used very often. Furthermore, Japanese Patent Laid-Open No. 52-53086 proposes a household glue composition containing a resin emulsion of cationic polymer particles as a main ingredient. When used, it lacks mechanical stability and gels at the valve of the aerosol injection port, making it impossible to spray uniformly. Additionally, aerosol pastes have drawbacks such as poor long-term stability. As a result of intensive research to solve these problems and obtain a composition particularly suitable for an aerosol type hardening agent, the present inventors have found that the amount of dispersed synthetic resin with a particle size of 0.6μ or more and 5μ or less can be reduced by dispersion synthesis. By using an acrylic or styrene synthetic resin that is 70% by weight or more based on the total amount of resin and whose dispersed synthetic resin has a glass transition temperature (hereinafter sometimes abbreviated as Tg) of 0°C to 80°C, the above-mentioned container can be manufactured. Excellent corrosion resistance, etc.
In addition, the valve button does not get stuck, and when used as an aerosol to tighten the creases of pants, pleats of skirts, etc., the spray properties are uniform when sprayed onto fabrics, making it easy to work with and can be used on processed fabrics. It has been discovered that the finish of woven fabric has a uniform and appropriate texture regardless of the type of fabric, and the texture does not always change, and furthermore, it has characteristics such as no staining of the finished fabric. , completed the invention. That is, the present invention provides an aerosol-type hardening agent composition containing an aqueous synthetic resin dispersion as a main component, wherein (a) the amount of dispersed synthetic resin with a particle size of 0.6 μ or more and 5 μ or less is based on the total amount of the dispersed synthetic resin; 70% by weight or more, and (b) the dispersed synthetic resin is an acrylic or styrene synthetic resin with a glass transition temperature of 0°C to 80°C. . The synthetic resin dispersed in the aerosol-type hardener composition containing the aqueous synthetic resin dispersion of the present invention as a main component (herein referred to as dispersed synthetic resin) preferably has a particle size of 0.6 μm or more and 5 μm or less. is 0.8μ or more
4μ or less, more preferably 1μ or more to 3μ or less, and the dispersed synthetic resin with the particle size accounts for 70% or more, preferably 80% of the weight of all particles of the dispersed synthetic resin.
% or more, more preferably 90% or more, is preferably used. If the particle size is less than 0.6 μm, there are drawbacks such as stains occurring when sprayed onto a woven fabric, and this phenomenon is particularly severe on colored base fabrics. If the particle size is too large than 5 μm, there will be disadvantages such as whitening even when ironed when sprayed onto a woven fabric, insufficient hardness, and easy settling due to the large particle size. On the other hand, if the dispersed synthetic resin with the particle size is less than 70% of the total weight of the dispersed synthetic resin particles, it will cause stains when sprayed with resin or ironed, as in the case where the particle size is 0.6μ or less. This results in disadvantages such as the occurrence of In addition, the glass transition temperature of the dispersed synthetic resin of the present invention is suitably 0 to 80°C, preferably 5 to 70°C, and more preferably 10 to 60°C. If the Tg is less than 0°C, the processed fabric will not have tension. It has disadvantages such as insufficient hardness, easy staining, and whitening even when ironed at temperatures above 80°C. The acrylic or styrenic synthetic resin dispersion used in the present invention may be a dispersion prepared by any method as long as it is a dispersion of an acrylic or styrene synthetic resin in water. For example, a dispersion obtained by emulsion polymerization, seed emulsion polymerization, suspension polymerization, etc. of an acrylic monomer or a styrene monomer may be used, and a dispersion such as a solution or melt of an acrylic polymer or a styrenic polymer may be used, but preferably as described below. This is a dispersion prepared by an emulsion polymerization method. That is, adding a predetermined amount of emulsifier and water to the reactor,
After raising the temperature to the reaction temperature, the catalyst and monomer are continuously added to react, and after the reaction is completed, the acrylic or styrene dispersion is obtained by cooling and adjusting the pH with aqueous ammonia, etc., which further enhances the effects of the present invention. It can be demonstrated. As the emulsifier, any of anionic, nonionic, cationic, and amphoteric emulsifiers can be used alone or in combination. Examples of anionic emulsifiers include alkyl carboxylates such as sodium oleate and potassium oleate, alkyl sulfates such as sodium lauryl sulfate and sodium higher alcohol sulfate, alkylbenzene sulfonates such as alkylnaphthalene sulfonates, and sodium dodecylbenzenesulfonate. Foonate,
There are dialkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkyl phenol ether sulfates. As a nonionic emulsifier,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene cetyl ether, polyoxyethylene alkyl phenol ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene sorbitan monolaurate, etc. Examples include polyoxyethylene fatty acid esters such as polyoxyethylene sorbitan fatty acid ester, polyethylene glycol, polyethylene glycol monolaurate, and polyoxyethylene polyoxypropylene block polymers. Examples of cationic emulsifiers include quaternary ammonium salts such as lauryltrimethylammonium chloride, alkylamine salts, and polyoxyethylene alkylamines, and examples of amphoteric emulsifiers include alkyl betaines. Also polyvinyl alcohol, partially saponified polyvinyl acetate, hydroxymethyl cellulose,
Protective colloids such as hydroxyethyl cellulose can also be used. In particular, it is preferable in the present application to mainly use an aluon emulsifier.
Examples of catalysts used in emulsion polymerization include persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, peroxides such as hydrogen peroxide and tert-butyl hydroperoxide, and water-soluble azo compounds. In addition, sodium bisulfite, sodium thiosulfate, L-
A reducing agent such as ascorbic acid, tartaric acid, Rongarit, etc. can be used in combination. Production is usually carried out at a reaction temperature of 40 to 80°C, but it is also easy to carry out the process outside this temperature range. The monomers may be added all at once at the beginning of the reaction, or added continuously or in several portions, but from the viewpoint of ease of production, the method of continuous addition is preferable. Further, the monomer may be added as it is or after being emulsified with an aqueous emulsifier solution. Other operations such as adding a polymerization degree regulator and a buffering agent, which are carried out in ordinary emulsion polymerization, are employed. If necessary, the pH may be adjusted after the reaction with ammonia, caustic soda, amine compounds, etc., or a film-forming agent such as butyl cellosolve or butyl carbitol acetate, or other solvents such as alcohol may be added. In the present invention, it is preferable to use ammonia as the PH adjuster since it is easily volatile. In addition, the acrylic polymers constituting the acrylic synthetic resin dispersion include, for example, methyl acrylate, ethyl acrylate, butyl acrylate,
Acrylic acid alkyl esters such as 2-ethylhexyl acrylate and/or methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, acrylic monomers such as acrylonitrile, preferably methyl acrylate, methyl methacrylate, ethyl At least 50% by weight, preferably 60% by weight or more, particularly preferably 90% by weight of a polymer or copolymer, or a mixture of such polymers, consisting of one or more monomers such as acrylate and butyl acrylate.
It contains the above. The styrenic polymer constituting the styrenic synthetic resin dispersion is, for example, a polymer or copolymer made of at least one monomer selected from styrene, 2-methylstyrene, vinyl toluene, and the like, and the above-mentioned acrylic monomers. Examples include polymers and mixtures of these polymers and copolymers, and more preferably a copolymer consisting of the styrene monomer and the acrylic monomer. The styrenic monomer constituting these styrenic polymers is preferably used in an amount of 50% by weight or more, particularly preferably 60% by weight or more, still more preferably 70% by weight or more, based on the total monomers. In addition, examples of copolymerizable monomers other than the acrylic monomer and styrene monomer suitable for polymerizing the acrylic polymer and styrenic polymer include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleic anhydride. acids, unsaturated acids such as fumaric acid or their esters, ethylene, vinyl compounds such as propylene d-olefin, acrylamide, n-methylol acrylamide, vinyl ether, etc., divinylbenzene, diallyl phthalate, triallyl in cyanurate, etc. , preferably acrylic,
Examples include unsaturated acids such as methacrylic acid, itaconic acid, and maleic acid. The unsaturated acid copolymerized with the polymer is preferably in an amount of 0.1 to 5% by weight, preferably 0.2 to 4% by weight, more preferably 0.3 to 3% by weight, based on the polymer. Further, other physical properties of the acrylic or styrenic dispersion of the present invention are not particularly limited, but generally the viscosity is 500 cps or less, preferably 200 to 200 cps.
2csp, more preferably 100 to 5 is suitable, and PH
is 2 to 10, preferably 3 to 9, more preferably 4
~8 is suitable, the solid content is 10 to 70%, preferably 20 to 55%, and the surface tension is
A suitable value is 60 dyn/cm or less, preferably 55 to 30 dyn/cm, and more preferably 50 to 35 dyn/cm. As used herein, the "main component" of the aqueous synthetic resin dispersion as the main component includes any amount as long as it substantially exhibits the effects of the present invention, but for example, water and dispersion resin. The total solid content is 70% by weight or more, preferably 80% by weight or more, based on the aerosol hardening composition, and the dispersed resin solid content is 2 to 20% by weight, based on the aerosol hardening composition. , preferably 3 to 10% by weight, more preferably 4 to 7% by weight. In addition to the synthetic resin dispersion, the composition also contains water-soluble auxiliaries, preservatives, solvents, surfactants, fragrances, antifoaming agents, rust preventives, polyhydric alcohols, insect repellents, silicones, Other additives and auxiliaries can be used. Examples of water-soluble auxiliary agents include starch, starch esters (sodium starch phosphate, starch phosphate, etc.), starch ethers (carboxymethyl starch, hydroxyethyl starch, hydroxypropyl starch, etc.), crosslinked starch (crosslinked starch with phosphate, etc.) ), modified starch, hydroxyethyl cellulose,
Preferred examples include carboxymethyl cellulose, polyvinyl alcohol, sodium alginate, pectin, dextrin, sodium polyacrylate, polyethyleneimine, and preferably starch ethers. Examples of preservatives include benzoic acid, sorbic acid, dehydroacetic acid, para-hydroxybenzoic acid, methyl para-hydroxybenzoate, ethyl para-hydroxybenzoate, butyl para-hydroxybenzoate, and preferably dehydroacetic acid and sorbic acid. Examples include acids. Solvents include saturated monohydric alcohols such as ethanol, methanol, and isopropanol, ethylene glycol, triethylene glycol, diethylene glycol, ethyl cellosolve, butyl cellosolve, methyl carbidol, ethyl carbisol, and polyethylene glycol (average molecular weight 300
~500) Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc., preferably diethylene glycol, triethylene glycol, etc. can be mentioned. Examples of the surfactant include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylaryl ether, polyoxyethylene cetyl alcohol ether, polyoxypropylene polyoxyethylene cetyl alcohol ether, polyoxyethylene castor oil derivative, alkyl phosphate ester, Examples include polyoxyethylene alkyl ether phosphates, preferably alkyl phosphates, polyoxyethylene alkyl ether phosphates, and the like. In addition, antifoaming agents such as ammonium benzoate, amines, aqueous ammonia, phosphoric acid activators, antifoaming agents such as silicone, octanol, isopropyl alcohol, and commercially available antifoaming agents, fragrances such as essential oils and synthetic fragrances,
Mention may be made of other additives such as glycols, ethylene glycol, silicones, petroleum solvents and the like. The amount of additives such as these auxiliaries used varies depending on their characteristics and purpose, and is not particularly limited, but in general, when water-soluble auxiliaries are used in aerosol type hardener compositions, the amount is 0.5 to 0.5. 10% by weight, preferably 1~
5% by weight, 0.1-0.5% by weight for preservatives, 1-10% by weight for solvents, 0.1% by weight for surfactants.
~0.5% by weight, 0.1-0.5% by weight for fragrances, 0.2-3% by weight for antifoaming agents, 0.05-1.0% for rust preventives.
Preferably, weight percentages are used. The aerosol type hardener composition of the present invention is filled into a sealed aerosol pressure container. At this time,
Fill with propellant at the same time. As the propellant, dimethyl ether, liquefied petroleum gas, etc. are generally used alone or in combination. In addition, the pressure of the product is 2.0 to 5.0Kg/cm ² at 25℃.
Used within the range of When hardening was performed using the above product, the aerosol hardener composition was sprayed uniformly, and the processed surface was hardened uniformly without unevenness or stains. Very good jetting workability was achieved with no liquid dripping or nozzle clogging. Even after the aerosol product was left for one year, its workability was exactly the same as that of the aerosol product immediately after manufacture. Fabrics, clothing, etc. that can be hardened with the composition of the present invention may be synthetic fibers such as polyester, acrylic, or vinylon, cotton cloth, hand-woven cloth, or blends thereof. Finishing is possible. The terms "particle size,""glass transition temperature (Tg)," and "surface tension" used herein have the following meanings, respectively. (1) Dilute a launyl acetate solution with a particle size of 11% 15 to 200 times, put 25 ml of this diluted solution into a test tube, and add 1 drop of the resin dispersion into it. After that, shake it by hand about 10 times, vibrate with ultrasonic vibration for another 4 minutes, and then
Cool in tap water for 15 minutes. This dispersion is poured into small holes in paraffin, and the sample is placed on a wire mesh for electron microscopy that has been previously treated with collodion and reinforced with carbon. After drying this, 10 fields of view were photographed using a transmission electron microscope, and the particle distribution at this time was measured. (2) Glass transition temperature (Tg) The glass transition temperature of individual polymers can be found in “Chemistry of Polymer Latex” by Soichi Muroi,
"Mechanical Properties of Polymer" LE
The method described in Nielsen was adopted.
Further, the Tg of the copolymer is calculated according to the following formula. 1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...
Wn/Tgn Tg, Tgn: absolute temperature, Wn: weight fraction in copolymer composition Each value of Tg is: Methyl acrylate (MA) 278〓 Ethyl acrylate (EA) 246 Butyl acrylate (BA) 216 2-ethylhexyl acrylate (2EHA)
213 Methyl tacrylate (MMA) 376 Vinyl acetate (VAc) 306 Styrene (ST) 363 Methacrylic acid (MAA) 458 Acrylic (AA) 439 (3) Surface tension After diluting the emulsion 5 times with distilled water, measure it using a JUNUI surface tension meter. Moreover, the test method and its evaluation in this specification are as follows. After spraying on the fabric, ironing, and pasting, (a) Texture: Check the texture by lightly squeezing the fabric in your palm to examine its thickness, stiffness, and pliability. is measured using the 5-point method. 5 Very good 4 Good 3 Fairly good 2 Fairly poor 1 Poor (B) Sprayability: Shake the sample well and spray with the spray nozzle 15 cm away from the base fabric to determine the diameter (cm) of the circular pattern of the composition adhered to the base fabric. ). The diameter is measured by measuring the longest diameter of the circular pattern, then measuring the maximum diameter of a straight line that intersects this longest diameter at right angles, and averaging the two diameters. Also, if the sprayability is less than 9cm, the spread will be poor and workability will be poor, but if it is over 9cm, the workability will be good.
The larger the number, the better the workability. (c) Clogged valve button: 30 samples were heated at 35°C.
Tested for 3 months at 90% humidity with a spray cycle of 5 to 7 seconds 3 days, during which time valve buttons were clogged. (d) Stability of contents: Test at 45℃ and observe the viscosity, coloration, odor, etc. of the contents. (e) Container corrosion: Number of months in which corrosion occurred when tested at 45℃. (F) Stains and whitening of base fabric: Cut a 10cm x 10cm square in the cardboard, place this pattern on top of the base fabric, and spray about ^2g of spray liquid per 100cm2. Two samples, one immediately after spraying and one after 5 minutes.
Iron at 170℃ ironing temperature. Measure the presence or absence of stains after ironing. The color difference (ΔE) between the spray surface and the base fabric is measured using a color difference meter (Nippon Denshoku Kogyo Co., Ltd.'s Color Difference Direct Reading Digital Colorimeter Model ND-504DE). The smaller ΔE is, the less the color difference is, and conversely, the larger ΔE is, the more there is a color difference. The relationship between the numerical value of ΔE and the discrimination of color difference by the naked eye is as follows. △E0～0.4 It is completely impossible to distinguish colors with the naked eye. 0.5-0.7 There is a slight color difference. 0.8 to 1.0 Color difference can be distinguished. 1.0 or higher Can be identified at a glance. Reference example 1 In the reactor of 2, 1000 ml of water, 25 g of methyl methacrylate (MMA), 25 g of ethyl acrylate (EA),
Methacrylic acid (MAA) 0.5g, Emulgen 950
Add 0.1 g of emulsifier (manufactured by Kao Soap Co., Ltd.), and after thoroughly purging with nitrogen, the temperature is raised to 60°C. Next, add 10ml of a 3% aqueous solution of potassium persulfate and sodium sulfite.
Add one by one and keep for 10 minutes. Subsequently, a mixed solution of 225 g of methyl methacrylate, 225 g of ethyl acrylate, and 4.5 g of methacrylic acid was continuously added over a period of 4 hours. Furthermore, during the continuous addition of monomers, 50 ml each of 3% aqueous solutions of potassium persulfate and sodium sulfite were continuously added. Also, during the continuous addition of monomers, 50 ml of a 10% Emulgen 950 (emulsifier, manufactured by Kao Soap Co., Ltd.) aqueous solution was added.
is added continuously. After continuous addition of monomer 1
Keep at 60℃ for an hour and cool. The particle size (aμ) of the resulting polymer dispersion is 0.4
It had a relatively uniform distribution of ≦a<0.6, and the nonvolatile content was 30%. Other physical properties are shown in Table-1. Reference Example 2 200 g of the polymer dispersion of Reference Example 1 was added to the flask of No. 2, and after the flask was sufficiently purged with nitrogen, the temperature was raised to 60°C. Using a similar procedure, methyl methacrylate
300g, ethyl acrylate 300g, methacrylic acid 6
g, potassium persulfate and sodium sulfite, 3
% aqueous solution, 50ml each, 0.1% Emulgen 950 aqueous solution
Add 800 ml continuously over 8 hours. The particle size of the obtained polymer dispersion was 0.8 to 1.0μ. Other physical properties are shown in Table-1. Reference Examples 3 to 14 Polymerization was carried out using the same method as in Reference Examples 1 and 2, considering the emulsifiers, dispersions, and monomers listed in Table 1, and polymer dispersions with various compositions and particle sizes were obtained. Created. These results are summarized in Table-1. Reference example 15 Commercially available vinegar beer emulsion (Nicazol CL-
101, manufactured by Nippon Carbide Co., Ltd.). Examples 1 to 21 and Comparative Examples 1 to 7 The resin dispersions of Reference Examples 1 to 14 were used at a resin solid content concentration of 5% by weight, and other additives were blended in the proportions shown in Table 2 to produce aerosol products. . The stability of the contents of this aerosol product and its condition when sprayed and ironed on a base fabric were observed.
The results are shown in Table-2. As can be seen from this, the product of the present invention is extremely stable and the condition of the base fabric is also good.

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Claims (1)

[Scope of Claims] 1. In an aerosol-type hardener composition containing an aqueous synthetic resin dispersion as a main component, (a) the amount of the dispersed synthetic resin having a particle size of 0.6 μm or more and 5 μm or less is the same as that of the dispersed synthetic resin. 70% by weight or more based on the total amount, and (b) the dispersed synthetic resin is an acrylic or styrene synthetic resin with a glass transition temperature of 0°C to 80°C. . 2 The dispersed synthetic resin contains 0.1 to 5% by weight of unsaturated acid.
The composition for an aerosol type hardening agent according to claim 1, which contains: