JPS6257746B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] The present invention relates to a highly stable aqueous emulsion type adhesive for spray cleaning glue. [Prior art] There are two types of washing glue: the dipping type, in which the fabric or clothing is washed, then immersed in the washing glue solution, dried and then ironed, and the other is in which the washing glue solution is sprayed directly onto the washed and dried fabric or clothing. There is a spray-type glue that can be used with an iron. Problems with washing glue in general include how well it slips on the iron, and how well it adheres to the iron.
This problem can be solved by adding emulsions such as wax, polyethylene, and fluorine resins, as well as polyethylene glycol, polypropylene glycol, glycerin, and the like. However, regarding spray-type washing glue,
Furthermore, the following severe conditions must be satisfied. The first thing to consider is its suitability for spraying. This is mainly due to nozzle clogging and the shape of the spray pattern. In order to improve the shape of the spray pattern, the washing glue must have a low viscosity and no stringiness. Due to these problems, modified starch with a lower viscosity is used as the main component of the glue for spray washing glue that is generally commercially available. However, although modified starch has an excellent sizing effect on cotton products, it is known that it is still insufficient for synthetic fiber products such as nylon and polyester, and products blended with cotton. Therefore, synthetic resin emulsions have been attracting attention and various studies have been made. When synthetic resin emulsions are diluted to lower their viscosity in order to eliminate their spinnability and improve the spray pattern, the stability of the emulsion deteriorates and precipitates form, which can lead to nozzle clogging. There is a problem. Further, in the case of emulsion, rust on the container is a major problem as another cause of nozzle clogging. In the case of spray-type cleaning paste, the container had to be made of metal due to internal pressure, so it was difficult to avoid rusting. Next is the texture. Emulsion-type wash glue, which is suitable for spraying, has the problem that even if the resin is improved, the texture of the fabric after ironing is poor and it lacks elasticity. To solve this problem, it must be used in conjunction with modified starch. However, the spray type washing glue is different from the dipping type glue as mentioned above.
It is usually used immediately after spraying on fabric or clothing, while the glue is still undried, for ironing or other areas. In this case, if the washing paste contains modified starch, when sprayed, a portion of the spray mist will not penetrate into the fabric and will remain on the fluff of the fabric.
During ironing, these mist dry on the fluff before penetrating the fabric, forming fine starch flakes (called flaking) that seriously impair the appearance of the finish. When urea or thiourea was added to prevent this, the flaking phenomenon disappeared, but there was a risk that the stability of the emulsion would be destroyed, and if precipitation occurred, it would cause clogging of the nozzle. [Structure of the present invention] As a result of repeated research on these points, the present inventors produced an acrylic polymer emulsion in the presence of a chain transfer agent, neutralized some of its carboxyl groups, and An extremely stable spray that solves all of the above problems by using an emulsion that has been crushed to a particle size of 0.1 μm or less, and combining it with a rust preventive agent, modified starch, urea or thiourea, and a metal sequestering agent. I got a glue for mold washing. That is, the present invention provides one or more monomers selected from (a) esters of acrylic acid or methacrylic acid and _C1 - _C20 aliphatic saturated alcohols.
85 to 99 mol% and 1 of the carboxyl group-containing monomer
~15 mol% is emulsion polymerized in the presence of a chain transfer agent, and 0.1 to 0.7 equivalents of aqueous ammonia, alkaline solution, or amine of the carboxyl group are added to reduce the particle size.
(b) modified starch selected from hydroxyalkylated starch or carboxyalkylated starch; (c) sodium benzoate and/or sodium nitrite; and (d) urea and/or thiourea. e) one or more selected from polyethylene glycol, polypropylene glycol, and glycerin; (f) one or more selected from water-dispersible silicone, wax, polyethylene, and fluorine resin; and (g) metal sequestration. This is a paste for spray cleaning and glue, which is composed of a glue agent and other compounding agents if desired, and has a viscosity of 50 centipoise or less at a solid content concentration of 5% and a temperature of 20°C. In this way, in emulsion-type spray adhesive pastes, the combination of a rust preventive agent and modified starch prevents the occurrence of rust and weakening of the elasticity, and also prevents the occurrence of flaking caused by the combined use of modified starch. In the presence of a chain transfer agent, in order to solve the problem of reduced stability of the emulsion which is prevented by the addition of urea or thiourea and which is newly caused by these additions,
The synergistic effect of each component is achieved through a special composition in which a part of the acid groups of a polymer emulsion containing emulsion-polymerized carboxyl groups is neutralized and a sequestering agent is used in combination. was played, and all problems are considered to have been resolved. Therefore, even if any one of these configurations is missing, the object of the present invention cannot be achieved. Esters of acrylic acid or methacrylic acid and _C1 - _C20 aliphatic saturated alcohols for making the emulsion used in the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, These include 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, nonyl acrylate, and nonyl methacrylate. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and half esters thereof. Chain transfer agents for making the emulsion used in the present invention include methanol, ethanol, _C1 - _C4 alcohols, halogen-substituted _C1 - _C4 hydrocarbons such as carbon tetrachloride, and acetaldehyde. C ₂ to C ₄ aldehydes such as
Mercaptans such as dodecyl mercaptan are used. The amount used is based on the total amount of monomer.
0.5-5% by weight is preferred. As the neutralizing agent for making the emulsion used in the present invention, volatile neutralizing agents such as ammonia water, alkali hydroxides such as caustic soda and caustic potash, and amines such as triethanolamine are used. Since the purpose of the degree of neutralization is to reduce the emulsion particles to 0.1 μm or less, the amount of neutralizing agent used is within the range of 0.1 to 0.7 equivalents of the acid groups in the polymer. The hydroxyalkylated starch or carboxyalkylated starch used in the present invention includes hydroxypropyl starch, hydroxyethyl starch, carboxymethyl starch, and the like. Sodium benzoate or sodium nitrite acts as a rust preventive agent, and the amount used is preferably 0.1 to 2 parts by weight based on the total amount of the paste. Urea or thiourea is used to prevent flaking caused by modified starch, and the amount used is preferably 10 to 100 parts by weight per 100 parts by weight of modified starch. Polyethylene glycol, glycerin, and polypropylene glycol are mainly useful for preventing adhesion to irons. Water-dispersible silicone, wax, polyethylene, and fluororesin mainly have the effect of improving ironing slippage and stain removal. Sequestering agents are substances that combine with metal ions in aqueous solutions to form soluble complex salts and prevent metal ions from being precipitated by other chemicals, such as condensed phosphates, ethylenediamine, etc. Tetraacetate (EDTA), nitrotriacetate, dihydroxyethylglycine, gluconic acid, citric acid, tartaric acid, etc. are used. The amount used is preferably 0.01 to 0.5% based on the total amount of the glue. The weight ratio of the copolymer to the modified starch in the emulsion is preferably 9:1 to 2:8, more preferably 7:3 to 3:7. The total amount of copolymer and modified starch in the sizing agent is 1~
10% by weight is preferred, preferably 3-6% by weight. If desired, additives such as lower alcohols such as ethanol and propanol, fluorescent dyes, bactericides, preservatives, and perfumes may be added to the paste for spray cleaning paste of the present invention. Although the sizing agent of the present invention may be used in a pump-type spray container, it is usually used by filling it into an aerosol pressure-resistant can together with a propellant. Liquefied propane or butane or mixtures thereof are preferably used as propellant. The ratio of the propellant to the sizing agent of the present invention is 1:9 to 1:9.
3:7 is preferred. [Effects of the Invention] The spray-washing glue of the present invention has no stringiness, so it has a good spray pattern, and even when ironed immediately after spraying, it does not flake, has good ironing gliding, and does not stick to the iron. do not have. It also has good stability, does not cause rust, and therefore does not clog the nozzle. The texture after finishing is very good, and the adhesion is particularly good for blended fabrics such as cotton/Tetoron. Also, if necessary, glue and dirt can be easily removed by using a mildly alkaline detergent such as a heavy duty detergent. Next, the present invention will be explained with reference to Examples and Comparative Examples. Example 1 50 parts by weight of methyl methacrylate, 40 parts by weight of butyl acrylate, and 10 parts by weight of methacrylic acid were mixed in the presence of 1 part by weight of dodecyl mercaptan using a nonionic surfactant and an anionic surfactant as emulsifiers. After emulsion polymerization by the method, 0.5 equivalent of aqueous ammonia to the methacrylic acid used was added to subdivide the emulsion particles to obtain a hydrosol with an average particle diameter of about 0.03 μm and a concentration of 30%, and then a sizing agent with the following composition was added. Created. Above hydrosol (concentration 30%) 10 parts by weight hydroxyethylated starch (solid content)
3 〃 Sodium benzoate 0.5 〃 Urea 1 〃 Polyethylene glycol 2 〃 Silicone emulsion (30% concentration) 0.5 〃 Ethylenediaminetetraacetic acid (EDTA) 0.1 〃 Water 82.9 〃 5% of this glue has a viscosity of 30 centipoise at 20℃. It was hot. Example 2 20 parts by weight of 2-ethylhexyl acrylate, 73 parts by weight of methyl methacrylate, and 7 parts by weight of acrylic acid in the presence of 2 parts by weight of carbon tetrachloride, using a nonionic surfactant and an anionic surfactant as emulsifiers. hand,
After emulsion polymerization by a conventional method, triethanolamine in an amount of 0.7 equivalent to the acrylic acid used was added to finely divide the emulsion particles, and the average particle size was approximately
A hydrosol with a diameter of 0.02 μm and a concentration of 30% was obtained. Then, a glue having the following composition was prepared. Above hydrosol (concentration 30%) 10 parts by weight carboxyethylated starch (solid content)
2 Sodium nitrite 0.5 Urea 1 Polypropylene glycol 2 Wax emulsion (concentration 30%) 0.5 Citric acid 0.1 Water 83.9 The viscosity of this glue at 5% and 20°C was 40 centipoise. Comparative Example 1 A sizing agent prepared in exactly the same manner as in Example 1 except that dodecyl mercaptan was not used. Comparative Example 2 A paste prepared in exactly the same manner as in Example 1 except that it was not neutralized with aqueous ammonia. Therefore, the average particle size of the emulsion was 0.2 μm. Comparative Example 3 A sizing agent prepared in exactly the same manner as in Example 2 except that no carboxyethylated starch was used. Comparative Example 4 A paste prepared in exactly the same manner as in Example 1 except that sodium benzoate was not added. Comparative Example 5 A paste prepared in the same manner as in Example 2 except that urea was not added. Comparative Example 6 A paste prepared in exactly the same manner as in Example 1 except that EDTA was not added. Comparative Test The following test was conducted on a spray cleaning glue prepared by filling an aerosol can with the glue obtained in the Examples and Comparative Examples and liquefied propane gas at a weight ratio of 8:2. The results were as shown in Table 1. (Spray pattern) Sprayed on a black cotton cloth at a distance of 15 cm. If it spread evenly, it was rated as ○, and if it was uneven, it was rated as ×. (Flaking) The black cotton cloth sprayed in the above test was immediately ironed, and those that whitened were rated x, and those that did not were rated ○. (Rust-prone) Take the glue solution in a beaker, put a nail in it,
The rusting property was examined after one week. Rusted items ×,
Those that did not do so were marked as ○. (Nozzle clogging) One week later, each spray cleaning glue was sprayed again and the state of clogging was examined. Items that were clogged were rated ×, and items that could be sprayed were rated ○. (Texture) Regarding the cotton cloth that was sprayed, dried, and ironed, those with a smooth feel were rated as ○, and those without were rated as ×. (Adhesive removal property) I washed it with a heavy detergent and checked the adhesive removal. 【table】

Claims (1)

[Claims] 1 (a) Acrylic acid or methacrylic acid and C ₁ ~
85 to 99 mol% of one or more monomers selected from esters with _C20 aliphatic saturated alcohols and 1 to 15 mol% of a carboxyl group-containing monomer are added as a chain transfer agent. emulsion polymerization in the presence of
(b) A modified starch selected from hydroxyalkylated starch or carboxyalkylated starch, and (c) an emulsion whose particle size has been refined to 0.1 μm or less by adding 0.1 to 0.7 equivalents of carboxyl group aqueous ammonia, alkaline solution, or amine; ) Sodium benzoate and/or sodium nitrite; (d) urea and/or thiourea; and (e) one or two selected from polyethylene glycol, glycerin, and polypropylene glycol.
(f) one or more selected from water-dispersible silicone, wax, polyethylene, and fluororesin, and (g) a sequestering agent and optionally other compounding agents, and the viscosity depends on the solid content concentration. 5%, a glue for spray cleaning that has a value of 50 centipoise or less at a temperature of 20°C.