JPH0118186B2 - - 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, which can be glued even under conditions such as electric washing machines, where the bath ratio (clothing/water weight ratio) is 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. Regarding the form, there is a desire to solve the problem with an economical and easy-to-handle powdered glue, 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, ie, 2 g/400 c.c., for example, 1 Kg/10. It does not show good solubility under high concentration conditions and is still not sufficient. 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] In order to solve the problems, the present inventors have conducted intensive research and found that sodium sulfate, silicone, and boric acid can be used in combination, and particles in a specific particle size range can be used. They discovered this and completed the present invention. That is, the present invention provides a powdered laundry thickening agent whose main ingredient is starch partially or entirely alpha-ized, modified starch partially or totally alpha-ized, or a combination thereof, based on 100 parts by weight of the starch. , sodium sulfate 1-9 parts by weight, silicone 0.01-3
The present invention provides a powdered laundry glue composition containing 0.1 to 3 parts by weight of boric acid and 70% by weight or more of the powder particles having a particle size in the range of 40 to 250μ. . 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 9 parts by weight, preferably 2 to 7 parts by weight, per 100 parts by weight of starch partially or entirely alpha-ized or modified starch partially or totally alpha-ized. When it is less than 1 part by weight, a sufficient solubility improvement effect is not exhibited, and when it is more than 9 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 modified products thereof. Modified polysiloxanes include epoxy modified, alkyl modified, amino modified, carboxyl modified, alcohol modified, fluorine modified, alkyl aralkyl polyether modified, epoxy/polyether modified, polyether modified, olefin modified, α-methylstyrene modified, and high grade. There are various methods of modification such as fatty acid modification. 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, boric acid is used in an amount of 0.1 to 3 parts by weight per 100 parts by weight of starch partially or entirely alpha-ized or modified starch partially or entirely alpha-ized. If it is less than 0.1 part by weight, sufficient tension and hardness cannot be obtained, and if it is used in excess of 3 parts by weight, no further effect can be obtained. Furthermore, when boric acid is added during the alphaning process, it also has the effect of suppressing the adhesion of starch to equipment. 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. Further, phosphoric acid, silicic acid, etc. can be added in appropriate amounts, that is, within a range in which the content of partially or wholly 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, no glue is wasted, and it is possible to achieve the same tension performance as conventional products with half the amount of glue 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 took for all of the applied sizing agent 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 the washing gutter, add 2g of sizing agent, and after dispersing it well, wash 1/2 cotton sheet (approx. 150g) or 1 T/C mixed Y shirt (approx. 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 starching 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. ○ to △: 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 25 sheets or Y-shirts after starch application test
After leaving it in a constant temperature and humidity room at 65% RH for a day and a night, spray 30 sheets or Y-shirts with the specified amount of water, then iron (chrome plating).
After hand finishing, the iron slippage and adhesion of the glue to the iron were evaluated according to the following criteria. ○: Good slippage and no adhesion even after finishing 30 sheets or more. ○ to △: 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. ×: When 5 or fewer sheets were finished, there was a decrease in slippage and adhesion. Example 1 100 parts of starch, 5 parts of sodium sulfate, 0.5 parts of boric acid
A suspension consisting of 100 parts of tap water was alpha-ized with a heating roller at 150°C, dried, and crushed to form silicone (TSA-730, emulsion type, silicone content 40%, manufactured by Toshiba Silicone Corporation). 2.5 parts of the mixture was after-blended 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] Example 2 A suspension consisting of 100 parts of hydroxypropylated starch, 5 parts of sodium sulfate, 1 part of boric acid, and 100 parts of tap water was alpha-ized by heating at 95°C for 2 hours, and then heated at 130°C. After drying with a roller and further pulverizing, silicone (manufactured by Toshiba Silicone Co., Ltd.)
TSA-730, emulsion type, silicone content 40%) is mixed with the dry and crushed product in X part (see Table 2) using a Nauta mixer in an amount converted to pure silicone, and sieved to obtain particles with a particle size of 40 to 250μ. The particles were sieved to a concentration of 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] Example 3 100 parts of starch, 5 parts of sodium sulfate, 1 part of boric acid,
A suspension consisting of 100 parts of tap water was turned into alpha with a heated roller at 150°C, dried, and then crushed to form a suspension containing X parts of silicone (KF-96 manufactured by Shin-Etsu Silicone Co., Ltd., oil type, 100 cps) (see Table 3). ) 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. 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. Incidentally, the gluing was carried out using a washing gutter.

[Table] Example 4 100 parts of starch, X parts of sodium sulfate (see Table 4),
A suspension consisting of 1 part of boric acid and 100 parts of tap water was added to 150
After alphaning and drying with a heating roller at ℃,
Grind and silicone (KF made by Shin-Etsu Silicone Co., Ltd.)
96, oil type, 10 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 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] Example 5 A suspension consisting of 100 parts of starch, 5 parts of sodium sulfate, X parts of boric acid (see Table 5), and 100 parts of tap water was
After alphaning and drying with a heating roller at ℃,
Grind and silicone (KF made by Shin-Etsu Silicone Co., Ltd.)
After spraying 2 parts of 96, oil type, 10 cps), particles with a particle size of 40 to 250μ are 85
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. The gluing was done in a washing machine (bath ratio 1/
5).

【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.
- 9 parts by weight, 0.01 to 3 parts by weight of silicone, and 0.1 to 3 parts by weight of boric acid, and 70% by weight or more of the powder particles have a particle size in the range of 40 to 250μ. agent composition.