JP2001294899A - Sheet laundry products - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the solubility of a sheet-like laundry product obtained by laminating a water-soluble substrate on a detergent composition. SOLUTION: A thin layer comprising a water-soluble substrate is laminated on one or both sides of a thin layer of a laundry composition containing at least one selected from a detergent for clothing, a fabric softener and a bleaching agent. A sheet-like laundry product, wherein a water-insoluble material having a property of swelling when it comes into contact with water, in a thin layer composed of the water-soluble substrate, or in both a thin layer of the laundry composition and a thin layer composed of the water-soluble substrate. It is characterized by containing a disintegrant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet detergent excellent in handleability, and more particularly to a detergent having improved solubility.

[0002]

2. Description of the Related Art Recently, detergents in the form of tablets, sheets and the like, which are easy to handle, have attracted attention. For example,
Japanese Patent Application Laid-Open No. 8-165549 discloses a composite of a polymer and a surfactant that can be formed into a sheet or stick shape.

[0003] However, in the conventional sheet-like detergent obtained by molding the detergent composition into a sheet, the solubility tends to decrease when importance is placed on the sheet formability. There was a problem such as adhesion. On the other hand, if the composition is made with emphasis on solubility, it may be difficult to form a detergent composition containing a surfactant or the like into a sheet, or even if molded, the strength may not be sufficient and shape retention may be poor. .

[0004]

SUMMARY OF THE INVENTION Therefore, Japanese Patent Application Laid-Open No. Hei 10-2
No. 04499 discloses a sheet-like detergent in which a sheet-like water-soluble substrate is disposed on both sides of a thin layer made of a detergent composition. With such a configuration, shape retention can be improved, but there is still dissatisfaction with the solubility of the sheet-shaped detergent, particularly the solubility of the sheet-shaped water-soluble substrate, and the sheet-shaped laundry product having excellent solubility. In order to achieve the above, it has been desired to improve the solubility of the water-soluble substrate. Also, improvement of the solubility of the detergent composition thin layer itself has been a more important issue than before.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to improve the solubility of a sheet-like laundry product obtained by laminating a water-soluble substrate on a detergent composition.

[0006]

In order to solve the above-mentioned problems, a sheet-like laundry product of the present invention comprises a laundry containing at least one selected from a detergent for clothing, a fabric softener, and a bleaching agent. A sheet-like laundry product obtained by laminating a thin layer made of a water-soluble substrate on one or both sides of a thin layer of the composition for washing, wherein the thin layer made of the water-soluble substrate, or the thin layer of the laundry composition A water-insoluble disintegrating agent having a property of swelling upon contact with water is contained in both of the thin layers comprising the water-soluble substrate. The water-insoluble disintegrant includes a) cellulose, b) a layered clay mineral, c) a clay mineral having a patchwork structure in water, and / or
Or at least one selected from quaternary ammonium salt-containing clay minerals.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The laundry composition thin layer of the present invention contains at least one selected from a detergent for clothing, a fabric softener, and a bleaching agent.

[Cleaning agent for clothing] The cleaning agent for clothing which can be used in the present invention includes anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants generally used in this field. Surfactants, water-soluble inorganic salts,
Alkali builder, chelate builder, anti-redeposition agent,
Enzymes, reducing agents, soil release agents, dye transfer inhibitors, fluorescent dyes, fragrances, clays, foam inhibitors such as silicones, percarbonates, perborates, bleach activators, granulation aids such as polyethylene glycol And the like, and is not particularly limited.

Specific examples of the anionic surfactant include a linear or branched alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms,
Alkylsulfuric acid (AS) salt or alkenyl sulfate, α-olefinsulfonic acid having 10 to 20 carbon atoms (A
OS) salt, alkanesulfonic acid having 10 to 20 carbon atoms,
It has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and has an average of 0.5 to 8 mol of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide =
Alkyl ether sulfate (AES) or alkenyl ether sulfate added in a ratio of 0.1 / 9.9 to 0.9 / 0.1, a linear or branched alkyl group or alkenyl having 10 to 20 carbon atoms Alkyl ether having a group and having an average of 0.5 to 8 mol of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide added in a ratio of 0.1 / 9.9 to 9.9 / 0.1 Carboxylate or alkenyl ether carboxylate, alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms, higher fatty acid salt having 10 to 20 carbon atoms, saturated or having 8 to 20 carbon atoms or Unsaturated α-sulfofatty acids (α-S
F) Salts or their methyl, ethyl or propyl esters and the like. Preferably, for example, alkali metal salts (for example, sodium or potassium salts) of linear alkylbenzene sulfonic acid (LAS), AOS, α-
Examples thereof include alkali metal salts of SF and AES (for example, sodium or potassium salts) and alkali metal salts of higher fatty acids (for example, sodium or potassium salts).

[0010] Examples of the cationic surfactant include the following. 1) Dilong-chain alkyldi-short-chain alkyl-type quaternary ammonium salt [R ₁ R ₂ R ₃ R ₄ N] + .X- (wherein, R ₁ and R ₂ usually have 12 to 26 carbon atoms, preferably And represents an alkyl group having 14 to 18. R ₃ and R _{4 each} are usually an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, a benzyl group, and usually having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. X represents a hydroxyalkyl group or a polyoxyalkylene group, and X represents halogen, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , 1 /
_{2SO 4, OH, HSO 4,} CH 3 CO 2 or CH ₃ -
C ₆ H ₄ —SO ₃ is shown. )

As the di-long chain alkyl di-short chain alkyl type quaternary ammonium salt, specifically, distearyl dimethyl ammonium salt, di hydrogenated tallow alkyl dimethyl ammonium salt, di hydrogenated tallow alkyl benzene methyl ammonium salt, distearyl Examples include methylbenzylammonium salt, distearylmethylhydroxyethylammonium salt, distearylmethylhydroxypropylammonium salt, distearyldihydroxyethylammonium salt, dioleyldimethylammonium salt, and dicoconut alkyldimethylammonium salt. Specific examples of halogen as X include a chlorine atom,
And a bromine atom.

2) Mono-long-chain alkyl tri-short-chain alkyl type quaternary ammonium salt [R ₁ R ₂ R ₃ R ₄ N] + .X- (wherein, R ₁ usually has 12 to 26 carbon atoms; Preferably 14
And represents an alkyl group of 1818. R ₂ , R ₃ and R ₄ are usually an alkyl group having 1 to 4, preferably 1 to 2 carbon atoms,
A benzyl group, usually a hydroxyalkyl group having 2 to 4, preferably 2 to 3 carbon atoms, or a polyoxyalkylene group. X represents halogen, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , 1
/ 2SO ₄ , OH, HSO ₄ , CH ₃ CO ₂ or CH ₃
-C ₆ H ₄ -SO ₃ is shown. )

Specific examples of the mono-long-chain alkyltri-short-chain alkyl quaternary ammonium salt include lauryltrimethylammonium salt, stearyltrimethylammonium salt, hydrogenated tallow alkyltrimethylammonium salt,
Examples include hydrogenated tallow alkylbenzene dimethyl ammonium salt, stearyl dimethyl benzyl ammonium salt, stearyl dimethyl hydroxyethyl ammonium salt, stearyl dimethyl hydroxy propyl ammonium salt, stearyl trihydroxyethyl ammonium salt, oleyl trimethyl ammonium salt, coconut alkyl trimethyl ammonium salt, and the like. Specific examples of halogen as X include a chlorine atom and a bromine atom.

3) Tetra short chain alkyl type quaternary ammonium salt [R ₁ R ₂ R ₃ R ₄ N] + .X- (wherein R ₁ , R ₂ , R ₃ and R ₄ are usually carbon atoms) Is 1-4, preferably 1-3 alkyl groups, benzyl groups,
Usually, it has 2 to 4, preferably 2 to 3 hydroxyalkyl groups or polyoxyalkylene groups. X is
_{Halogen, CH 3 SO 4, C 2} H 5 SO 4, 1 / 2SO 4
_{, OH, HSO 4, CH 3} CO 2 or CH ₃ -C ₆ H ₄
Shows the -SO _3. Examples of the tetra-short-chain alkyl type quaternary ammonium salt include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydroxide tetrabutylammonium hydrogen sulfate, benzyltrimethylammonium chloride, and benzyltrimethyl. Examples thereof include ammonium hydroxide, benzyltriethylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium chloride, and trimethylphenylammonium chloride.

4) Tri long chain alkyl mono short chain alkyl type
Quaternary ammonium salt [R₁ R_Two R_ThreeR_Four N] +. X- (where R₁ , R_Two And R_Three Usually has 12 to 2 carbon atoms
6, preferably 14 to 18 alkyl groups. R_Four Is
Usually, it has 1 to 4 carbon atoms, preferably 1 to 2 alkyl groups,
Benzyl group, usually having 2 to 4, preferably 2 to 3 carbon atoms.
Represents a hydroxyalkyl group or a polyoxyalkylene group
You. X is halogen, CH_Three SO_Four , C_Two H _Five SO_Four ,
1 / 2SO_Four , OH, HSO_Four , CH_Three CO_Two Or CH
_Three -C₆ H_Four-SO_Three Is shown. ) Tri long chain alkyl mono short chain alkyl type quaternary ammonium
As the salt, specifically, trilaurylmethylammonium
Um chloride, tristearylmethylanium chloride
Ride trioleyl methyl ammonium chloride,
Coconut alkyl methyl ammonium chloride
And so on.

Examples of the nonionic surfactant include the following. (1) For example, an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and an alkylene oxide having 2 to 4 carbon atoms, for example, an average of 3 to 30 mol, preferably 5 to 2 mol
0 mole-added polyoxyalkylene alkyl (or alkenyl) ether. Among them, polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl)
Ethers are preferred. As the aliphatic alcohol used here, a primary alcohol or a secondary alcohol is used. Further, the alkyl group may have a branched chain. As preferred aliphatic alcohols, primary alcohols are used. (2) polyoxyethylene alkyl (or alkenyl)
Phenyl ether.

(3) An alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester, for example,
A fatty acid alkyl ester alkoxylate represented by the following formula: R ₁ CO (OA) _n OR ₂ (R ₁ CO represents a fatty acid residue having 6 to 22, preferably 8 to 18 carbon atoms. OA represents a fatty acid residue having 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably Represents an additional unit of 2 to 3 alkylene oxides, n represents an average number of moles of the alkylene oxide added, and is generally 3 to 30, preferably 5 to 30;
It is the number 20. R ₂ represents a lower alkyl group which may have a substituent having 1 to 3 carbon atoms. (4) Polyoxyethylene sorbitan fatty acid esters. (5) Polyoxyethylene sorbite fatty acid ester. (6) Polyoxyethylene fatty acid esters. (7) Polyoxyethylene hydrogenated castor oil. (8) Glycerin fatty acid ester. (9) fatty acid alkanolamides.

Among the above-mentioned nonionic surfactants, the melting point is 40 ° C. or less, preferably 5-35 ° C., and the HLB is 9-90.
16, preferably 10 to 15 polyoxyethylene alkyl (or alkenyl) ethers, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers, and fatty acid methyl ester ethoxylates obtained by adding ethylene oxide to fatty acid methyl esters are particularly suitable.

Examples of the amphoteric surfactant include the following. 1) Betaines represented by the following formula

[0020]

Embedded image (Wherein, R ₁ is usually an alkyl group having 12 to 18, preferably 12 to 16 carbon atoms. R ₂ and R ₃ are each CH ₃ , C ₂ H ₅ , C ₃ H ₇ , CH ₂ COOH
And so on. n shows the integer of 1-3. )

Specific examples of the above betaines include amidopropyl betaine laurate and amidoethyl betaine stearate. 2) imidazoline derivatives represented by the following formula

[0022]

Embedded image (In the formula, R ₁ is usually an alkyl group having 12 to 18, preferably 12 to 16 carbon atoms.)

Specific examples of the above imidazoline derivatives include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and N-coconut fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium. And the like.

3) Phosphate type As the phosphate type, for example, lecithin (phosphatidylcholine) represented by the following formula is preferable.

[0025]

Embedded image (Wherein, R ₁ and R ₂ usually have 14 to 22 carbon atoms,
Preferably it is a 14-18 alkyl group. )

Incidentally, the cationic surfactant and the amphoteric surfactant are deteriorated when treated at a high temperature. For example, 80 ° C
Under the above conditions, it decomposes while generating a cationic odor and an ammonia odor and changes to another compound. Therefore, a step of treating at 80 ° C. or higher in the production process, for example, a step of spray-drying a slurry containing the compound at 80 ° C. or higher must be avoided. The amount of the surfactant is 1 to 60% by weight, preferably 3 to 40% by weight, based on the detergent thin layer. If it is less than 1% by weight, the detergency tends to be insufficient, and if it exceeds 60% by weight, the strength of the sheet-like detergent is reduced and the sheet-like detergent is easily deformed.

As the detergent builder, an inorganic alkali builder and an inorganic or organic chelate builder are preferable. Specific examples of the alkali builder include alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, and the like. Examples thereof include alkali metal hydroxides, alkali metal carbonates, alkali metal silicates, layered silicates, and mixtures thereof. Examples of the alkali metal include sodium and potassium. The alkali metal silicate has a molar ratio of SiO ₂ : M ₂ O of about 1: 1.
Preferred are those from 2 to about 2.5: 1, where M is sodium or potassium. Preferred examples of the alkali builder include sodium carbonate (soda ash), sodium hydrogen carbonate, potassium carbonate, sodium silicate, and layered sodium silicate.
Specific examples of the chelate builder include an inorganic chelate builder such as a layered silicate, a crystalline aluminosilicate, and an amorphous aluminosilicate, and an organic chelate builder such as a polycarboxylate and an aminopolyacetate. As the above-mentioned chelate builder, particularly preferred are A-type, P-type, X-type and Y-type zeolites, polyacrylates, copolymers of acrylic acid and maleic acid, and the like.
The mixing amount of the alkali builder and the chelate builder is such that the concentration in the detergent thin layer is 5 to 60% by weight, preferably 10 to 50% by weight. 5% by weight
If it is less than 60%, the detergency tends to decrease, and if it exceeds 60% by weight, the content of other detergent components such as surfactants tends to decrease relatively and the balance tends to be lost.

[Fiber softening agent] As the fiber softening agent that can be used in the present invention, a known softening agent using a cationic surfactant such as a quaternary ammonium salt as a softening base can be used. Particularly, a quaternary ammonium salt of a di-long-chain alkyl type is preferable, and -COO- and-are contained in the alkyl group.
It may include a linking group such as OCO-, -NHCO-, and -CONH-. Further, as an optional component, a fragrance, a pigment, a silicone compound, an antibacterial agent, a solvent, a water-soluble salt, or the like may be contained.

[Bleach] The bleach used in the present invention is:
Anionic surfactants commonly used in this field,
Surfactants such as nonionic surfactants, water-soluble inorganic salts such as sodium carbonate, chelate builders such as zeolite, anti-soil refining agents, enzymes, reducing agents, soil release agents,
It may be composed of a dye transfer inhibitor, a fluorescent dye, a fragrance, a foaming inhibitor such as clay and silicone, a bleaching activator such as percarbonate and perborate, and a granulation auxiliary such as polyethylene glycol. However, there is no particular limitation. As a preferred example, a known bleach containing a peroxide that is a source of hydrogen peroxide can be used. As the peroxide, sodium carbonate / hydrogen peroxide adduct, sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyropolyphosphate / hydrogen peroxide adduct, urea / hydrogen peroxide adduct, 4Na
Examples include ₂ · SO ₄ · H ₂ O ₂ · NaCl, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium peroxide, calcium peroxide and the like. Among these, sodium carbonate / hydrogen peroxide adduct, sodium perborate monohydrate and sodium perborate tetrahydrate are particularly preferred. The peroxide is present in the bleach used in the present invention in an amount of from 1 to 9%.
5% by weight, preferably 10 to 90% by weight.

Further, in the present invention, the following components which are usually blended in detergents can be blended as optional components to be used in combination with a detergent for clothing, a fabric softener, and / or a bleaching agent. (1) Fluorescent agent: bis (triazonylamino) stilbene disulfonic acid derivative, bis (sulfostyryl) biphenyl salt [Tinopearl CBS] and the like. (2) Enzymes: lipase, protease, cellulase, amylase and the like. (3) Antistatic agents: cationic surfactants such as dialkyl-type quaternary ammonium salts. (4) Surface modifier: fine calcium carbonate, fine zeolite, polyethylene glycol and the like. (5) Anti-redeposition agent: cellulose derivatives such as carboxymethyl cellulose. (6) Extenders: sodium sulfate, potassium sulfate, sodium chloride and the like. (7) Reducing agents: sodium sulfite, potassium sulfite and the like. (8) Fragrances (9) Dyes

In the sheet-like laundry product of the present invention, a thin layer composed of a water-soluble substrate is laminated on one or both sides of the laundry composition thin layer. The water-soluble substrate in the present specification is preferably one that dissolves in water at 50 ° C or lower, preferably 40 ° C or lower, particularly preferably 10 ° C or lower. here,
The term "dissolves" means that when 0.5 g of a water-soluble substrate is put into 1 liter of water at 50 ° C. or lower, it is within 10 minutes,
Within a minute, and further passed through a 2 mm sieve with no residue. In addition to those that “dissolve”, those that show water dispersibility, and those that show water degradability,
It is included in the water-soluble substrate in the present invention. Here, the water dispersibility means a state in which the substrate is not dissolved but suspended as a fine insoluble substance when put in water, and the water dissolvability is dispersed in a macroscopic size rather than the water dispersibility ( Suspended).

As the water-soluble substrate in the present invention, a water-soluble film, a nonwoven fabric or woven fabric composed of a water-soluble polymer fiber, or a laminated substrate of a nonwoven fabric or woven fabric composed of a water-soluble film and a water-soluble polymer fiber is preferable. . Among these water-soluble substrates, the water-soluble nonwoven fabric has a problem that the stickiness to the hand when touched by wet or extremely wet hands is reduced and the feel is good, and the problem that the sheet-like laundry articles adhere to each other during storage. It is more preferable in that it is reduced. On the other hand, in the case of a water-soluble film, embossing the water-soluble film is preferable since a similar effect can be obtained by embossing the surface. These water-soluble substrates are composed of a water-soluble polymer. Specifically, polyvinyl alcohol, polyvinylpyrrolidone, pullulan, polyacrylamide,
Polyacrylic acid, polymethacrylic acid, polyitaconic acid,
Polyethylene oxide, polyvinyl methylene ether,
Xanthan gum, guar gum, collagen, carboxymethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, methylcellulose, carboxyethylcellulose, hydroxypropylmethylcellulose, sodium polyacrylate, starch, agar, casein and the like are exemplified. These materials may be used alone or in combination of two or more. In particular, polyvinyl alcohol (PVA) or PVA modified with maleic acid or itaconic acid is preferred. Among them, PVA having a saponification degree of 80% or more and an average polymerization degree of 200 to 3000 or a modified product thereof is preferable. In particular, the degree of denaturation is 1 to 6 mol% and the degree of saponification is
95% or more of itaconic acid-modified PVA shows excellent solubility and anti-exudation properties. When a PVA film having a low degree of saponification or a modified product thereof, or an itaconic acid-modified PVA film having a modification ratio of more than 6 mol% is used,
When stored for a long period of time under humid conditions, the film may deteriorate and the surfactant may ooze out of the film.

Among such water-soluble substrates, examples of the water-soluble nonwoven fabric include JP-A-8-127919 and JP-A-8-279919.
JP-A-3848, JP-A-5-321105, JP-A-7-42019, JP-A-3-86530, JP-A-3-279410, JP-A-3-199
408, JP-A-2-112406 and JP-A-61-75862. As the woven fabric, those obtained from the various water-soluble polymer fibers described above can be used. In addition, the diameter of the water-soluble polymer fiber constituting the nonwoven fabric or the woven fabric is preferably from 5 to 200 μm, particularly preferably from 5 to 50 μm. Examples of the water-soluble film include U.S. Pat. No. 3,186,869, U.S. Pat. No. 3,198,740, and U.S. Pat.
No. 3,322,674;
Nos. 37, 48-88343 and 50-14.
Nos. 0958, 51-150, 52-77
Nos. 961 and 55-151853 and 57-
No. 1851, JP-A-59-180085, JP-A-61-57700, JP-A-61-97348,
Nos. 61-98752, 61-200146, 61-200147 and 61-20425
No. 4, No. 61-228057, No. 62-57
492, 62-156112, 62-
275,145, 63-8496, 63
-8497, 63-12466, 63
-12467, 64-29408, 6
JP-A-4-29438, JP-A-2-60906,
JP-A-2-108534, JP-A-2-163149, JP-A-3-59059, JP-A-4-53900, JP-A-4-57989, JP-A-4-63899, JP-A-4-72180, 4-1447000, 4-164998, 4-174792,
No. 4,202,600, and the like.

Further, as the water-soluble substrate in the present invention, a nonwoven fabric or a woven fabric composed of the above-mentioned water-soluble polymer fiber and a laminated substrate composed of a water-soluble film can be used. As a method for obtaining such a laminated substrate, other than a method in which a water-soluble film is overlaid on one surface of a nonwoven fabric or the like and bonded by heat sealing or the like, a film is formed by applying a water-soluble polymer to one surface of a nonwoven fabric or the like. Method. When such a laminated substrate is used, it is preferable that the water-soluble film is arranged so as to be in contact with the detergent thin layer, and the outside is made of a nonwoven fabric or the like. Among the water-soluble substrates exemplified above, a non-woven fabric or a woven fabric made of a water-soluble polymer fiber is preferable because of the easiness of tearing when adjusting the amount of use, and is particularly modified with polyvinyl alcohol, maleic acid, or itaconic acid. Nonwoven fabrics or woven fabrics obtained by using fibers made of polyvinyl alcohol are preferred. Further, a water-soluble laminated substrate in which a water-soluble film made of polyvinyl alcohol or polyvinyl alcohol modified with maleic acid or itaconic acid is laminated on the inside of a nonwoven fabric or woven fabric made of this water-soluble polymer fiber, is also preferable. When the thickness of the thin layer comprising the water-soluble substrate in the present invention is too small, the liquid component tends to exude from the thin layer of the laundry composition and the sheet tends to be sticky. Or it takes time to dissolve, so it should be selected appropriately depending on its solubility, etc.
Although not particularly limited, it is preferably, for example, about 0.01 to 1 mm.

In the sheet-like laundry product of the present invention, a water-insoluble disintegrant is contained in a thin layer composed of a water-soluble substrate, or in both a thin layer of a laundry composition and a thin layer composed of a water-soluble substrate. The water-insoluble disintegrant according to the present invention is insoluble in water and has a property of swelling upon contact with water. Preferably, a) cellulose, b) layered clay mineral,
And c) at least one selected from a clay mineral having a patchwork structure in water and / or a quaternary ammonium salt-containing clay mineral. a) As the cellulose, for example, densified cellulose such as thermomechanical pulp and chemothermomechanical pulp can be used, and beech cellulose, beech-sulfite-cellulose, cotton cellulose, spruce cellulose and the like are preferably used. Can be

B) Specific examples of the layered clay mineral include clay minerals such as smectite used as a fiber softening component in conventional clothing detergents.

C) The clay mineral having a patchwork structure in water is, for example, a swellable clay mineral exemplified below, whose crystal end face is surface-treated with a silane coupling agent such as alkyltrialkoxysilane. As the swellable clay mineral, those which belong to the smectite group and have a crystal structure of a dioctahedral type three-layer structure or a trioctahedral type three-layer structure are particularly preferable. Such a swellable clay mineral has cleavage properties and has a layered structure. In addition,
The swellable clay mineral has a property of swelling as it holds a nonionic surfactant or the like inside. The swellable clay mineral has an oil absorption of less than 80 ml / 100 g, preferably 3 ml.
It is desirable that the bulk density is 0 to 70 ml / 100 g and the bulk density is 0.1 g / cc or more, preferably 0.2 to 1.5 g / cc.

Specific examples of such a swellable clay mineral include:
For example, as a swellable clay mineral having a dioctahedral type three-layer structure, montmorillonite (oil absorption: 50 ml / 1
00g, bulk density: 0.3g / cc), nontronite (oil absorption: 40ml / 100g, bulk density: 0.5g / c)
c), beidelite (oil absorption: 62 ml / 100 g, bulk density: 0.55 g / cc), pyrophyllite (oil absorption: 70 ml / 100 g, bulk density: 0.63 g / cc)
On the other hand, as a swellable clay mineral having a trioctahedral type three-layer structure, saponite (oil absorption: 7
3 ml / 100 g, bulk density: 0.15 g / cc), hectorite (oil absorption: 72 ml / 100 g, bulk density: 0.1 g).
7g / cc), Stephensite (oil absorption: 30ml /
100 g, bulk density: 1.2 g / cc) and talc (oil absorption: 70 ml / 100 g, bulk density: 0.1 g / cc).

The swellable clay mineral generally includes those naturally produced and those artificially hydrothermally synthesized, but is not particularly limited. In addition, the swelling clay mineral is 10% by X-ray analysis.
As long as a peak derived from the spread of the clay layer detected at ~ 20 ° and a peak derived from the clay three-layer structure detected at 4-5 ° are developed, they can be used without particular limitation. In addition, swelling clay minerals, especially in the case of natural products, may contain a large amount of impurities such as quartz, cristobalite, calcite, and opal feldspar.Those having such a large amount of impurities are not suitable for the present invention and have a high purity. At least 60%, more preferably at least 70%, and most preferably 100%. Particularly preferred swellable clay minerals are Na-type montmorillonite, Ca-type montmorillonite, activated bentonite (Na / Ca-type montmorillonite), Na-type hectorite, and Ca-type hectorite.

The quaternary ammonium salt-containing clay mineral is
Preferably, a surfactant containing a positively charged nitrogen atom is intercalated between crystal layers of the clay mineral. Such a quaternary ammonium salt-containing clay mineral is commercially available under a trade name such as "organobennite" or "lipophilic smectite". As a method of intercalating a surfactant into a quaternary ammonium salt-containing clay mineral, for example, after finely dispersing the clay mineral in water, a surfactant containing a positively charged nitrogen atom is added thereto, After the ion exchange reaction (intercalation) with the alkali metal ions or alkaline earth metal ions existing between the crystal layers of the clay mineral, the by-product salts are removed by washing and filtration, and the filter cake is dried. It is suitable. As the clay mineral used here,
In particular, those belonging to the smectite group and having a crystal structure of a dioctahedral three-layer structure or a trioctahedral three-layer structure are preferable. Further, specifically, those exemplified above as the swellable clay mineral can be used. As the surfactant containing a positively charged nitrogen atom to be intercalated, various surfactants can be used without limitation as long as the surfactant contains a positively charged nitrogen atom in the molecule. Specific examples of preferable ones include those exemplified as the above-mentioned cationic surfactant and amphoteric surfactant.

By blending one or more water-insoluble disintegrants selected from a) to c) into a thin layer composed of a water-soluble substrate, the solubility of the thin layer composed of a water-soluble substrate is improved. In addition, if it is blended in both the thin layer of the laundry composition and the thin layer composed of the water-soluble substrate, the solubility of these two layers can be improved. The water-insoluble disintegrant is used in an amount of 0.1 to 2 with respect to a thin layer composed of a water-soluble substrate or a thin layer of a laundry composition.
0% by weight, preferably 0.5 to 10% by weight.
If the amount is less than 0.1% by weight, the effect of addition cannot be obtained,
If the amount is more than% by weight, the effect is saturated. In order to contain the water-insoluble disintegrant in the thin layer composed of the water-soluble substrate, a water-insoluble disintegrant is added when the composition comprising the components of the water-soluble substrate is prepared, and the water-insoluble disintegrant is contained. The composition to be formed may be processed into a fibrous or sheet form. In addition, in order to include the water-insoluble disintegrant in the laundry composition thin layer, a water-insoluble disintegrant is added when preparing a dough-like laundry composition comprising the components of the laundry composition. What is necessary is just to shape the dough-like laundering layer composition containing a water-insoluble disintegrant into a sheet. In the present invention, the thickness of the laundry composition thin layer is preferably 0.05 to 5 mm. When the thickness is less than 0.05 mm, when a plurality of sheet-like detergents are stacked and stored in a container, it may be difficult to remove one by one. It becomes necessary to increase the area of the detergent. On the other hand, if it exceeds 5 mm, it is inconvenient to break the sheet. The method of laminating a thin layer composed of a water-soluble substrate to the thin layer of the laundry composition is not particularly limited. For example, a method in which both layers are each processed into a sheet shape, laminated, and integrated by heat sealing is used. be able to. Alternatively, the dough-like washing composition is moved at a constant speed by rotating a roller or the like 2
It is also possible to use a method of compressing and laminating these layers with the same or different rollers while supplying between the thin layers of a water-soluble substrate.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. [Preparation of Water-Soluble Substrate A According to the Present Invention] The following polyvinyl alcohols (A) and (B) were mixed and dissolved in DMSO at 90 ° C. under nitrogen so as to be 85.5% by weight and 4.5% by weight, respectively. Then, 10% by weight of a water-insoluble disintegrant (hereinafter sometimes simply referred to as disintegrant) was added and mixed. This was used as a spinning dope and passed through a nozzle having a hole diameter of 0.08 mm and a number of holes of 500, and was wet-spun into a solidified solution of 70% by weight of methanol and 30% by weight of DMSO at 3 ° C. The solidified yarn is subjected to 5.0 times wet stretching, immersed in a methanol solution to extract and wash the DMSO in the solidified yarn, applied with a mineral oil-based oil, dried at 100 ° C, and then dried at 215 ° C. Dry heat stretching was performed so that the total stretching ratio was 13 times. The fiber is stapled, carded to form a web having a basis weight of 30 g / m ² , and subjected to a heat calender roll treatment under a thermocompression bonding condition of a temperature of 190 ° C., a linear pressure of 60 kg / cm and a treatment time of 1 second or less, to give 25 g / m 2. ^2. A water-soluble nonwoven fabric having a thickness of 1 mm and a dissolution temperature in water of less than 10 ° C. -Polyvinyl alcohol (A): itaconic acid-modified polyvinyl alcohol having a degree of polymerization of 1700 and a saponification degree of 99.5% (denaturation rate: 2 mol%)-Polyvinyl alcohol (B): having a degree of polymerization of 600 and a saponification degree of 88.0% Polyvinyl alcohol (undenatured)

[Preparation of Water-Soluble Substrate B According to the Present Invention] A water-soluble nonwoven fabric of the water-soluble substrate A and a water-soluble film “Hiselon” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. were laminated to form a laminated sheet.

[Preparation of Water-Soluble Substrate C as Comparative Example] The following polyvinyl alcohols (A) and (B) were prepared in 95 parts each.
It was mixed with and dissolved in DMSO at 90 ° C. under nitrogen so as to be 5% by weight and 5% by weight. As spinning dope this was spun in the same manner as the water-soluble substrate A, 25 g / m ^2, thickness 1
mm, a water-soluble nonwoven fabric having a water dissolution temperature of less than 10 ° C. -Polyvinyl alcohol (A): itaconic acid-modified polyvinyl alcohol having a degree of polymerization of 1700 and a saponification degree of 99.5% (denaturation rate: 2 mol%)-Polyvinyl alcohol (B): having a degree of polymerization of 600 and a saponification degree of 88.0% Polyvinyl alcohol (undenatured)

[Preparation of Water-Soluble Substrate D as Comparative Example] A water-soluble nonwoven fabric of the water-soluble substrate C and a water-soluble film “Hiselon” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. were laminated to form a laminated sheet.

(Examples 1 and 2 and Comparative Examples 1 and 2) Preparation of a detergent composition for clothing A raw material for a detergent composition for clothing shown in Table 1 was mixed with a universal stirring mixer (manufactured by Dalton Co., Ltd.). DM25 type) and mixed to obtain a dough-like laundry composition. Next, this dough-like washing composition was formed into a thin layer having a thickness of 2 mm using a noodle making machine “Titania” manufactured by Industria Producci Stamperch Torino Co.
The resultant was cut into a size of 0 × 100 mm to obtain a thin layer of the laundry composition.・ Manufacture of sheet-like laundry products Laminate a thin layer consisting of a water-soluble substrate on both sides of the above-mentioned laundry composition thin layer, and surround the periphery with FUJI IMPULSE AUTO SEALER (FA-6).
00-5) to produce a sheet-like laundry product. The water-soluble nonwoven fabrics of the above-mentioned water-soluble substrates A to D were used as the water-soluble substrates. Granular cellulose was used as a disintegrant to be added to the water-soluble substrate. For each of the obtained sheet-like laundry products, the disintegration rate was measured and a cloth adhesion test was performed as follows. The results are shown in Table 1.

<Measurement of Disintegration Rate> 0.742 g of the detergent was added to 1 liter of water at 5 ° C., and the mixture was stirred at 250 rpm using a magnetic stirrer. The time required for 90% of the detergent to dissolve was determined as the electric conductivity. It was measured using a meter.

<Cloth Adhesion Test> In a two-tub washing machine (Mitsubishi Electric: CW-225), 30 liters of tap water at a water temperature of 10 ° C. was placed, and two dark blue cotton skin shirts and two black acrylic sweaters were added.
A total of 1.5 kg (bath ratio: 20 times) of two black nylon slips and five skin shirts as charge cloths are put therein, and a recess is made in the center of the cloth to be washed, and 30 g of detergent is placed there (three sheet-like detergents). Intensively. After leaving the detergent immersed in water for 2 minutes, it was washed in a weak water flow for a washing time of 5 minutes. After natural drainage and dehydration for 1 minute, the amount of detergent particles (aggregates) adhering to the cloth was visually evaluated according to the following criteria. 0 point: No adhesion at all 1 point: Very slight adhesion, but good level after rinsing 2 points: Level where some adhesion is observed 3 points: Slightly large adhesion to the entire cloth, after rinsing Unsatisfactory thigh 4 points: considerably adheres to the entire cloth 5 points: adheres violently to the entire cloth

[0049]

[Table 1]

[Raw Materials] AO: dodecyldimethylamine oxide (manufactured by Yokkaichi Gosei Co., Ltd.) AES-Na: Na salt of POE (4.5) alkyl (C12-C15) ether sulfate (manufactured by Mitsubishi Chemical Corporation, Nonitet R) -7) AEP: C12-C15 secondary alcohol POE (7) PO
P (4.5) glycol (manufactured by Nippon Shokubai Chemical Co., Ltd., sophthanol EP7045) Aluminosilicate A: A4 type zeolite (Toyo Soda Co., Ltd.)
Aluminosilicate B: Amorphous zeolite (manufactured by Kofuran Chemical Co., Thixorex 25) MA: K salt of acrylic acid-maleic acid copolymer (manufactured by Nippon Shokubai Chemical Co., Ltd., average molecular weight 60000) Ash : Heavy sodium carbonate (Asahi Glass Co., Ltd., granulated ash) Disintegrant: Granular cellulose (Rettenmeier, A
rbocel-TF-30-HG) PPG: polypropylene glycol (manufactured by Lion Chemical Co., Ltd., average molecular weight: 1000) Enzyme A: protease (API-2, manufactured by Showa Denko KK)
1) Enzyme B: Cellulase (manufactured by Novo Industries, Cellzyme 1.0T) Enzyme C: Amylase (manufactured by Novo Industries, Termamyl 6.0T) Enzyme D: Lipase (manufactured by Novo Industries, Lipolase 100T) Fluorescent agent: biphenyl type Fluorescent brightener (Tinopearl CBS-X, manufactured by Ciba Specialty Chemicals Inc.) Fragrance: d-limonene Other small components: moisture, impurities, etc.

(Examples 3 and 4 and Comparative Examples 3 and 4) Preparation of Fiber Softener Composition Raw materials for the fiber softener composition shown in Table 2 were mixed with a universal stirring mixer (Dalton Co., Ltd.) DM25 type) and mixed to obtain a dough-like fiber softener composition. Next, the dough-like composition was formed into a thin layer having a thickness of 2 mm using a noodle making machine “Titania” manufactured by Industria Producci Stamperch Torino Co.
The fiber was cut into a size of 0 × 100 mm to obtain a thin layer of the fiber softener composition.・ Manufacture of sheet-like laundry products Laminate a thin layer consisting of a water-soluble substrate on both sides of the above-mentioned thin layer of the fabric softener composition, and surround the periphery with FUJI IMPULSE AUTO SEALER
(FA-600-5) to produce a sheet-like laundry product. The water-soluble nonwoven fabrics of the above-mentioned water-soluble substrates A to D were used as the water-soluble substrates. As the disintegrant added to the water-soluble substrate, a layered clay mineral was used. For each of the obtained sheet-like laundry products, the disintegration rate was measured and a cloth adhesion test was performed in the same manner as in Example 1 above. The results are shown in Table 2.

[0052]

[Table 2]

[Raw Materials] DADNC: Dihydrogenated tallow alkyldimethylammonium chloride (manufactured by Lion Akzo) MATMC: Monoalkyl (C16) trimethylammonium chloride (manufactured by Lion Akzo) Glycerin: Purified glycerin (Lion Oleo) Chemical Co., Ltd.) PG: Propylene glycol (reagent) Fragrance: d-limonene Disintegrant: Na-type montmorillonite (Toyojun Yoko Co., Ltd.
Wenger 23)

(Examples 5 and 6 and Comparative Examples 5 and 6) Preparation of Bleach Composition The raw materials for the bleach composition shown in Table 3 were placed in a universal stirring mixer (model DM25, manufactured by Dalton Co., Ltd.). The mixture was added and mixed to obtain a dough-like bleaching composition. Next, this dough-like composition was applied to a thickness of 2 using an noodle-making machine “Titania” manufactured by Industria Prodotchi Stamperch Torino.
mm thin layer, and then the thin layer is 50 × 100 m
m, and a thin layer of the bleach composition was obtained.・ Manufacture of sheet-like laundry products Laminate a thin layer consisting of a water-soluble substrate on both sides of the above-mentioned bleach composition thin layer and surround the periphery with FUJI IMPULSE AUTO SEALER (FA-6).
00-5) to produce a sheet-like laundry product. The water-soluble nonwoven fabrics of the above-mentioned water-soluble substrates A to D were used as the water-soluble substrates. As a disintegrant added to the water-soluble substrate, a clay mineral having a patchwork structure in water was used. For each of the obtained sheet-like laundry products, the disintegration rate was measured and a cloth adhesion test was performed in the same manner as in Example 1 above. The results are shown in Table 3.

[0055]

[Table 3]

[Raw materials used] PC: sodium percarbonate (average particle diameter 500 μm) Bleach activator: tetraacetylethylenediamine AOBS: sodium alkanoyloxybenzenesulfonate (coconut fatty acid composition) Stabilizer: PEG fumarate: polyethylene glycol ( Average molecular weight 200
0) Ash: Sodium carbonate Disintegrant: Synthetic clay mineral obtained by surface-treating montmorillonite with alkyl trialkoxysilane (manufactured by Toysun Yoko Co., Ltd.
Wenger-5H)

(Reference Example 1) Preparation of detergent composition for clothing The raw materials for the detergent composition for clothing shown in Table 4 were put into a universal stirring mixer (model DM25, manufactured by Dalton Co., Ltd.) and mixed. Thus, a dough-like detergent composition was obtained. In addition, this dough-like detergent composition contained granular cellulose (Arbocel-TF-30-HG, manufactured by Rettenmeier) as a disintegrant. Next, a three-roll stainless steel roll having a diameter of 305 mmφ and a width of 600 mm, which is designed to rotate in directions opposite to each other, with three clearances of 3.5 mm and 1.5 mm (Ashizawa Tekko Co., Ltd.) The above-mentioned dough-like detergent composition was introduced into the product, and the roll was formed while keeping the peripheral speed ratio of the roll at 1: 2: 4 to form a sheet-like thin layer. The thin layer of the detergent composition for clothing thus obtained was subjected to the measurement of the disintegration rate and the cloth adhesion test in the same manner as in Example 1 above. The results are shown in Table 4. In Table 4, the raw materials used are the same as those in Table 1 above.

(Comparative Reference Example 1)
A thin layer of the detergent composition for clothing was obtained in the same manner except that no disintegrant was added to the dough-like detergent composition. With respect to this thin layer of the detergent composition for clothing, the disintegration rate was measured and a cloth adhesion test was carried out in the same manner as in Example 1 above. The results are shown in Table 4.

(Example 7) A thin layer composed of a water-soluble substrate was laminated on both sides of the thin layer of the detergent composition for clothing obtained in the above-mentioned Reference Example 1, and the periphery thereof was FUJI IMPULSE AUTO SEALER (FA-600-).
Heat sealing was performed in 5) to produce a sheet-like laundry product. The water-soluble nonwoven fabric of the water-soluble substrate A was used as the water-soluble substrate. Granular cellulose was used as a disintegrant to be added to the water-soluble substrate. The obtained sheet-like laundry product was subjected to the measurement of the disintegration rate and the cloth adhesion test in the same manner as in Example 1 above. The results are shown in Table 4.

[0060]

[Table 4]

Reference Example 2 Preparation of Fiber Softening Agent Composition Raw materials for the fiber softening agent composition shown in Table 5 were put into a universal stirring mixer (model DM25, manufactured by Dalton Co., Ltd.) and mixed. Thus, a dough-like fiber softening agent composition was obtained. In addition, this fiber softening agent composition contained a layered clay mineral as a disintegrant. Next, roll forming was performed in the same manner as in Reference Example 1 to form a sheet-like thin layer. With respect to this thin layer of the fiber softener composition, the disintegration rate was measured and a cloth adhesion test was carried out in the same manner as in Example 1 above. The results are shown in Table 5. In Table 5, the raw materials used are the same as those in Table 2 above.

(Comparative Reference Example 2)
A thin layer of the fiber softener composition was obtained in the same manner except that no disintegrant was added to the dough-shaped fiber softener composition. With respect to this thin layer of the fiber softener composition, the disintegration rate was measured and a cloth adhesion test was carried out in the same manner as in Example 1 above. The results are shown in Table 5.

(Example 8) A thin layer composed of a water-soluble substrate was laminated on both sides of the thin layer of the fiber softening agent composition obtained in Reference Example 2 above, and the periphery thereof was FUJI IMPULSE AUTO SEALER (FA-600-).
Heat sealing was performed in 5) to produce a sheet-like laundry product. The water-soluble nonwoven fabric of the water-soluble substrate A was used as the water-soluble substrate. As the disintegrant added to the water-soluble substrate, a layered clay mineral was used. The obtained sheet-like laundry product was subjected to the measurement of the disintegration rate and the cloth adhesion test in the same manner as in Example 1 above. The results are shown in Table 5.

[0064]

[Table 5]

Reference Example 3 Preparation of Bleach Composition The raw materials for the bleach composition shown in Table 6 were put into a universal stirring mixer (model DM25, manufactured by Dalton Co., Ltd.) and mixed to form a dough. A bleach composition was obtained. The bleaching composition contained a clay mineral having a patchwork structure in water as a disintegrant. Next, roll forming was performed in the same manner as in Reference Example 1 to form a sheet-like thin layer. With respect to this thin layer of the bleaching composition, the disintegration rate was measured and a cloth adhesion test was carried out in the same manner as in Example 1 above. The results are shown in Table 6. In Table 6, the raw materials used are the same as those in Table 3 above.

(Comparative Reference Example 3)
A thin layer of the bleach composition was obtained in the same manner except that no disintegrant was added to the dough-like bleach composition. With respect to this thin layer of the bleaching composition, the disintegration rate was measured and a cloth adhesion test was carried out in the same manner as in Example 1 above. The results are shown in Table 6.

(Example 9) A thin layer comprising a water-soluble substrate was laminated on both sides of the thin layer of the bleaching composition obtained in Reference Example 3 above, and the periphery thereof was FUJI IMPULSE AUTO SEALER (FA-600-5). To produce a sheet-like laundry product. As the water-soluble substrate, a water-soluble nonwoven fabric of the above-mentioned water-soluble substrate B was used. As a disintegrant added to the water-soluble substrate, a clay mineral having a patchwork structure in water was used. The obtained sheet-like laundry product was subjected to the measurement of the disintegration rate and the cloth adhesion test in the same manner as in Example 1 above. The results are shown in Table 6.

[0068]

[Table 6]

From the results shown in Tables 1 to 6, it was confirmed that in the examples according to the present invention, both the disintegration speed and the cloth adhesion were good.

[0070]

As described above, the sheet-like laundry product of the present invention comprises a single layer of a laundry composition thin layer containing at least one selected from a clothing detergent, a fiber softener and a bleaching agent. Or a sheet-like laundry product obtained by laminating a thin layer comprising a water-soluble substrate on both sides, wherein the thin layer comprises the water-soluble substrate, or the thin layer comprising the laundry composition thin layer and the water-soluble substrate. Both layers are characterized by containing a water-insoluble disintegrant having a property of swelling upon contact with water. Therefore, a sheet-like laundry product having good shape retention properties, excellent solubility, and less likely to adhere to cloth during washing can be obtained.

Claims (2)

[Claims] 1. A laminating layer comprising a water-soluble substrate is laminated on one or both sides of a laminating composition thin layer containing at least one selected from a laundry detergent, a fiber softener and a bleaching agent. A sheet-like laundry product comprising: a thin layer comprising the water-soluble substrate, or both a thin layer comprising the laundry composition and a thin layer comprising the water-soluble substrate; A sheet-like laundry product comprising an insoluble disintegrant. 2. The water-insoluble disintegrant according to claim 1, wherein
The sheet-like laundry product according to claim 1, wherein the product is at least one member selected from the group consisting of: a) Cellulose b) Layered clay mineral c) Clay mineral and / or quaternary ammonium salt-containing clay mineral having a patchwork structure in water