JPH0118187B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention provides a powdered laundry glue composition that is inexpensive, has excellent properties as a glue such as tension hardness, has good dispersibility and solubility, and has no uniformity in glue. It is related to. [Prior art] Conventionally used laundry glues include those containing starch as the main component, natural polymers such as carboxymethyl cellulose, and synthetic polymers such as polyvinyl alcohol and vinyl acetate copolymers. There are those whose main components are molecules, and their forms include powder, paste, liquid, and aerosol. Sizing agents based on starch are inexpensive and widely used. In addition, glues containing natural polymer derivatives as main ingredients have been used for a long time to bring out the characteristics of clothes made from natural materials. Furthermore, those whose main components are synthetic polymers such as polyvinyl alcohol and vinyl acetate copolymers are widely used because they do not rot or mold. Furthermore, in recent years, synthetic polymers with high adsorption properties for clothing that can be glued even under conditions such as electric washing machines with a bath ratio (clothing/water weight ratio) of 1/20 to 1/30 have been put on the market. ing. [Problems to be Solved by the Invention] In general, starch-based glues that have been alpha-ized at high temperatures are used, but this powder product tends to become gel-like when dissolved, resulting in uneven adhesiveness. is likely to occur. In liquid form, problems such as alpha starch aging, rotting, and mold growth occur. natural polymer derivatives such as carboxymethyl cellulose,
Gluing agents whose main component is synthetic polymers such as polyvinyl alcohol do not spoil, but when used in powder form, they tend to become gel-like when dissolved, resulting in uneven adhesiveness. On the other hand, sizing agents whose main component is vinyl acetate copolymer are mainly used in liquid form, which is uneconomical as they transport water. It cannot be made too large, and therefore a product with sufficient tension performance cannot be obtained. Further, it is difficult to use this product in powder form due to problems with solubility and dispersibility in water. Various glues have problems that need to be solved in this way, but in order to achieve the same tension performance, which is the original purpose of glue, the cheapest starch-based glue is the best. The most important thing is to solve the problem regarding the drug. In addition, regarding the form, it is desired to solve the problem of a powdered paste that is easy to handle and can be administered easily, and several inventions have been made. For example, JP-A-51-102196 discloses that an aqueous dispersion of starch, a vinyl acetate copolymer, an alkaline agent, and an acidic substance is alpha-ized at 90 to 150°C, dried,
He proposed producing a sizing agent with good water solubility by powdering it, and published JP-A-50-46991.
The publication proposes a powdered laundry glue with good solubility in water, which is composed of partially saponified polyvinyl alcohol, glyoxal, and an inorganic salt with a high coagulability. Although these technologies show improved solubility in water compared to conventional methods, solubility evaluations are performed at low concentrations, i.e., 2 g/400 cc, and at high concentrations such as 1 Kg/10. It does not show good solubility under these conditions and is still not satisfactory. Such conditions are commonly implemented in places such as cleaning shops, for example. In addition, JP-A-54-68491 proposes a granular powder paste consisting of etherified starch, a dispersant, and a smoothing agent, which is sieved to 15 meshes or less, but the amount of the smoothing agent added to the etherified starch is 10. The amount is as high as ~15% by weight, which has the disadvantage of reducing tension performance. On the other hand, another problem that needs to be solved with powdered adhesives is the improvement of adsorption to clothing.
Publication No. 121671 discloses a cationic powder laundry paste made of water-dispersible cationic resin powder obtained by drying a cationic vinyl polymer aqueous emulsion. However, even with this technology, sufficient solubility cannot be obtained under conditions of high concentration and high usage amount, and furthermore, since the main ingredient is something other than starch or modified starch, it is difficult to impart the same tension performance to clothing. This results in the disadvantage of being uneconomical. [Means for Solving the Problems] As a result of intensive research in order to solve the problems, the present inventors have developed a method that uses sodium sulfate, silicone, and a specific cationic compound in combination, and particles in a specific particle size range. They discovered that it could be used and completed the present invention. That is, the present invention provides a powdered laundry thickening agent based on starch partially or entirely alpha-ized, modified starch partially or entirely alpha-ized, or a mixture thereof, in which sulfuric acid is added to 100 parts by weight of the starch. Sodium 1-20 parts by weight, silicone 0.01-3
part by weight, and 0.1 to 15 parts by weight of a cationic surfactant or cationic polymer, and 70% by weight or more of the powder particles have a particle size in the range of 40 to 250μ. The present invention provides a drug composition. Starch partially or entirely alpha-ized and partially or totally alpha-ized modified starch provided in the present invention are used as the main base material to impart tension and hardness to clothing, but in order to provide sufficient tension performance, teeth,
It is desirable that the powdered laundry glue composition of the present invention contains 66.6% by weight or more. The raw material starch may be ordinary starch such as corn, potato, wheat flour, or tapioca. Modified starches may be obtained from these starches by well-known methods such as etherification, esterification, and oxidation, such as hydroxypropylated starch, hydroxyethylated starch, phosphorylated starch, acetated starch, and cyanoethyl starch. There are modified starches. From these raw starches, partially or completely alpha-alphaped starch can be obtained by well-known methods as described below. In the present invention, sodium sulfate is used as a water solubility improver and an apparent specific gravity adjuster for powdered laundry size compositions. Sodium sulfate is used in an amount of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of starch that has been partially or completely alpha-ized or modified starch that has been partially or completely alpha-ized. When the amount is less than 1 part by weight, a sufficient solubility improvement effect is not exhibited, and when it is more than 20 parts by weight, sufficient tension and hardness cannot be obtained. Sodium sulfate may be mixed with the raw starch before alphaning the raw starch, or may be after-blended after the alphaning and formulation are completed. The silicone used in the present invention may be either an oil type or an emulsion type, and preferably has a viscosity of 5 to 5000 cps. What is generally referred to as silicone includes dimethylpolysiloxane and its modified products. Modified polysiloxanes include epoxy modified, alkyl modified,
A variety of products can be produced by modification methods such as amino modification, carboxyl modification, alcohol modification, fluorine modification, alkyl aralkyl polyether modification, epoxy/polyether modification, polyether modification, olefin modification, α-methylstyrene modification, and higher fatty acid modification. be. In the present invention, materials produced by any of these modification methods can be used. The silicone oil emulsion may generally be any emulsion prepared by emulsifying dimethylpolysiloxane with an emulsifier, but oil-in-water type emulsions using a nonionic surfactant as the emulsifier are particularly preferred. Silicone is used as a dispersibility improver in water for powdered laundry starch compositions, and is 0.01 to 3 parts by weight per 100 parts by weight of starch that has been partially or completely alpha-ized or modified starch that has been partially or completely alpha-ized.
It is desirable to add 0.1 to 2 parts by weight, preferably 0.1 to 2 parts by weight. If the amount added is less than 0.01 part by weight, the particles cannot be made sufficiently hydrophobic, and if it is more than 3 parts by weight, sufficient tension performance will not be achieved, and furthermore, the hydrophobization of the particles will be too strong, resulting in a powdery laundry glue. This is undesirable because the dissolution rate of the composition in water is significantly reduced. Furthermore, silicone is expensive and therefore uneconomical. Silicone adsorbs on the surface of alpha-alpharated starch or alpha-fumed modified starch, makes the particles hydrophobic, and prevents the particles from sticking to each other when the powdered laundry starch composition is added to water, thus preventing them from forming lumps. prevent,
Dissolve and disperse uniformly. For this purpose,
Although the silicone may be mixed with the raw starch before alphaning the raw starch, it is more desirable to carry out after-blending after the alphaning and formulation are completed. Silicones also exhibit an organic synergistic effect with other essential ingredients, giving garments a unique and desirable finish. Furthermore, silicone's smoothness-improving effect also improves workability such as ironing. In the present invention, the cationic surfactant or the cationic polymer increases the adsorption performance of the powdered laundry starch composition of the present invention to clothing, and therefore can be used for dehydration by squeezing after gluing or by using an electric washing machine. This prevents the sizing agent from being wastefully drained, and also exhibits an organic synergistic effect with other essential ingredients, giving clothing a unique and desirable finish. Cationic surfactants are well known in the art, and any of them may be used in the present invention, but preferably mono-long chain alkyl ammonium salts, di-long chain alkyl Ammonium salts and long-chain alkylamide imidazolinium salts are good. As the mono-long chain alkyl ammonium salt, for example, one represented by the following formula (1) is used. [In the formula, R is an alkyl group having 8 to 22 carbon atoms, R ₁
~ _R3 is a benzyl group or an alkyl group having 1 to 3 carbon atoms, or ( _-CH2CH2O ) _{-o1H group} ( _n1 is a number of 1 to 10),
X represents an anion such as chloride ion, methyl sulfate ion, ethyl sulfate ion, glycolate ion, para-toluenesulfonate ion, etc.] Preferred examples of the mono-long chain alkyl ammonium salt represented by formula (1) include beef tallow, Examples include trimethylammonium salt, tetradecyltrimethylammonium salt, and dodecyltrimethylammonium salt, and preferred examples of the salt include chloride, methosulfate, and ethosulfate. As a di-long chain alkyl ammonium salt, the following formula
The one shown in (2) is used. [In the formula, R, R ₂ , R ₃ and Examples include ethoxyammonium salts, and preferred salts include chloride, methosulfate, and ethosulfate. As the long-chain alkylamide imidazolinium salt, for example, one represented by the following formula (3) is used. [In the formula, R, R ₂ and Examples include merging. As the cationic starch or cationic cellulose, for example, those represented by the following formula (4) are preferable. (wherein A is a starch residue or a cellulose residue,
R′ represents an alkylene group or a hydroxyalkylene group, and R ₄ , R ₅ , and R ₆ are the same or different and form a heterocycle containing an alkyl group, aryl group, aralkyl group, or a nitrogen atom in the formula. You may. X is chlorine, bromine, iodine, sulfuric acid, sulfonic acid,
Indicates anions such as methyl sulfate, phosphoric acid, nitric acid, etc. _L
represents a positive integer) Such cationic starch can be obtained, for example, by reacting starch with glycidyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride under alkaline conditions. It can also be obtained by quaternizing dimethylaminoethylated starch. Furthermore, it can also be obtained by reacting starch with 4-chlorobutene trimethylammonium chloride. On the other hand, cationic cellulose can be obtained, for example, by subjecting hydroxyethyl cellulose to the above reaction. The degree of cation substitution of the cationic cellulose or cationic starch is preferably 0.01 to 1, that is, 0.01 to 1, preferably 0.02 to 0.5 cationic groups are introduced per anhydroglucose unit. The degree of substitution is
Less than 0.01 is not sufficient, and it may be greater than 1, but from the viewpoint of reaction yield, it is preferably 1 or less. In addition, as a cationic vinyl polymer, the following formula
Examples are those represented by (5) to (8). (In the formula, R ₇ is a hydrogen atom or a methyl group, R ₈ , R ₉ ,
R ₁₀ is the same or different, hydrogen atom, carbon number 1
~4 alkyl group or substituted alkyl group, Y represents an oxygen atom or an NH group in an amide bond, and X is a formula (4)
(m is an integer from 1 to 10) (In the formula, R ₁₁ , R ₁₂ , and R ₁₃ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a substituted alkyl group, and X is the same as in formula (4)) (In the formula, X is the same as formula (4)) Poly(N-vinyl-2,3-dimethylimidazolinium chloride) A ring-closing polymer of a cationic diallyl compound is exemplified by one represented by the following formula (9). (In the formula, R ₁₄ and R ₁₅ are the same or different,
It represents an alkyl group or substituted alkyl group having 1 to 2 carbon atoms, and X represents an anion. ) Among these cationic polymers, the cationic polymer represented by formula (4) is preferred. In the present invention, the cationic surfactant or cationic polymer is preferably 0.1 to 15 parts by weight, based on 100 parts by weight of starch partially or entirely alpha-ized or modified starch partially or entirely alpha-ized. It is desirable to use 0.2 to 5 parts by weight. If it is less than 0.1 part by weight, there will be no sufficient adsorption performance improvement effect, and 15
Adding more than part by weight does not increase the effect and is therefore uneconomical. These cationic surfactants or cationic polymers may be added before alphaning the raw starch, or may be after-blended after alphaning and formulation, but if the cationic polymer is a starch derivative Alternatively, in the case of a cellulose derivative, it is preferable to add it to the raw material starch and alphanize it together with the raw material starch. Methods for alphaning raw starch are well known, but the following method is preferred, for example. That is,
Raw starch or modified starch as described above was added to an appropriate amount of water, then a suspension was made with or without the addition of other essential ingredients, alpha-ized at 90 to 180°C, dried, and powdered. After that, the unadded essential ingredients are added, and the particles with a particle size of 40 to 250μ are added to the laundry glue composition.
The product can be obtained by sieving to a content of 70% by weight or more. When alphaning raw starch by heating, carbonates such as soda carbonate, sodium bicarbonate, and sodium sesquicarbonate, phosphates such as sodium pyrophosphate, sodium tripolyphosphate, sodium orthophosphate, and sodium tetraphosphate are used as alphaning aids. It is preferable to add appropriate amounts of borates and silicates such as borax, phosphoric acid, boric acid, silicic acid, etc., that is, within a range where the content of partially or fully alphaned starch does not become less than 66.6%. The degree of alphaning can be determined by the following method. (1) Pour 5.0g of the powder after alphaning into a 100ml graduated cylinder, add water to make 100ml, and disperse and dissolve the powder well. (2) After leaving to stand for 1 hour, an opaque layer will be formed on the bottom layer and a transparent layer will be formed on the top layer, so read the volume occupied by the opaque layer portion. (3) It is judged that the larger this value is, the more alpha conversion is progressing. Although the degree of alphaning can be determined by this method, it is preferable that the read value is 60 ml or more, and it is desirable to adjust the heating temperature, the concentration of the raw starch suspension, the amount of alphaning aid added, etc. Powdering and sieving may be carried out by conventional methods, but it is necessary to adjust the pulverizer or sieve so that particles with a particle size of 40 to 250 μm account for 70% by weight or more of the total.
If there are many particles smaller than 40μ, the particles are too fine and dispersibility deteriorates, and if there are many particles larger than 250μ, the particles are too coarse and cause uneven adhesive on clothing. Further, fragrances, bactericides, preservatives, fluorescent dyes, pigments, etc. may be added as necessary. [Effect of the invention] In the present invention, like a cleaning shop,
Even when a large amount of starch agent is used for laundering large quantities of clothing, it has excellent solubility and dispersibility in water under conditions of high concentration and high usage amount, and does not cause uneven glue, making it easier to wash clothes. Because of its excellent adsorption performance, adhesive is not wasted, and it is possible to achieve the same tension performance as conventional products with half the amount of adhesive used. Furthermore, due to the organic synergistic effect of each component, it has a much better finish (texture) than conventional products, and of course, there is no need for heat treatment to prepare the size liquid, and it is easily dispersed in cold water. ,melt. [Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited in any way by these Examples. In the examples, parts indicate parts by weight. In the examples, the following test method was used. Test method (dispersibility, dispersion speed) Dispersion speed Pour 1 kg of glue sample into 15 plastic buckets filled with 25°C tap water. The dispersion speed was evaluated based on the time it takes for all of the applied glue to sink below the water surface. Dispersibility Pour 1 kg of glue sample into 15 plastic buckets filled with 25°C tap water. The dispersibility is
Immediately after adding the glue, it was thoroughly stirred with a stirring rod, poured into a wire mesh of 60 tiler mesh, and the coarse particles remaining on the wire mesh were evaluated according to the following criteria. ○: All passed through the wire mesh. ◯ to △: There were a few small particles of 5 mm or less. Δ: Particles of 5 to 10 mm were present. Δ to ×: Particles of 10 to 30 mm were present. ×: Particles of 30 mm or more were present. (Gluing method) Washing machine treatment: 30 cotton sheets (approximately 10
(kg), 50 T/C mixed Y shirts (approximately 10 kg) were added, 6 kg of 5% glue solution was added, water was added to achieve the specified bath ratio, the mixture was stirred for 5 minutes, dehydrated for 1 minute, and air-dried. It was later used as a fabric for evaluation. Hand processing: Pour 500ml of water into a washing tub, add 2g of sizing agent, disperse well, and then wash 1/2 cotton sheet (approx. 150g) or 1 T/C mixed Y shirt (approximately 150g).
g), rub it in by hand for 2 minutes, dehydrate it for 1 minute in the dehydration tank of a washing machine, and then air dry it to prepare a test cloth. (Evaluation method for test fabric) Tension hardness After the gluing test, the sheets or Y-shirts were sprayed with mist (30 g water/1 m ² ), pressed (130°C, 1 minute), and kept at a constant temperature and humidity of 25°C and 65% RH. After leaving it in a room for a day and night, it was cut into a predetermined size, and its tensile hardness was measured using a pure bending tester manufactured by Kato Tekko Co., Ltd. The larger the bending stiffness value, the harder the cloth is finished. Preference for finish The sheets or Y-shirts after the starching test were sprayed (30g water/1m ² ) and pressed (130℃, 1 minute), and left in a constant temperature and humidity room at 25℃ and 65% RH for one day and night. A female panel of 10 women gave scores based on the following evaluation standards through pairwise comparison with standards, and judgment was made based on the total score of 10 people. +2: Like the standard +1: Slightly like the standard 0: Same as the standard -1: Slightly dislike the standard -2: Dislike the standard Adhesive unevenness After the adhesion test, the sheets or Y-shirts were heated at 25°C.
After leaving it in a constant temperature and humidity room at 65%RH for a day and night,
The fabric was carefully observed with the naked eye and evaluated according to the following criteria. ○: No unevenness observed. ○～△: Adhesion of glue of 3 mm or less is observed. Δ: Adhesion of 3 to 5 mm of glue is observed. Δ to ×: Adhesion of glue of 5 to 10 mm is observed. ×: Adhesion of glue of 10 mm or more is observed. Workability After the gluing test, heat the sheets or Y-shirts at 25℃.
After leaving it in a constant temperature and humidity room at 65%RH for a day and night,
After actually spraying 30 sheets or Y-shirts with a predetermined amount of water, we hand-finish them with an iron (chrome plating) to ensure smooth ironing and adhesion of starch to the iron, in accordance with the following standards: evaluated. 〇: Even after finishing 30 sheets or more, it is smooth and does not stick. 〇～△: After finishing 20 to 30 sheets, there was a decrease in slippage and adhesion. △: After finishing 10 to 20 sheets, there was a decrease in slippage and adhesion. Δ to ×: After finishing 5 to 10 sheets, there was a decrease in slippage and adhesion. x: When 5 or fewer sheets were finished, there was a decrease in slippage and adhesion. Example 1 From 100 parts of starch, 5 parts of sodium sulfate, cationic starch (trimethylaminohydroxypropylated starch, nitrogen content 0.6%, 1% aqueous solution viscosity 40 cps) or 2 parts of monotallow alkyltrimethylammonium chloride, 100 parts of tap water suspension at 150℃
After turning into alpha with heated rollers, drying, and crushing, silicone (TSA made by Toshiba Silicone Co., Ltd.)
730, emulsion type, silicone content 40%)
After blending was carried out in an amount of 2.5 parts in terms of pure silicone content, and the mixture was sieved using a sieve as shown in Table 1. These samples were tested for dispersibility and dispersion speed according to the test method described above, tension hardness by gluing test,
Adhesive unevenness was measured. The results are shown in Table 1. As is clear from Table 1, all of the products of the present invention were very good. The gluing was done in a washing machine (bath ratio 1/
5).

[Table] Muchloride was used.
Example 2 100 parts of hydroxypropylated starch, 5 parts of sodium sulfate, cationic cellulose {JR-400,
Manufactured by Union Carbide Comp., degree of hydroxyethyl substitution (average number of hydroxyethyl groups introduced per unit of anhydroglucose) 1.6 to 2.1,
Cation degree of substitution 0.35-0.45, nitrogen content 1.7-2.2
%} or a suspension consisting of 2 parts of di-tallow alkyldimethylammonium chloride and 100 parts of tap water,
After alphaning by heating at 95℃ for 2 hours
After drying with heated rollers at 130℃ and further pulverizing,
Silicone (TSA-730 manufactured by Toshiba Silicone Co., Ltd., emulsion type, silicone content 40%) is mixed with the dry and pulverized product in a Nauta mixer in an amount converted to pure silicone (see Table 2), and sieved. at 40
Particles with a particle size of ~250μ were sieved to 85% by weight. These samples were evaluated for dispersibility, dispersion speed, and workability using a gluing test according to the test method described above. The results are shown in Table 2. As is clear from Table 2, all of the products of the present invention were very good. The gluing was done in a washing machine (bath ratio 1/
5).

【table】

[Table] In Nos. 7 and 8, di-tallow alkyl dimethyl ammonium chloride was used.
Example 3 100 parts of starch, 5 parts of sodium sulfate, 2 parts of the same cationic starch used in Example 1, tap water
A suspension consisting of 100 parts was turned into alpha with a heated roller at 150°C, dried, and then ground to form silicone (KF-96, oil type, manufactured by Shin-Etsu Silicone Co., Ltd.).
100 cps) X part (see Table 3) was mixed with the dry pulverized product in a Nauta mixer and sieved using a sieve so that particles with a particle size of 40 to 250 μm were 85% by weight. These samples were evaluated for tension hardness and finish preference in a gluing test according to the test method described above. The results are shown in Table 3. As is clear from Table 3, all of the products of the present invention were very good. Note that gluing was done in a washing tub.

[Table] Example 4 100 parts of starch, X parts of sodium sulfate (see Table 4),
A suspension consisting of 2 parts of the same cationic starch or di-tallow alkyldimethylammonium methosulfate as used in Example 1 and 100 parts of tap water,
After alphaning with a heated roller at 150℃, drying, and crushing, silicone (manufactured by Shin-Etsu Silicone Co., Ltd.)
Mix 2 parts of KF-96, oil type, 10cps with the dry crushed product in a Nauta mixer, and sieve for 40~
The particles were sieved to contain 85% by weight of particles with a particle size of 250μ. The dispersibility and dispersion rate of these samples were measured according to the test method described above. The results are shown in Table 4. As is clear from Table 4, all of the products of the present invention were very good. The gluing was done in a washing machine (bath ratio 1/
5).

[Table] Methosulfate used.
Example 5 A suspension consisting of 100 parts of starch, 5 parts of sodium sulfate, X parts of the same cationic cellulose used in Example 2 (see Table 5), and 100 parts of tap water was mixed with 150 parts of starch.
After turning into alpha with heated rollers at ℃, drying, crushing, silicone
After spraying 2 parts (200, oil type, 50cps), 85 particles with a particle size of 40 to 250μ are sieved.
It was sieved to make the weight percentage. The tension hardness of these samples was measured by a gluing test according to the test method described above. The results are shown in Table 5. As is clear from Table 5, all of the products of the present invention were very good. Note that the gluing was done using a washing machine.

[Table] Example 6 A suspension consisting of 100 parts of starch, 5 parts of sodium sulfate, part X of various cationic surfactants or cationic polymers (see Tables 6 and 7), and 100 parts of tap water was prepared.
After turning into alpha with a heating roller at 150℃ and drying,
Grind and silicone (SH- manufactured by Toray Silicone Co., Ltd.)
200, oil type, 5 cps) was mixed with the dry crushed product in a Nauta mixer, and sieved to 40 to 250μ
It was sieved so that particles with a particle size of 85% by weight were contained. The tension hardness of these samples was measured by a gluing test according to the test method described above. The results are shown in Tables 6 and 7. As is clear from Tables 6 and 7, the products of the present invention were all very good. Note that the pasting was carried out in a washing machine, and the test cloth used was only a T/C mixed Y shirt.

【table】

【table】

【table】

Claims (1)

[Claims] 1. In a powdered laundry thickening agent whose main ingredient is starch partially or entirely alpha-ized, modified starch partially or totally alpha-ized, or a mixture thereof, 1 part by weight of sodium sulfate is added to 100 parts by weight of the starch.
~20 parts by weight, 0.01 to 3 parts by weight of silicone, and 0.1 to 0.1 parts by weight of cationic surfactant or cationic polymer.
15 parts by weight of a powdered laundry glue composition, wherein 70% by weight or more of the powder particles have a particle size in the range of 40 to 250μ.