KR101014888B1 - Sheet-type Bleach Containing Eco-friendly Non-Aqueous Composition and Method for Producing thereof - Google Patents

Abstract

The present invention comprises a solid peroxide, a non-aqueous organic solvent, an anionic surfactant, a nonionic surfactant, an organic binder and a stabilizer, wherein the peroxide is dispersed in a liquid component to form a suspension (non-aqueous) The present invention relates to a sheet-type bleach containing an oxygen-based bleach composition.

It is expected that the non-aqueous oxygen-based sheet bleaching agent of the present invention may be widely used commercially due to low loss of effective oxygen, excellent impregnation property, shape retention, and dissolution rate. In addition, the sheet-type bleach is convenient to carry and easy to quantitatively can suppress over-use, which is advantageous in terms of economy.

Peroxides, Sheet Bleaches, Suspensions, Surfactants

Description

Sheet-type Bleach Containing Eco-friendly Non-Aqueous Composition and Method for Producing Applications

The present invention comprises a solid peroxide, a non-aqueous organic solvent, an anionic surfactant, a nonionic surfactant, an organic binder and a stabilizer, wherein the peroxide is dispersed in a liquid component to form a suspension (non-aqueous) The present invention relates to a sheet-type bleach containing an oxygen-based bleach composition.

Currently used bleach is divided into chlorine bleach and oxygen bleach.

First, as a chlorine bleach, British Patent No. 2,229,460 discloses a bleach which contains sodium hypochlorite as a main component, but such a chlorine bleach has a strong bleaching power but discolors color clothing or destroys fiber structure when bleaching clothes. there is a problem. In addition, there is a disadvantage that generates an unpleasant smell due to the generation of chlorine harmful to the human body when using.

On the other hand, the oxygen-based bleaching agent does not have the above-mentioned disadvantages that the chlorine-based bleaching agent has, and its usage has recently increased. These oxygen-based bleaches are largely divided into liquid bleaches and powder bleaches depending on the form.

Most of the oxygen-based bleaches currently on the market are powder bleaches using sodium percarbonate or sodium perborate, and they have a disadvantage in that they are hardly soluble in water at room temperature, especially cold water. Furthermore, when the powder bleach is prepared, it is difficult to uniformly mix the solid components, and when the powder bleach is used, there is an inconvenience in that dust is generated, and in particular, there is a disadvantage in that partial bleaching of the stain is difficult.

Recently, however, liquid bleaches are more convenient to use than powder bleach products and thus tend to be favored by consumers. Liquid bleaches have the advantages of being easier to weigh than powder bleaches, dissolving quickly in water, no dust, and no caking that commonly occurs in powder bleaches during storage.

U.S. Pat.Nos. 6,235,699, 5,929,012, 4,900,468, etc. disclose liquid bleaches using hydrogen peroxide as bleach. The liquid bleach using hydrogen peroxide expands the storage container due to decomposition of hydrogen peroxide during storage, or bleaching power. There is a problem such as being reduced. In addition, in order to stabilize the hydrogen peroxide, the pH of the bleach solution must be kept acidic, but under such low pH, the bleaching power and the washing power are significantly reduced.

U.S. Patent Nos. 3,499,844, 4,130,501 and the like disclose a method of increasing the viscosity of a composition in order to increase the chemical stability of the liquid bleach. However, the above method is also pointed out that the pH of the bleaching agent is markedly lowered in the bleaching power and washing power, and the viscosity of the composition changes due to the decomposition of hydrogen peroxide during storage has a problem that is difficult to commercialize.

Although the bleaches of the above patents are specialized in bleaching compositions and used in fiber bleaching, there has been a demand from consumers for a new type of bleach that is more easy to handle and ensures stability.

U.S. Patent No. 4,356,099 discloses a detergent in the form of a plastic bag, which has a problem that the detergent and bleaching ingredients contained in the plastic bag are released due to moisture or impact on storage, and it is difficult to quantitate as desired when washing. Holding it.

U.S. Patent No. 4,532,063 uses a water-soluble nonwoven fabric to impregnate bleach to produce a sheet-shaped bleach. In order to impregnate the nonwoven fabric with a solid component, water or a general organic solvent is used. need. However, the drying process or the use of the organic solvent required at this time is not economical, it can be seen that the process harmful to the human body. In addition, there is an additional problem that it is difficult to maintain the stability of the bleaching component when using an oxygen-based bleach.

U.S. Patent No. 4,654,395 discloses a sheet-shaped bleach in the form of a mixture of a water-soluble nonwoven fabric and a water-insoluble nonwoven fabric to improve usability through effective storage of the bleaching component, but various production processes are additionally required. Disadvantages include sodium dichloroisocyanate and borax pentahydrate as bleach, which damages the fiber and is not environmentally friendly.

US Pat. No. 7,094,744 describes a method for producing a sheet-type detergent, which is prepared using a detergent and a bleach mixture composition using water as a solvent, and thus requires an additional drying process and a problem of securing stability of the peroxide-based bleach. have.

Looking at the patent, the sheet-type bleach containing the oxygen-based bleaching material mainly due to the use of water as a solvent it can be seen that there is a limitation in commercialization because there is a problem in stability, such as not specializing the product only bleaching ingredients. In addition, there is a problem in maintaining the price competitiveness for the conventional powder bleach or liquid bleach because the manufacturing cost increases because the additional drying process is required when manufacturing the sheet bleach. Therefore, the situation is required to develop a sheet-type bleach that can stably preserve the oxygen-based bleaching material with high bleaching power.

Accordingly, the inventors of the present invention have been researched to develop a sheet-type bleach excellent in physical properties and bleaching power, and as a result, in a liquid phase containing a specific organic solvent having a nonpolar property and water solubility, and a surfactant defining a type and content It is capable of producing hydrogen peroxide, and the sheet-type bleach obtained by dispersing a solid peroxide and impregnating a composition containing a specific organic binder in a nonwoven fabric has excellent surface properties such as flexibility and excellent bleaching power, so that it is excellent in a small amount. It has been found that the bleaching effect can be obtained to complete the present invention.

Therefore, an object of the present invention is to provide a sheet-like bleach containing the environmentally friendly non-aqueous composition and a method for producing the same.

The present invention,

50 to 85 wt% of solid peroxide, 10 to 38 wt% of non-aqueous organic solvent, 0.1 to 10 wt% of anionic surfactant, 0.1 to 10 wt% of nonionic surfactant, 0.1 to 10 wt% of organic binder, 0.01 to Stabilizer It comprises 10% by weight,

 The anionic surfactant and the nonionic surfactant is included in the weight ratio of 3: 1 to 1: 3,

A water content of 1.0% by weight or less and a viscosity of 1,000 to 15,000 cps (50 ° C), wherein the solid peroxide is dispersed in a liquid component to form a suspension (non-aqueous oxygen) The bleach composition is characterized by a sheet bleach in which the sheet nonwoven fabric is impregnated.

In addition,

Supplying the nonwoven fabric to the coating tank containing the non-aqueous oxygen-based bleach composition so that the bleach composition is impregnated into the nonwoven fabric; And

Controlling the amount of impregnation by passing the nonwoven fabric impregnated with the bleach composition through a roller

It characterized by another method for producing a sheet-like bleach comprising a.

It is expected that the non-aqueous oxygen-based sheet bleaching agent of the present invention may be widely used commercially due to low loss of effective oxygen, excellent impregnation property, shape retention, and dissolution rate. In addition, the sheet-type bleach is convenient to carry and easy to quantitatively can suppress over-use, which is advantageous in terms of economy.

The present invention is 50 to 85% by weight of solid peroxide, 10 to 38% by weight of non-aqueous organic solvent, 0.1 to 10% by weight of anionic surfactant, 0.1 to 10% by weight of nonionic surfactant, 0.1 to 5% by weight of organic binder, It comprises 0.01 to 10% by weight of the stabilizer, the anionic surfactant and the nonionic surfactant is included in the weight ratio of 3: 1 to 1: 3, the water content is 1.0% by weight or less, the viscosity is 1,000 to 15,000 cps (50 ° C.), wherein the solid peroxide is dispersed in a liquid component to form a suspension, and a non-aqueous oxygen-based bleach composition is characterized by a sheet-type bleach impregnated into a sheet-like nonwoven fabric. .

The present invention will be described in detail by way of examples for each component of the composition.

The non-aqueous oxygen-based bleach composition of the present invention includes a solid peroxygen compound, a non-aqueous organic solvent, an anionic surfactant, a nonionic surfactant, an organic binder and a stabilizer, and additionally a thickening agent, an antifoaming agent, a fluorescent agent Brighteners, enzymes, flavors and the like.

The solid peroxide used in the present invention is a material capable of forming hydrogen peroxide, percarbonate, perborate, persulfate, urea peroxide and metal peroxide (ZnO _2). , MnO ₂ , CaO ₂ ) and the like can be used. Preferably, percarbonate is used. The percarbonate is a compound consisting of a combination of sodium carbonate and hydrogen peroxide is an environmentally friendly compound having a high effective oxygen content and high solubility in water. It is preferable to use a peroxide having a mean particle size in the range of 1 to 300 μm. If the average particle size is large, the peroxide content can be increased. However, when the peroxide is too large, the peroxide is impregnated to the hand. Since is increased, it is preferably pulverized to 100 µm or less, more preferably 10 µm or less. The amount of the solid peroxide used is 50 to 85% by weight. If the amount is less than 50% by weight, the effect as a bleaching agent is not effective, and when it exceeds 85% by weight, the physical stability is lowered.

Since the non-aqueous organic solvent has a great influence on the chemical and physical stability of the whole composition, special attention should be paid to its selection, and the selective use of such a non-aqueous organic solvent is one of the features of the technical construction of the present invention.

As a non-aqueous organic solvent, an organic solvent (water-miscible solvent) mixed well with water may be used. The peroxide (particularly in the case of percarbonate) is decomposed when dissolved in water and adversely affects the chemical stability of the composition. Therefore, in the present invention, as the non-aqueous organic solvent, there should be almost no moisture (less than 0.5 wt%), and it is preferable to select and use the organic solvent that does not absorb water in the air well.

In addition, the non-aqueous organic solvent to be used in the present invention is selected to use a very low polarity. In other words, a solvent having a high polarity tends to dissolve peroxides such as percarbonate, so it is not recommended to use a solvent having a high polarity such as ethanol or propanol. In addition, the non-aqueous organic solvent to be used in the present invention should be free of chemical reactions with other components used together. In addition, it is necessary to select a solvent capable of controlling the viscosity of the composition and preventing gelation.

As the non-aqueous organic solvent that satisfies the above conditions, an organic solvent which can be used in the present invention is specifically, for example, polyalkylene glycol, polyhydric alcohol, alkylene glycol monoalkyl ether, alkyl ester and alkylamide, etc. One or more mixtures selected from among them can be used.

The organic solvent is present in the liquid phase within the range of 30 ~ 100 ℃, more preferably 40 ~ 60 ℃ so as not to decompose the peroxide, at room temperature to ensure the flexibility and strength of the sheet-type bleach prepared, high molecular weight for this purpose, It is better to use a lower polarity. Particularly, among the polyalkylene glycols, it is preferable to use polyethylene glycol having a weight average molecular weight in the range of 400 to 6000, and more preferably two or more polyethylene glycols having different molecular weights are mixed, and at this time, the weight average molecular weight 400 to A low molecular weight polyethylene glycol of 2000 and a high molecular weight polyethylene glycol having a weight average molecular weight of 2000 to 6000 are mixed at a weight ratio of 9: 1 to 1: 1. When polyethylene glycols having a weight average molecular weight of 400 to 6000 are used, the nonwoven fabric can be impregnated with a liquid composition having a constant viscosity at a high temperature during the manufacturing process, and after the impregnation process, the surface of the sheet hardens at room temperature to reduce additional drying process. It is possible to obtain an effect that does not come out on the hand even during use. At this time, the use amount of the non-aqueous organic solvent is 10 to 38% by weight, when the amount is less than 10% by weight or more than 38% by weight physical stability is lowered.

The nonaqueous oxygen-based bleach composition of the present invention uses anionic surfactants and nonionic surfactants as surfactants.

The anionic surfactant is a linear alkylbenzene sulfonate represented by the following formula (1), a fatty acid salt represented by the following formula (2), a linear alkyl sulfonate represented by the following formula (3) and an alpha olefin sulfonate represented by the following formula (4) One or more mixtures selected from the like and the like may be used.

R ¹ -C ₆ H ₄ -SO ₃ X

R ² -CH ₂ -COOX

R ³ -CH ₂ -SO ₃ X

R ³ -CH = CHCH ₂ -SO ₃ X

In Formulas 1 to 4, R ¹ is a C ₉ to C ₁₅ alkyl group, R ² is a C ₁₁ to C ₁₆ alkyl group, R ³ is a C ₁₁ to C ₁₈ alkyl group, and X is an alkali metal.

The anionic surfactant is preferably used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, but when the amount is less than 0.1% by weight, the washing power is lowered, and when it exceeds 10% by weight, the physical stability is lowered.

The nonionic surfactant is one selected from fatty acid alcohol polyoxyethylene glycol represented by the following formula (5), fatty acid polyoxyethylene glycol represented by the following formula (6), alkylphenyl polyoxyethylene glycol represented by the following formula (7), or the like The above mixture can be used.

R ⁴ -CH _2- (OCH ₂ CH ₂ ) _n -OH

R ⁴ -CO- (OCH ₂ CH ₂ ) _n -OH

R ⁴ -C ₆ H _4- (OCH ₂ CH ₂ ) _n -OH

In Formulas 5 to 7, n is an integer of 5 to 25, R ⁴ is an alkyl group of C ₁₁ ~ C ₁₈ .

Such nonionic surfactants are preferably used in an amount of 0.1 to 10% by weight, preferably 0.5 to 15% by weight, but when the amount is less than 0.1% by weight, the washing power is lowered, and when used in excess of 20% by weight, the physical stability is lowered. do.

In the present invention, the amount and ratio of the anionic surfactant and the nonionic surfactant described above greatly affect the chemical and physical stability of the composition. Therefore, the selective use of the kind of the surfactant and the limitation of the use ratio are one of the features of the technical construction of the present invention.

That is, in the non-aqueous oxygen-based liquid bleach composition of the present invention, the anionic surfactant and the nonionic surfactant are used in a weight ratio of 3: 1 to 1: 3, and when the use ratio is outside the above range, the physical stability is lowered.

An organic binder is used to improve surface properties when the bleach composition of the present invention is applied to a sheet-like nonwoven fabric. At this time, the organic binder used is a mixture of one or two of cellulose-based, such as ethyl cellulose, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol and polyvinyl butyral, which are well dissolved in the non-polar organic solvent and water. Can be used. The use amount of the organic binder is 0.1 to 10% by weight, preferably 1 to 5% by weight of the total composition. If the amount is less than 0.1% by weight, the surface improvement effect is inferior, and when the amount is more than 10% by weight, the surface improvement effect is insignificant.

The stabilizer (ion blocking agent) may be used by selecting one or more of organic acids, salts of organic acids, amino polyphosphonate compounds and the like. Specifically, the organic acid may be one selected from citric acid, dipicolinic acid, gluconic acid, and the like. Specific examples of the amino polyphosphonate-based compound include hydroxy ethylene diphosphonic acid, ethylene diamine tetra (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), aminotri (methylene phosphonic acid), and the like. You can use the selected one. In particular, stabilizers used should not contain water. Such stabilizer is used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight. At this time, if the amount of use is less than 0.01% by weight, the chemical stability is lowered, and if it exceeds 5% by weight, the synergistic effect of the chemical stability is lost. Commercially available stabilizers include Solutia's Dequest ™ series.

In the present invention, it is possible to prepare a suspension having excellent physical stability without the use of a thickener, but if necessary, a more preferable effect can be obtained. The thickener is a fatty acid, a crosslinked acrylic acid copolymer, colloidal silica, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone One or more mixtures selected from polyvinyl pyrrolidone, sodium polyacrylate, and the like may be used.

The fatty acid may be a mixture of two or more selected from saturated or unsaturated fatty acids having 10 to 18 carbon atoms, preferably capric acid, lauric acid, and myristic acid. And a mixture of two or more of palmitic acid. The amount of such fatty acids used is 0.01 to 5% by weight, preferably 0.1 to 3.0% by weight.

As the crosslinked acrylic copolymer, an acrylic acid copolymer crosslinked with 0.75 to 1.5% by weight of polyallyl sucrose may be used. The amount of the crosslinked acrylic copolymer is 0.01 to 1.5% by weight, preferably 0.1 to 2% by weight.

The colloidal silica may be a hydrophilic fumed silica having a surface area of 200 m 2 / g, an average particle size in the range of 10 to 12 nm, or a hydrophobic fumed silica having a surface area of 100 m 2 / g and an average particle size in the range of 10 to 20 nm. The amount of colloidal silica used is 0.01 to 5% by weight, preferably 1 to 3% by weight. Commercially available thickeners include B and F. Goodrich's Carbopol 934, 937, Degussa's Aerosil 200, and Cabot's Cabosil fumed silica.

Raw materials and metal materials introduced during manufacture (for example iron, manganese, copper, chromium, etc.) promote the decomposition of peroxides, which lowers the chemical stability of the final composition and should be ruled out wherever possible. It may include components conventionally used in the art. That is, various other optional components such as antioxidants, colorants, optical brighteners, anti-fouling agents, cleaning enzymes, and flavoring agents may be included, and the amount thereof is 0.01 to 5% by weight.

As described above, the non-aqueous bleach composition of the present invention is a solid dispersion of particles in a non-aqueous liquid phase, a peroxide generating hydrogen peroxide, an organic solvent (water-miscible solvent) mixed with water, a surfactant, an organic binder, and a stabilizer ( Ion blocking agent), thickening agent (thickening agnet), and other small amount additives, including fluorescent brightener, antifoaming agent, enzyme, fragrance, etc., viscosity of 1,000 ~ 50,000cps (shear rate 20 sec ^-1 at 50 ℃) Moisture content is 1.0% by weight or less, preferably 0.5% by weight or less, physically and chemically stable for a long storage time, easy to use, can be used for general washing and immersion washing, and is an eco-friendly non-aqueous sheet type with excellent bleaching power. It can be used for the preparation of bleaches.

The sheet-shaped nonwoven fabric is preferably made of one kind or a mixture of two or more kinds selected from polypropylene, polyethylene, polycaprolactam, rayon / polyester, polyethylene terephthalate, polybutylene terephthalate, polyvinyl alcohol and carboxymethyl cellulose, Use is made of one of melt blown, thermal bonding, air through or spun bonding methods.

Particularly, the production of sheet-type bleach is mainly performed at high temperature, so it maintains thermal stability in the working temperature range so that no deformation occurs, and polypropylene, polyethylene terephthalate, and polycapro which are stable in the temperature range of 150 to 250 ° C without melting harmful substances. It is preferable to use lactam or polybutylene terephthalate nonwoven fabric, and when using a water-soluble nonwoven fabric, it is preferable to use polyvinyl alcohol or carboxymethyl cellulose nonwoven fabric which is completely dissolved in low temperature water so that the remaining components of the nonwoven fabric remain after washing. good.

Physical properties of the nonwoven fabric should be capable of impregnating a large amount of bleach composition, it is good that the strength is excellent, such as not damaged or scattered tissue after washing. For this purpose, it is preferable to use a sheet having a basis weight (gsm) of 20 to 150 and a thickness of 0.15 to 0.40 mm. The amount of the bleach composition impregnated in a single nonwoven fabric is preferably as large as possible because a small amount of impregnation requires the introduction of several sheets into the washing tank. In the present invention, the amount and thickness of the bleach composition impregnated into the sheet-like nonwoven fabric are controlled by adjusting the roll-to-role spacing of the roller, and the weight ratio of the non-aqueous oxygen-based bleach composition impregnated with the sheet-shaped nonwoven fabric is 1: 5 to 1:20, more preferably 1:10 to 1:15. The impregnation thickness is 50 to 1500 µm, more preferably 150 to 1000 µm, in consideration of the flexibility, shape retention and dissolution rate of the sheet-shaped bleach after impregnation.

In addition, the present invention provides a non-aqueous oxygen-based bleach composition of the sheet-type bleaching agent comprising the step of supplying a nonwoven fabric, the bleach composition is impregnated in the nonwoven fabric, the bleach composition impregnated nonwoven fabric through a roller to adjust the amount of impregnation The manufacturing method is another feature.

More specifically, a nonwoven fabric having an arbitrary length is wound on a drum such as a roller and supplied in a constant path, and the nonwoven fabric is saturated in a coating bath containing a non-aqueous bleach composition so that the bleach composition is impregnated in the nonwoven fabric, and then the nonwoven fabric is roller The amount of impregnation is adjusted while passing through. At this time, unlike the conventional aqueous bleach composition, the bleach composition impregnated on the nonwoven fabric without additional drying process for water removal is solidified at room temperature while completing the sheet-type bleach.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

Examples 1-15 and Comparative Examples 1-7

Into a 1L glass reactor equipped with a three-blade propellar agitator and a jacket, an organic solvent and an organic binder were added to dissolve the polyvinylpyrrolidone having an average molecular weight of 90,000, and then completely dissolved. The active agent was first added, and then a thickener, anionic surfactant, stabilizer, and fluorescent brightener were added while stirring at 400 rpm or more, and then dissolved for about 1 hour. In this case, the stabilizer may not be dissolved.

Peroxide and enzyme in powder form was slowly added to the mixed solution to the mixed solution. After completely adding the peroxide, the mixture was stirred for about 1 hour at about 30 minutes, and the foam formed during the stirring was removed in vacuo, and finally, perfume was added to prepare a non-aqueous bleach composition.

The non-aqueous bleach composition prepared above was applied to a polypropylene sheet-like nonwoven fabric, and the doctor blade was used to prepare an impregnating thickness of 600 μm through interval setting, and then left at room temperature to complete the sheet-type bleach.

The composition components and the amount used in Examples 1 to 15 and Comparative Examples 1 to 7 are shown in Tables 1 to 3 below.

Experimental Example 1 Measurement of Chemical Stability, Impregnation Properties, Shape Preservation, and Dissolution Rate

[Chemical Stability]

After storing the sheet-type bleach prepared according to the above Examples and Comparative Examples for one month in an oven at 50 ℃ for chemical stability by calculating the loss of active oxygen by titration method using potassium permanganate (KMnO ₄ ) It was determined that the loss of active oxygen is 10% or less (stable 90% or more).

[Coating property]

It was evaluated that the sheet-type bleach prepared by using a rheometer was rotated at 25 ° C. at a shear rate of 1000 sec ⁻¹ , and there was no bleach composition particles on the surface of the sheet. For evaluation, the following criteria were distinguished.

A. The thickness of the sheet remains constant, and no particles come out.

B. Slight deformation occurs in the thickness of the sheet, and fine particles come out.

C. Particles stick to the surface.

[Shape retention]

After the sheet bleach manufactured using rheometer was rotated at a shear rate of 200 sec ⁻¹ at 25 ° C., there was no deformation of the sheet bleach due to pressure, and if it was not broken, it was evaluated to have excellent shape preservation. In order to distinguish from the following criteria.

A. No deformation is observed on the sheet and it does not break.

B. Fine deformation is observed on the sheet.

C. Severe deformation is observed in the sheet.

[Measuring Dissolution Rate]

To measure how well the impregnated active ingredient of the prepared sheet bleach dissolves at low temperature, add a sheet bleach impregnated with 1 g of bleach in a 1 L beaker, stir at 500 rpm at 10 ° C. for 3 minutes, and dry the sheet to completely drain water. The weight of the dried sheet was measured to calculate the amount dissolved. At this time, by applying the following criteria was evaluated that the dissolution rate is excellent when all the bleach composition is dissolved within 3 minutes, to distinguish more objectively to the following criteria.

A. Bleach composition dissolves at least 90% within 3 minutes.

B. Bleach composition dissolves 80-90% or more within 3 minutes.

C. Bleach composition dissolves up to 80% within 3 minutes.

ingredient Example (% by weight) Comparative Example (wt%) One 2 3 4 One 2 3 ⁵⁾ 4 ⁶⁾ Sodium lauryl sulfonate 2.37 2.37 2.37 2.37 2.37 2.37 Polyoxyethylene lauryl ether
(9 mol ethylene oxide) 3.4 3.4 3.4 3.4 3.4 3.4 Polyvinylpyrrolidone 0.92 0.92 0.92 0.92 0.92 0.92 Sodium percarbonate ^{1 )} 61 55 - 61 61 Sodium perborate ^{2 )} - - 61 - - 61 D2016D ^{3 )} 0.57 0.57 0.57 0.57 0.57 0.57 Lauric acid 0.73 0.73 0.73 0.73 0.73 0.73 Myristic acid 0.17 0.17 0.17 0.17 0.17 0.17 Fluorescent Dyes ^{4 )} 0.24 0.24 0.24 0.24 0.24 0.24 incense 0.1 0.1 0.1 0.1 0.1 0.1 PEG 200 - - - 30.5 - - PEG 1500 30.5 36.5 30.5 - - - Anhydrous alcohol - - - - 30.5 30.5 Stability Impregnation Properties B B B B C C - - Shape preservation A A A B B B - - Dissolution rate A A A A B B C B Chemical stability
[50 ℃ Oven] 96.0% 95.5% 94.5% 90.3% 71.0% 69.5% 91.0% 45.0% 1) Average particle size 10 ㎛
2) Average particle size 10 ㎛
3) Solutia, stabilizer
4) AMS-GX, Ciba Specialty
5) Powder A bleach (Main ingredient: Sodium percarbonate)
6) B company liquid bleach (main ingredient: hydrogen peroxide)

As shown in Table 1, it was confirmed that the sheet-type bleach according to the present invention has excellent chemical stability and excellent sheet-type bleach, which shows a fast dissolution rate. Particularly, when anhydrous ethanol having high polarity was used, the chemical stability of the sheet-type bleach was very poor, and the higher the molecular weight of polyethylene glycol was, the better the chemical stability and the impregnated physical properties were confirmed. In addition, commercially available powder bleach of A company and liquid bleach of B company were not prepared as a sheet bleach, and it was confirmed that dissolution rate and chemical stability were lower than those of the sheet bleach of the present invention.

Experimental Example 2 Selection of the Optimal Organic Solvent

In order to optimize the organic solvent used in the present invention was prepared in the same manner as in the sheet-like bleach of Example 1, the physical properties and stability was measured by changing the type of organic solvent as shown in Table 2.

Organic Solvents Used Example (% by weight) 5 6 7 8 9 10 PEG 400 30.5 PEG 2000 30.5 PEG 600 + PEG 4000
(Weight ratio 9: 1) 30.5 PEG 600 + PEG 4000
(Weight ratio 8: 2) 30.5 PEG 1500 + PEG 4000
(Weight ratio 9: 1) 30.5 PEG 1500 + PEG 4000
(Weight ratio 8: 2) 30.5 Stability Impregnation Properties B A A B A A Shape preservation B B A B A B Dissolution rate A A A A A A Chemical stability
[50 ℃ Oven] 95.3% 96.9% 97.3% 96.0% 97.5% 96.3%

In Examples 5 to 10 of Table 2, when the average molecular weight of polyethylene glycol, which is an organic solvent, was changed and prepared alone or mixed, respectively, a bleach composition was prepared. In the case of using polyethylene glycol having a weight average molecular weight of 400, the sheet bleaching agent was used. It was observed that the surface was sticky and particles came out. When polyethylene glycol with a weight average molecular weight of 2000 was used, the surface of the sheet was not sticky, but the flexibility was not good, indicating a problem in shape preservation. It was confirmed that it was reduced. In Examples 7 to 10, when polyethylene glycols having different average molecular weights were mixed and used, it was confirmed that the physical properties were different depending on the type of polyethylene glycol to be mixed and the respective mixing ratios. Excellent preservation and impregnation properties could be further improved, and polyethylene glycol having a weight average molecular weight of 1500 and polyethylene glycol having a weight average molecular weight of 4000 was found to have the best effect.

Experimental Example 3 Selection of Organic Binder

In order to optimize the type and content of the organic binder used in the present invention was prepared in the same manner as the sheet bleach of Example 9, the physical properties and stability was measured by changing the type and content of the organic binder as shown in Table 3 below.

Organic binder Example (% by weight) Comparative example (% by weight) 11 12 13 14 15 5 6 6 7 Polyvinylpyrrolidone (PVP) 0.31 1.55 2.5 Polyvinyl Butyral (PVB) 0.92 Carboxymethyl Cellulose (CMC) 0.92 Polyvinylpolypyrrolidone 0.92 Polyethylene oxide 0.92 Polyacrylonitrile 0.92 PEG 1500 + PEG 4000 31.11 29.87 28.92 30.5 30.5 31.42 30.5 30.5 30.5 Stability Impregnation Properties B A A B B C C C C Shape preservation A A A A B C C C C Dissolution rate A A A B B B C C C Chemical stability
[50 ℃ Oven] 96.0% 97.1% 97.0% 92.5% 93.0% 96.0% 92.0% 91.5% 92.0%

It can be seen that the impregnated properties are improved when the organic binder is used through the experiment, and polyvinylpyrrolidone and polyvinyl than the organic binders such as polyvinyl polypyrrolidone, polyethylene oxide, and polyacrylonitrile are used. When butyral and sodium carboxymethyl cellulose were used, the impregnation properties and shape retention were improved, and the dissolution rate was also excellent.

Experimental Example 4: Bleaching power comparison test

1L of water (water temperature 20 ° C, hardness 50 CaCO ₃ ppm) and one sheet of bleach of Examples 1 to 4 and Comparative Examples 1 to 4 were added to a Terg-O-tometer, and red wine (EMPA) was added thereto. 114), 10 sheets of each contaminated cloth (7cm × 7cm) were washed for 10 minutes using standard contaminants such as coffee (wfk BC-2), red pepper (wfk 10P) and tea (wfk BC-3). Rinse with tap water for 3 minutes and dry naturally. After washing the cotton cloth, the whiteness was measured using a colorimeter, and then bleaching power was calculated by substituting the Kubellka-Munk equation of Equation 1 as follows. Shown in

Bleaching rate (%) = [(1- Rs) 2 / 2Rs - (1-Rb) 2 / 2Rb] / [(1-Rs) 2 / 2Rs - (1-Ro) 2 / 2Ro] x 100

In Equation 1, Rs is the surface reflectance of the contaminated cotton cloth, Rb is the surface reflectivity of the cotton cloth after decontamination, and Ro is the surface reflectance of the white cotton cloth.

Bleaching power (%) Red wine pollution Coffee pollution Pepper pollution Secondary pollution Example 1 75 78 77 68 Example 2 72 71 71 60 Example 3 72 72 70 57 Example 13 75 80 79 70 Comparative Example 1 65 75 68 55 Comparative Example 2 63 74 61 50 Comparative Example 3 70 78 70 63 Comparative Example 4 40 55 58 33

In Table 2, Examples 1 to 3 and 13 of the sheet-type bleaching agent of the present invention was confirmed that the overall bleaching effect is superior to the sheet-type bleaching agent of Comparative Examples 1 to 2 using anhydrous ethanol, in particular liquid bleach sold on the market Compared to Comparative Examples 3 to 4 impregnated with excellent chemical stability, it was confirmed that the bleaching effect was excellent as the impregnation of the bleach component is made well.

Claims (19)

50 to 85 wt% of solid peroxide, 10 to 38 wt% of non-aqueous organic solvent, 0.1 to 10 wt% of anionic surfactant, 0.1 to 10 wt% of nonionic surfactant, 0.1 to 10 wt% of organic binder, 0.01 to Stabilizer It comprises 10% by weight, The anionic surfactant and the nonionic surfactant is included in the weight ratio of 3: 1 to 1: 3, The non-aqueous organic solvent is a mixture of a low molecular weight polyethylene glycol having a weight average molecular weight of 400 to 2000 and a high molecular weight polyethylene glycol having a weight average molecular weight of 2000 to 6000 in a weight ratio of 9: 1 to 1: 1, The organic binder is one or more mixtures selected from sodium carboxymethylcellulose, polyvinylpyrrolidone and polyvinyl butyral, A water content of 1.0% by weight or less, the viscosity is 1,000 to 15,000 cps (50 ℃), the non-aqueous oxygen bleach, characterized in that the solid peroxide is dispersed in a liquid component to form a suspension (suspension) A sheet-like bleach, wherein the composition is impregnated into a sheet-like nonwoven fabric. The sheet-like bleach according to claim 1, further comprising 0.01 to 5% by weight of a thickener in addition to the nonaqueous bleach composition. The sheet-type bleach according to claim 1, wherein the peroxide has an average particle size in the range of 1 to 300 µm. The bleach according to claim 1, wherein the peroxide is selected from percarbonate, perborate, persulfates and urea peroxide. The sheet-type bleach according to claim 1, wherein the non-aqueous bleach composition further comprises 0.01 to 5% by weight of one or a mixture thereof selected from fluorescent brighteners, antifoaming agents, enzymes and flavors. delete The method of claim 1, wherein the anionic surfactant is a linear alkylbenzenesulfonate represented by the following formula (1), a fatty acid salt represented by the following formula (2), a linear alkylsulfonate represented by the following formula (3) and A sheet-like bleach, characterized in that one or more mixtures selected from the alpha olefin sulfonates represented; [Formula 1] R ¹ -C ₆ H ₄ -SO ₃ X [Formula 2] R ² -CH ₂ -COOX (3) R ³ -CH ₂ -SO ₃ X [Formula 4] R ³ -CH = CHCH ₂ -SO ₃ X In Formulas 1 to 4, R ¹ is a C ₉ to C ₁₅ alkyl group, R ² is a C ₁₁ to C ₁₆ alkyl group, R ³ is a C ₁₁ to C ₁₈ alkyl group, and X is an alkali metal. According to claim 1, wherein the nonionic surfactant is selected from fatty alcohol polyoxyethylene glycol represented by the following formula (5), fatty acid polyoxyethylene glycol represented by the following formula (6) and alkylphenyloxyethylene glycol represented by the following formula (7) Sheet-like bleach, characterized in that one or more mixtures; [Chemical Formula 5] R ⁴ -CH _2- (OCH ₂ CH ₂ ) _n -OH [Formula 6] R ⁴ -CO- (OCH ₂ CH ₂ ) _n -OH [Formula 7] R ⁴ -C ₆ H _4- (OCH ₂ CH ₂ ) _n -OH In Formulas 5 to 7, n is an integer of 5 to 25, R ⁴ is an alkyl group of C ₁₁ ~ C ₁₈ . delete The bleach according to claim 1, wherein the stabilizer is one or more mixtures selected from organic acids, salts of organic acids, and amino polyphosphonate compounds. The sheet-type bleach according to claim 10, wherein the organic acid is one or more mixtures selected from citric acid, dipicolinic acid and gluconic acid. The method of claim 2, wherein the thickener is one or more mixtures selected from fatty acids, crosslinked acrylic copolymers, colloidal silica, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and sodium polyacrylate. Sheet bleach, The sheet-type bleach according to claim 12, wherein the fatty acid is a mixture of two or more selected from saturated or unsaturated fatty acids of C ₁₀ to C ₁₈ . The method of claim 1, wherein the sheet-like nonwoven fabric is selected from polypropylene, polyethylene, polycaprolactam, rayon / polyester, polyethylene terephthalate, polybutylene terephthalate, polyvinyl alcohol, and carboxymethyl cellulose. A sheet-like bleach comprising a mixture. 15. The sheet bleach according to claim 14, wherein the sheet nonwoven fabric has a basis weight (gsm) of 20 to 150. 15. The sheet bleach according to claim 14, wherein the sheet nonwoven fabric has a thickness of 0.15 to 0.40 mm. The sheet bleach according to claim 1, wherein the weight ratio of the nonaqueous oxygen-based bleach composition impregnated with the sheet nonwoven fabric is 1: 5 to 1:20. The sheet-type bleach according to claim 1, wherein the non-aqueous oxygen-based bleach composition is impregnated to a thickness of 100 to 1500 µm. Supplying the nonwoven fabric to the coating bath containing the non-aqueous oxygen-based bleach composition of claim 1 so that the bleach composition is impregnated into the nonwoven fabric; And Controlling the amount of impregnation by passing the nonwoven fabric impregnated with the bleach composition through a roller Method for producing a sheet-like bleach comprising a.