KR102440149B1 - Sheet type detergent and method of preparing the same - Google Patents

Abstract

The present invention relates to a sheet-type detergent and a manufacturing method thereof. The sheet-type detergent comprises: a polyvinyl alcohol-based compound; a first anionic surfactant containing C8 to C18 alkyl sulfate alkali metal salt; a second anionic surfactant represented by following chemical formula 3; and a nonionic surfactant represented by following chemical formula 4. (in chemical formula 3 and chemical formula 4, R^1, R^2, X, Y, m_1, m_2, n_1 and n_2 are as defined in the specification.) The sheet-type detergent according to an embodiment is completely dissolved in water and does not need to be removed after washing and has excellent washing and rinsing performance, and also has excellent formability and storage stability.

Description

Sheet-type detergent and manufacturing method thereof

It relates to a sheet-like detergent and a method for manufacturing the same.

So far, powder detergents or liquid detergents have been used as detergents used in washing machines. In the case of liquid detergent, there is a disadvantage that consumers are reluctant to use it because it is relatively heavy, and in the case of powder detergent, a phenomenon of powder flying occurs during use, so the need for a new type of detergent has been constantly raised.

In order to improve this problem, US Patent No. 4,605,509 discloses a technology for packaging a liquid detergent component and a fabric softener in a water-soluble film bag. However, in the case of fractional packaging using water-soluble polymer films, a phenomenon occurred in which the seal bursts during storage or transportation of the product and the contents leak. In addition, the storage stability of the product was very deteriorated, such as the active ingredients oozing out on the surface of the film. In addition, the water-soluble film used as a packaging material is designed to have stability against moisture in the atmosphere and durability against the contents, but it takes a considerable amount of time to dissolve at low temperatures and does not completely dissolve, leaving a residue of the film. This occurred.

In addition, although a laundry sheet using a liquid detergent adsorbed to the water-insoluble absorption sheet has been developed, there is a disadvantage in that the water-insoluble absorption sheet must be removed after washing.

US Patent No. 4,605,509

One embodiment provides a sheet-type detergent that is completely dissolved in water and does not need to be removed after washing, has excellent washing performance and storage stability, and is easy to use.

Another embodiment provides a method of manufacturing the sheet-type detergent.

One embodiment is a polyvinyl alcohol-based compound; a first anionic surfactant comprising a C8 to C18 alkyl sulfate alkali metal salt; a second anionic surfactant represented by the following formula (3); And it provides a sheet-type detergent comprising a nonionic surfactant represented by the following formula (4).

[Formula 3]

(In Formula 3,

R ¹ is a substituted or unsubstituted straight or branched C9 to C16 alkyl group, or a substituted or unsubstituted straight or branched C9 to C16 alkenyl group,

X is -SO ₃ or -COO,

Y is an alkali metal,

m ₁ is an integer from 1 to 9, and n ₁ is an integer from 1 to 3.)

[Formula 4]

(In Formula 4,

R ² is a substituted or unsubstituted straight or branched C9 to C16 alkyl group, or a substituted or unsubstituted straight or branched C9 to C16 alkenyl group,

m ₂ is an integer from 1 to 10, and n ₂ is an integer from 1 to 3.)

The polyvinyl alcohol-based compound may include polyvinyl alcohol, a copolymer of a vinyl alcohol monomer and a carboxyl group-containing anionic monomer, or a combination thereof.

The number average molecular weight of the polyvinyl alcohol-based compound may be 10,000 g/mol to 100,000 g/mol.

The C8 to C18 alkyl sulfate alkali metal salt may include sodium lauryl sulfate, potassium lauryl sulfate, or a combination thereof.

The sheet-type detergent is 20% to 30% by weight of the polyvinyl alcohol-based compound; 15% to 30% by weight of the first anionic surfactant; 10% to 35% by weight of the second anionic surfactant; and 5 wt% to 30 wt% of the nonionic surfactant.

The total content of the second anionic surfactant and the nonionic surfactant may be 1 wt% or more to less than 60 wt% based on the total amount of the sheet-type detergent.

The ratio of the total content of the second anionic surfactant and the nonionic surfactant to the content of the first anionic surfactant may be a weight ratio of 20:80 to 80:20.

The sheet-type detergent may further include starch.

The starch may be included in an amount of 0.1 wt% to 7 wt% based on the total amount of the sheet-type detergent.

The sheet-type detergent may further include an inorganic salt, glycerin, a silicone oil-containing enzyme, or a combination thereof.

The sheet-type detergent may have a specific gravity of 0.6 to 0.9.

Another embodiment is a polyvinyl alcohol-based compound, a first anionic surfactant comprising a C8 to C18 alkyl sulfate alkali metal salt, a second anionic surfactant represented by Formula 3, and a nonionic surfactant represented by Formula 4 mixing a surfactant; And it provides a method for producing a sheet-type detergent comprising the step of drying the mixed solution obtained by mixing.

Before the drying step, the method may further include bubbling the mixed solution.

The sheet-type detergent according to the exemplary embodiment is completely dissolved in water and does not need to be removed after washing, has excellent washing and rinsing performance, and has excellent formability and storage stability.

Hereinafter, the embodiments will be described in detail so that those of ordinary skill in the art can easily implement them. However, the embodiments may be embodied in many different forms and are not limited to the embodiments described herein.

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in a compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amino group Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, It means substituted with a substituent selected from a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, and combinations thereof.

In addition, unless otherwise defined herein, 'hetero' means containing 1 to 3 heteroatoms selected from N, O, S and P.

The sheet-type detergent according to an embodiment includes a polyvinyl alcohol-based compound, a first anionic surfactant, a second anionic surfactant, and a nonionic surfactant. Each of the above components will be described in detail below. The sheet-type detergent according to the exemplary embodiment is easily completely dissolved in water and does not need to be removed after washing, and has excellent washing performance, specifically, washing and rinsing performance. In addition, there is little smearing on the surface of the sheet, and it has a tensile strength that does not break during use, and has excellent film formability by having flexibility, and is excellent in storage stability because it is not absorbed by moisture in the air.

The polyvinyl alcohol-based compound may be used as a formulation agent in the sheet-type detergent according to an embodiment.

The polyvinyl alcohol-based compound may include polyvinyl alcohol, a copolymer of a vinyl alcohol monomer and a carboxyl group-containing anionic monomer, or a combination thereof. When the polyvinyl alcohol-based compound is used, a sheet-type detergent having excellent cleaning performance as well as film formability and solubility can be obtained.

The carboxyl group-containing anionic monomer constituting the copolymer may be a compound represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

[Formula 2]

(In Formulas 1 and 2,

R ³ to R ⁷ are each independently hydrogen or a methyl group, and a ₁ to a ₃ are each independently an integer of 0 to 3.)

The carboxyl group-containing anionic monomer may be included in an amount of 0.5 mol% to 5 mol%, for example, 1 mol% to 3 mol%, based on the total amount of the copolymer. When the copolymer composed of the above ratio is used, it is possible to obtain a sheet-type detergent having excellent cleaning performance as well as film formability and solubility.

The degree of saponification of the polyvinyl alcohol may be 80% to 90%, for example, 85% to 90%. In addition, the degree of saponification of the copolymer of the vinyl alcohol monomer and the carboxyl group-containing anionic monomer may be 60% to 90%, for example, 70% to 85%, 70% to 82%. When the degree of saponification of the copolymer is within the above range, a sheet-type detergent having excellent solubility can be obtained.

The polyvinyl alcohol-based compound may have a number average molecular weight of 10,000 g/mol to 100,000 g/mol, for example, 20,000 g/mol to 50,000 g/mol, 25,000 g/mol to 50,000 g/mol, 25,000 g/mol to 30,000 g/mol may be used. When a polyvinyl alcohol-based compound having a number average molecular weight in the above range is used, a sheet-type detergent having excellent film formability and easy preparation of a sheet-type detergent, as well as solubility, storage stability and washing performance can be obtained.

The polyvinyl alcohol-based compound may be included in an amount of 20 wt% to 30 wt%, for example, 22 wt% to 29 wt%, or 25 wt% to 29 wt% based on the total amount of the sheet-type detergent. When the polyvinyl alcohol-based compound is included within the above content range, a sheet-type detergent having excellent film formability can be obtained. Specifically, it is possible to obtain a sheet-type detergent having excellent solubility in water and high tensile strength, which is easy to mix ingredients in the manufacture of a sheet-type detergent, has an excellent surface feeling to the extent that the surface is not too hard or soft after drying, and is excellent in water solubility.

The first anionic surfactant may act as a main surfactant in the sheet-type detergent according to an embodiment to exhibit excellent cleaning performance. In addition, due to the excellent compatibility with the polyvinyl alcohol-based compound, it is possible to form a detergent having a high strength sheet formulation.

The first anionic surfactant may include a C8 to C18 alkyl sulfate alkali metal salt. The alkyl sulfate alkali metal salt may specifically include sodium lauryl sulfate, potassium lauryl sulfate, or a combination thereof. When the first anionic surfactant is used, it is possible to obtain a sheet-type detergent having excellent cleaning performance as well as securing a solid film form and excellent film formability.

The first anionic surfactant may be included in an amount of 15 wt% to 30 wt%, for example, 20 wt% to 28 wt%, 24 wt% to 28 wt%, based on the total amount of the sheet-type detergent. When the first anionic surfactant is included within the above content range, a sheet-type detergent having excellent cleaning performance and film formability can be obtained.

The second anionic surfactant may act as an auxiliary surfactant in the sheet-type detergent according to an embodiment, and may further improve cleaning performance while maintaining excellent film formability of the sheet-type detergent.

The second anionic surfactant may be a compound represented by the following formula (3).

[Formula 3]

In Formula 3, the substituent portion of R ¹ may exhibit excellent cleaning performance by controlling the adsorption of contaminants and fibers. R ¹ is a substituted or unsubstituted straight or branched C9 to C16 alkyl group, or a substituted or unsubstituted straight or branched C9 to C16 alkenyl group, for example, a substituted or unsubstituted straight or branched chain It may be a C9 to C16 alkyl group.

In Chemical Formula 3, X and Y portions may control washing power and solubility. X may be -SO ₃ or -COO, for example, -SO ₃ . In addition, Y is an alkali metal, for example, may be Na or K.

In Chemical Formula 3, the portion of m ₁ representing the repeating unit of ethylene oxide exhibits hydrophilicity to control washing power and solubility, and to control detergent residue on fibers. m ₁ is an integer of 1 to 9, for example, may be an integer of 1 to 8, 1 to 7, 1 to 6, or 1 to 5. When m ₁ is within the above range, it is possible to obtain a sheet-type detergent that is easily completely dissolved in water and has excellent cleaning and rinsing performance.

In Chemical Formula 3, the portion of n ₁ representing the repeating unit of propylene oxide exhibits lipophilicity, thereby controlling detergent residue on fibers and adsorption of contaminants. n ₁ is an integer of 1 to 3, for example, may be an integer of 1 to 2. When n ₁ is within the above range, a sheet-type detergent having excellent washing performance and rinsing performance can be obtained.

Specifically, the ratio of m ₁ representing the repeating unit of ethylene oxide and n ₁ representing the repeating unit of propylene oxide may be 1:1 to 5:1, for example, 1:1 to 4:1. . When the ratio of m ₁ and n ₁ is within the above range, it is possible to obtain a sheet-type detergent having excellent solubility as well as washing performance and rinsing performance.

The second anionic surfactant may be included in an amount of 10 wt% to 35 wt%, for example, 10 wt% to 25 wt%, 15 wt% to 20 wt% based on the total amount of the sheet-type detergent. When the second anionic surfactant is included within the above content range, it is possible to obtain a sheet-type detergent having little oozing phenomenon on the surface of the sheet-type detergent and having excellent solubility as well as washing performance and rinsing performance.

The nonionic surfactant may act as an auxiliary surfactant like the second anionic surfactant in the sheet-type detergent according to an embodiment, and may further improve cleaning performance while maintaining excellent film formability of the sheet-type detergent. .

The nonionic surfactant may be a compound represented by the following formula (4).

[Formula 4]

In Formula 4, the substituent portion of R ² may exhibit excellent cleaning performance by controlling the adsorption of contaminants and fibers. R ² is a substituted or unsubstituted straight or branched C9 to C16 alkyl group, or a substituted or unsubstituted straight or branched C9 to C16 alkenyl group, for example, a substituted or unsubstituted straight or branched chain It may be a C9 to C16 alkyl group.

In Chemical Formula 4, the portion of m ₂ representing the repeating unit of ethylene oxide exhibits hydrophilicity to control washing power and solubility, and to control detergent residue on fibers. m ₂ is an integer of 1 to 10, for example, may be an integer of 2 to 10, 3 to 10, 4 to 10, 5 to 10. When it has m ₂ within the above range, it is possible to obtain a sheet-type detergent that is easily completely dissolved in water and has excellent washing performance and rinsing performance.

In Chemical Formula 4, the portion of n ₂ representing the repeating unit of propylene oxide exhibits lipophilicity, thereby controlling detergent residue on fibers and adsorption of contaminants. n ₁ is an integer of 1 to 3, for example, may be an integer of 1 to 2. When n ₂ is within the above range, it is possible to obtain a sheet-type detergent having excellent washing performance and rinsing performance.

Specifically, the ratio of m ₂ representing the repeating unit of ethylene oxide and n ₂ representing the repeating unit of propylene oxide may be 6:1 to 10:1, for example, 7:1 to 10:1. . When the ratio of m ₂ and n ₂ is within the above range, a sheet-type detergent having excellent solubility as well as washing performance and rinsing performance can be obtained.

The nonionic surfactant may be included in an amount of 5% to 30% by weight based on the total amount of the sheet detergent, for example, 5% to 20% by weight, 5% to 15% by weight, 7% to 13% by weight. % may be included. When the non-ionic surfactant is included within the above content range, it is possible to obtain a sheet-type detergent having less oozing phenomenon on the surface of the sheet-type detergent and having excellent solubility as well as cleaning performance and rinsing performance.

In the sheet-type detergent according to an embodiment, the total content of the second anionic surfactant and the non-ionic surfactant acting as an auxiliary surfactant may be 1% by weight or more to less than 60% by weight based on the total amount of the sheet-type detergent, For example, 10 wt% or more and less than 60 wt%, 20 wt% or more and less than 60 wt%, 30 wt% or more and less than 60 wt%, 40 wt% or more and less than 60 wt%. When the sum of the contents of the two components of the auxiliary surfactant is within the above range, a sheet-type detergent having excellent solubility as well as washing and rinsing performance can be obtained.

In the sheet detergent according to an embodiment, the ratio of the total content of the second anionic surfactant and the nonionic surfactant acting as an auxiliary surfactant to the content of the first anionic surfactant acting as the main surfactant is 20 It may be a weight ratio of :80 to 80:20, for example, a weight ratio of 30:70 to 70:30, and a weight ratio of 40:60 to 60:40. When the sum of the two components of the auxiliary surfactant and the content ratio of the main surfactant are within the above range, a sheet-type detergent having excellent solubility as well as cleaning and rinsing performance can be obtained.

The sheet-type detergent according to an embodiment may further include starch.

The starch may be used as an additional formulating agent in a sheet-type detergent.

The starch may be included in an amount of 0.1% to 7% by weight, for example, 1% to 7% by weight, 3% to 7% by weight, 5% to 7% by weight based on the total amount of the sheet-type detergent. can When the starch is used within the above content range, a sheet-type detergent having excellent film formability can be obtained.

The sheet-type detergent may further include an additive to improve cleaning performance within a range that does not impair film formability, storage stability, ease of manufacture, and the like.

The additive may include an inorganic salt, a silicone oil-containing enzyme, glycerin, a cellulose derivative, sodium chloride, citric acid, propylene glycol, or a combination thereof.

The inorganic salt is sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium metasilicate, sodium alkali silicate, neutral sodium silicate, sodium tripolyphosphate, sodium pyrophosphate, sodium borate, zeolite (sodium aluminosilicate), sodium sesquicarbonate, or these may include a combination of

The silicone oil-containing enzyme may be a cellulase containing silicone oil, a protease, or the like.

In addition, the additive may further include a fabric softener, a bleach, a dispersant or emulsifier, a disinfectant or disinfectant, a fragrance, a preservative, an antibacterial agent, and the like.

Examples of the fabric softener include quaternary ammonium salt-based cationic surfactants, silicone-based fabric softeners, and the like. Examples of the bleaching agent include perborate, percarbonate, superphosphate, diacyl, and tetraacyl peroxide. Examples of the dispersant or emulsifier include polyoxyalkylene alkylphenyl ether, polyoxyalkylene alkyl ether, and polyoxyethylene polyoxypropylene block polymer. Examples of the disinfectant or disinfectant include sodium hypochlorite, hydrogen peroxide, and urea peroxide.

The additive may be included in an amount of 0.01 wt% to 10 wt%, for example, 0.1 wt% to 5 wt%, 0.5 wt% to 5 wt%, based on the total amount of the sheet-type detergent according to each purpose.

Since the sheet-type detergent according to an embodiment is completely soluble in water, a removal process is not required during washing.

The sheet-type detergent may be in a single layer, or in a form in which two or more layers are stacked.

The sheet detergent may have a thickness of 1 μm to 1 cm, for example, 5 μm to 0.5 cm, or 50 μm to 1 mm. When the sheet-type detergent has a thickness within the above range, the film has high strength and excellent solubility, thereby improving cleaning performance.

The sheet-type detergent according to one embodiment is obtained by mixing a polyvinyl alcohol-based compound, a first anionic surfactant, a second anionic surfactant, and a nonionic surfactant, and drying the mixed solution obtained by mixing, can be manufactured. The mixed solution may be prepared by dissolving a polyvinyl alcohol-based compound in water to prepare a polyvinyl alcohol-based compound solution, and then mixing the surfactant components thereto. It may be prepared by mixing an alcohol-based compound, but is not limited thereto.

The sheet-type detergent may be prepared by additionally performing bubbling before drying the mixed solution. By adjusting the specific gravity of the sheet-type detergent through the bubbling step, solubility in water can be improved, and thus, a sheet-type detergent having excellent cleaning performance can be obtained.

Hereinafter, specific embodiments of the present invention are presented. However, the examples described below are only for specifically illustrating or explaining the present invention, and the present invention is not limited thereto. In addition, since the contents not described herein can be technically inferred sufficiently by those skilled in the art, the description thereof will be omitted.

(Manufacture of sheet-type detergent)

Examples 1 to 11 and Comparative Examples 1 to 13

A mixed solution was prepared by dissolving the components in distilled water according to the composition of Tables 1 and 2 below, and then the mixed solution was placed on the release film, and then prepared to a predetermined thickness using Elcometer's film applicator, followed by 10 minutes in a drying oven at 115 ° C. It was dried to prepare a sheet-type detergent having a thickness of 0.01 cm.

The components used in Tables 1 and 2 below are as follows.

- As a polyvinyl alcohol-based compound, Kuraray's polyvinyl alcohol (PVA) 5-88 was used. The product has a number average molecular weight of 25,000 g/mol to 30,000 g/mol and a saponification degree of 86.5% to 89% of PVA.

- As the first anionic surfactant, sodium lauryl sulfate (SLS) was used.

- As the second anionic surfactant, a compound (LAEPS) represented by the following formula (5) was used.

- As a nonionic surfactant, a compound (LAEP) represented by the following formula (6) was used.

[Formula 5]

(In Formula 5, R ⁸ is a dodecyl group.)

[Formula 6]

(In Formula 6, R ⁹ is a dodecyl group.)

(Unit: % by weight) Example One 2 3 4 5 6 7 8 9 10 11 PVA 20 30 28 25 20 28 28 28 28 28 23 SLS 20 25 25 25 25 20 30 15 25 25 23 LAEPS 20 15 15 15 15 20 10 25 20 10 10 LAEP 10 10 10 10 10 10 10 10 5 15 20 NaHCO ₃ 9 9 9 9 9 9 9 9 9 9 9 glycerin 3 3 3 3 3 3 3 3 3 3 3 starch 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 Enzyme containing silicone oil One One One One One One One One One One One Spices remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount

(Unit: % by weight) comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 PVA 28 28 28 25 28 28 25 28 28 28 28 28 28 SLS 25 20 30 25 25 20 25 25 20 0 0 25 25 SLES 0 0 0 0 0 0 0 0 0 25 0 0 0 AOS 0 0 0 0 0 0 0 0 0 0 25 0 0 LAEPS 0 0 0 15 15 15 0 0 0 15 15 15 15 LAEP 0 0 0 0 0 0 10 10 10 10 10 0 0 LA7 0 0 0 0 0 0 0 0 0 0 0 10 0 LA9 0 0 0 0 0 0 0 0 0 0 0 0 10 NaHCO ₃ 9 9 9 9 9 9 9 9 9 9 9 9 9 glycerin 3 3 3 3 3 3 3 3 3 3 3 3 3 starch 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 Enzyme containing silicone oil One One One One One One One One One One One One One Spices remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount remaining amount

- SLES stands for Sodium Laureth Sulfate.

- AOS means alpha olefin sulfonate.

- LA7 means heptaoxyethylated lauryl alcohol.

- LA9 means nanooxyethylated lauryl alcohol.

Evaluation 1: Ease of mixing of sheet-type detergent

In the preparation of the sheet-type detergents according to Examples 1 to 11 and Comparative Examples 1 to 13, the ease of mixing of the components was evaluated based on the following criteria, and the results are shown in Table 3 below.

Evaluation criteria: ◎ Very good, ○ Excellent, △ Fair, X Poor (too hard or too soft)

Evaluation 2: Surface feeling of sheet-type detergent

For the sheet-type detergents prepared in Examples 1 to 11 and Comparative Examples 1 to 13, the surface feel after drying was evaluated based on the following criteria, and the results are shown in Table 3 below.

Evaluation criteria: ◎ Very good, ○ Excellent, △ Fair, X Poor (too hard or too soft)

Evaluation 3: Solubility of the sheet-like detergent

The solubility of the sheet-type detergents prepared in Examples 1 to 11 and Comparative Examples 1 to 13 was measured in the following manner, and the results are shown in Table 3 below.

The prepared film sheet was cut into 5 cm x 5 cm, and about 300 ml of purified water at 15° C. was put into a 500 ml beaker and stirred at a constant speed. The time taken for the film to completely disintegrate and dissolve was measured, and evaluation was made based on the following criteria.

◎ (very good): less than 3 minutes

○ (Excellent): More than 3 minutes and less than 5 minutes

△ (Normal): 5 minutes or more and less than 10 minutes

X (bad): more than 10 minutes

Evaluation 4: Film Formulation of Sheet-Type Detergent

The film formulation properties of the sheet-type detergents prepared in Examples 1 to 11 and Comparative Examples 1 to 13 were visually observed and evaluated according to the following criteria, and the results are shown in Table 3 below.

◎: The film formulation is flexible and there is no smearing phenomenon

○: The film formulation is flexible, but a slight smearing phenomenon occurs

△: Insufficient flexibility of the film formulation, a slight smearing phenomenon occurred

X: The film is not formulated, and the smearing phenomenon is severe.

Evaluation 5: Cleaning power of sheet-type detergent

The cleaning power of the sheet-type detergents prepared in Examples 1 to 11 and Comparative Examples 1 to 13 was measured as follows, and the results are shown in Table 3 below.

1g of sample per 1L of water and artificial stained cloth are put into agitation and mixing detergency tester (Terg-O-tometer, United States Testing Co., Inc.) 10 minutes and rinsing were performed twice each for 3 minutes each. The cleaning power of the artificial stained fabric before and after washing was measured by measuring the whiteness with a color difference meter (colormeter, Japan testing Co., INC.), and the washing power calculated according to Equation 1 below was determined as the evaluation criteria below.

At this time, the artificial stained fabric used W10D (Center For Testmaterials BV) and JIS (wet artificial stained fabric), the W10D stained fabric was a stained fabric made by oily stains on cotton fibers, and the W20D stained fabric was oily stained on the blended fiber. was cut into 8x8 cm in width x length and 6 sheets per sample. In addition, the JIS stained cloth was artificially made from contamination that may occur in the human body on cotton fibers, and was cut into 5x5cm in width and length and 8 sheets were used for each sample.

[Equation 1]

Cleaning power (%) = {(C-B)/(A-B)} X 100

(In Equation 1, A is the whiteness of the white cloth, B is the whiteness of the contaminated cloth before washing, and C is the whiteness of the soiled cloth after washing.)

◎ (Very good): More than 45% cleaning power

○ (Excellent): 40% or more and less than 45% of cleaning power

△ (Normal): 35% or more and less than 40% of cleaning power

X (poor): Less than 35% cleaning power

Evaluation 6: Rinseability of sheet-type detergent

The rinse properties of the sheet-type detergents prepared in Examples 1 to 11 and Comparative Examples 1 to 13 were measured as follows, and the results are shown in Table 3 below.

1.2 kg of cotton towel and the sheet-type detergent prepared in Examples 1 to 11 and Comparative Examples 1 to 13 were put into a front-load washing machine (LG Electronic) used at home, and the washing temperature was adjusted to 40°C. So, washing was performed for 30 minutes, and rinsing was performed twice each for 5 minutes each. By marking the scale from 0 to 25 on the transparent window of the drum type washing machine, the amount of bubbles generated in the rinsing step was measured, and the rinsing property was evaluated according to the following evaluation criteria, and the results are shown in Table 3 below.

◎ (Excellent): The amount of bubble generation is 1 or less on the display scale

○ (Excellent): The amount of bubble generation exceeds 1 to 3 on the display scale.

△ (Normal): The amount of bubble generation is more than 3 to 5 or less on the display scale

X (Bad): The amount of bubble generation exceeds 5 on the display scale

Evaluation 7: Fiber Persistence of Sheet-Type Detergent

The fiber residues of the sheet-type detergents prepared in Examples 1 to 11 and Comparative Examples 1 to 13 were measured in the following manner, and the results are shown in Table 3 below.

After measuring the total organic carbon (TOC) content by collecting the water drained in the process of washing the test load (towel) using the sample, it is compared with the total organic carbon content of the initial sample solution. The proportion of carbon to be used was calculated, and the residual rate of the surfactant including organic carbon was inversely calculated from this result. Washing was carried out at 20°C using a drum type washing machine (Front-Load Washing Machine, LG Electronic), and after measuring the total organic carbon content by collecting all the water drained during the washing process, the residual calculated according to Equation 2 below The rate was determined according to the following evaluation criteria.

[Equation 2]

Total organic carbon retention (%) = {A-(B-C)}/A X 100

(In Equation 2 above,

A represents the organic carbon concentration of the initial detergent solution. Specifically, after inputting the test load and the sample, measuring the amount of water supplied during the washing process, dividing the sample input amount by the corresponding amount, diluting the sample to the concentration obtained is the organic carbon concentration of the solution (mg/L),

B represents the organic carbon concentration of the test effluent, specifically, the organic carbon concentration (mg/L) of the water drained after the test load and sample are input and washing treatment is performed,

C represents the organic carbon concentration of the drained water from the blank test, specifically, the organic carbon concentration (mg/L) of the drained water after washing without a test load and sample before washing using a sample.)

◎ (Excellent): Less than 10% of surfactant residue after washing

○ (Excellent): After washing, the residual rate of surfactant exceeds 10% and less than 15%

△ (Normal): After washing, the surfactant retention rate is more than 15% and less than 20%

X (poor): After washing, the surfactant residue exceeds 20%

ease of mixing surface feeling Solubility film formulation cleaning power Rinseability Fiber Persistence Example 1 ◎ ○ ◎ ○ ◎ ○ ◎ Example 2 ○ ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ○ ◎ ◎ ◎ Example 5 ◎ ○ ◎ ○ ◎ ◎ ◎ Example 6 ○ ◎ ◎ ○ ◎ ○ ◎ Example 7 ◎ ◎ ◎ ◎ ○ ◎ ○ Example 8 ○ ◎ ◎ ○ ◎ ○ ○ Example 9 ○ ◎ ◎ ○ ◎ ○ ○ Example 10 ◎ ○ ◎ ○ ◎ ◎ ◎ Example 11 ◎ ○ ◎ ○ ○ ◎ ◎ Comparative Example 1 ○ △ △ X X ○ △ Comparative Example 2 ○ △ △ X X ○ △ Comparative Example 3 ○ △ △ X X ○ △ Comparative Example 4 △ ○ △ △ △ △ △ Comparative Example 5 △ ○ △ △ △ △ △ Comparative Example 6 △ ○ △ △ △ △ △ Comparative Example 7 ○ △ △ X X △ ○ Comparative Example 8 ○ △ △ X X △ ○ Comparative Example 9 ○ △ △ X X △ ○ Comparative Example 10 △ X △ X △ △ ○ Comparative Example 11 △ X △ X X ○ ○ Comparative Example 12 △ △ △ △ △ △ △ Comparative Example 13 △ △ △ △ X △ △

Through Table 3, it can be seen that the sheet-type detergents according to Examples 1 to 11 exhibit excellent film formability, washing performance, and low fiber retention compared to Comparative Examples 1 to 13.

Specifically, in the case of Comparative Examples 1 to 3 that did not use the second anionic surfactant and the nonionic surfactant acting as an auxiliary surfactant in one embodiment, compared to Examples 1 to 11, film formability, cleaning performance, and lower fiber Persistence was reduced.

In addition, in Comparative Examples 4 to 6 in which only the second anionic surfactant among the auxiliary surfactants was used alone, the film formability, washing performance, and low fiber retention properties were lowered compared to Examples 1 to 11.

In addition, in the case of Comparative Examples 7 to 9 in which only the nonionic surfactant was used alone among the auxiliary surfactants, the film formability, washing performance and low fiber retention were lowered compared to Examples 1 to 11.

In addition, in the case of Comparative Examples 10 and 11 in which other types of surfactants such as SLES and AOS were used instead of the first anionic surfactant used as the main surfactant in one embodiment, the film formability and cleaning performance compared to Examples 1 to 11 and low fiber retention.

In addition, as a nonionic surfactant according to an embodiment, instead of a compound having both an ethylene oxide repeating unit and a propylene oxide repeating unit, a compound having only an ethylene oxide repeating unit, that is, using other types of surfactants such as LA7 and LA9 In Comparative Examples 12 and 13, compared to Examples 1 to 11, film formability, washing performance, and low fiber retention were lowered.

From this, it can be seen that the sheet-type detergent according to one embodiment is excellent in film formability, washing performance, and low fiber retention.

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and it is possible to carry out various modifications within the scope of the claims, the detailed description of the invention, and the accompanying drawings. It goes without saying that it falls within the scope of the invention.

Claims (12)

polyvinyl alcohol-based compounds;
a first anionic surfactant comprising a C8 to C18 alkyl sulfate alkali metal salt;
a second anionic surfactant represented by the following formula (3); and
A sheet-type detergent comprising a nonionic surfactant represented by the following formula (4).
[Formula 3]

(In Formula 3,
R ¹ is a substituted or unsubstituted straight or branched C9 to C16 alkyl group, or a substituted or unsubstituted straight or branched C9 to C16 alkenyl group,
X is -SO ₃ or -COO,
Y is an alkali metal,
m ₁ is an integer from 1 to 9, and n ₁ is an integer from 1 to 3.)
[Formula 4]

(In Formula 4,
R ² is a substituted or unsubstituted straight or branched C9 to C16 alkyl group, or a substituted or unsubstituted straight or branched C9 to C16 alkenyl group,
m ₂ is an integer from 1 to 10, and n ₂ is an integer from 1 to 3.) In claim 1,
The polyvinyl alcohol-based compound is a sheet-type detergent comprising polyvinyl alcohol, a copolymer of a vinyl alcohol monomer and an anionic monomer containing a carboxyl group, or a combination thereof. In claim 1,
The polyvinyl alcohol-based compound has a number average molecular weight of 10,000 g/mol to 100,000 g/mol. In claim 1,
The C8 to C18 alkyl sulfate alkali metal salt is a sheet-type detergent comprising sodium lauryl sulfate, potassium lauryl sulfate, or a combination thereof. In claim 1,
The sheet-type detergent is
20% to 30% by weight of the polyvinyl alcohol-based compound;
15% to 30% by weight of the first anionic surfactant;
10% to 35% by weight of the second anionic surfactant; and
A sheet-type detergent comprising 5% to 30% by weight of the nonionic surfactant. In claim 1,
The total content of the second anionic surfactant and the nonionic surfactant is 1% by weight or more to less than 60% by weight based on the total amount of the sheet-type detergent. In claim 1,
The ratio of the total content of the second anionic surfactant and the nonionic surfactant to the content of the first anionic surfactant is a weight ratio of 20:80 to 80:20. In claim 1,
The sheet-type detergent is a sheet-type detergent further comprising starch. In claim 8,
The starch is included in an amount of 0.1% to 7% by weight based on the total amount of the sheet-type detergent. In claim 1,
The sheet-type detergent further comprises an inorganic salt, glycerin, a silicone oil-containing enzyme, or a combination thereof. A polyvinyl alcohol-based compound, a first anionic surfactant comprising a C8 to C18 alkyl sulfate alkali metal salt, a second anionic surfactant represented by the following formula (3), and a nonionic surfactant represented by the following formula (4) are mixed step; and
A method of manufacturing a sheet-type detergent comprising the step of drying the mixed solution obtained by mixing.
[Formula 3]

(In Formula 3,
R ¹ is a substituted or unsubstituted straight or branched C9 to C16 alkyl group, or a substituted or unsubstituted straight or branched C9 to C16 alkenyl group,
X is -SO ₃ or -COO,
Y is an alkali metal,
m ₁ is an integer from 1 to 9, and n ₁ is an integer from 1 to 3.)
[Formula 4]

(In Formula 4,
R ² is a substituted or unsubstituted straight or branched C9 to C16 alkyl group, or a substituted or unsubstituted straight or branched C9 to C16 alkenyl group,
m ₂ is an integer from 1 to 10, and n ₂ is an integer from 1 to 3.) In claim 11,
Before the drying step, the method of manufacturing a sheet-type detergent further comprising the step of bubbling (bubbling) the mixed solution.