CN1177025C

CN1177025C - Sheetlike article for washing

Info

Publication number: CN1177025C
Application number: CNB971820678A
Authority: CN
Inventors: 林宏光; 西条宏之; 花田弘彦; 西俊纪; 中尾真治
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 1997-01-23
Filing date: 1997-12-26
Publication date: 2004-11-24
Anticipated expiration: 2017-12-26
Also published as: EP0957158A1; EP0957158B1; CN1248998A; DE69726314D1; WO1998032835A1; EP0957158A4; JPH10204499A; JP3126675B2; DE69726314T2

Abstract

A sheetlike detergent which is freed from the scattering or leak of contents, facilitates arbitrary dispensing, and exhibits excellent detergency even when used alone can be produced by arranging sheetlike water-soluble supporting members on both surfaces of a thin layer made of a doughy non-phosphate detergent composition which comprises a nonionic surfactant, an alkaline agent and a sequestering agent and exhibits a penetration hardness of 0.1 to 10 kg/cm<2> at 25 DEG C.

Description

Sheetlike article for washing

Technical field

The present invention relates to wash the goods of usefulness, it is convenient to regulate consumption and in fact can uses easily, has reduced wherein dispersing or seepage of material considerably.More specifically, the present invention relates to be used for the detergent compositions in tablet form of clothing.

Background technology

Conventional Powdered or problem that granulated detergent has micro mist to disperse.As the method that solves this problem of dispersing effectively, the washing composition and the detergent tablet of 1 package-type have been proposed, it forms (JP-A 2-228398, GB-B 2084176 etc.) by the water-soluble or water-insoluble film or the non-woven fabrics that have soaked with detergent component.Yet in a kind of method in back, detergent composition exposes from the teeth outwards and adheres on hand or the container.When making insoluble film of water or non-woven fabrics as the matrix that will be soaked, it should be handled after the use, therefore cause the handling properties of difference.In addition, in this case, cause another problem, promptly in the whipping process in washing machine, insoluble pars fibrosa ground falls down from matrix, after the drying, remains on the surface of clothes.This problem is very serious, especially under the situation of dark clothes, because the fiber resistates on such garment surface is very tangible.

As the example of the article for washing that uses water-insoluble matrix, US-A 4170565 discloses a kind of product of being made up of the activated detergent that is clipped between the non-woven fabrics with specific gas permeability except dipping detergent active composition mode., in this patent, used tri-polyphosphate as the washing assistant in the high washing assistant clothes washing composition, in addition, this washing composition has high moisture content.As well known, should use phosphatic detergent for washing clothes in minimum level ground, because it causes the problem of overnutrition (eutrophication).Yet, contain 15% or more high-load tri-polyphosphate as washing assistant and 15% or more the composition of high-content water have all inaccessiable advantage of other any washing assistant.That is, such composition is being fabulous aspect the transport properties of activated detergent raw material under the viscosity that limits.When only replacing tri-polyphosphate and give this detergent raw material with enough viscosity so that when forming sandwich structure with zeolite for example, reduced widely with conveying activated detergents such as pump effectiveness.As a result, only carried out the coating on matrix or activated detergent has been worked in the sheet with extremely low efficient.It is very difficult promptly producing without phosphorus goods according to above-mentioned patent.When the quid pro quo of the insoluble non-woven fabrics of water with poor handling properties that uses water-soluble conduct to use in this patent, much less moisture content has been reduced widely.Therefore, in this case, almost can not do not produced the without phosphorus detergent tablet of resistates.

US-A 5202045 has advised another method, and wherein activated detergent component and/or active bleaching agent are packaged in the insoluble non-woven fabrics of water of 2 S shapes.In this case, used be similar to above-mentioned US-A 4170565 methods contain 15% or the tri-polyphosphate and 15% or the high lotion-aid combination of high-content water more of a large amount more.That is to say, this patent in fact openly do not contain washing assistant especially zeolite as phosphoric acid salt quid pro quo and the washing composition that is used for clothes with low moisture content.

As the method that solves these problems that run in the prior art, JP-A61-12796 proposes a kind ofly to be processed into sheet and with its 2 goods that the surface obtains of coatings such as water-solubility membrane by the non-powdered detergent composition that will contain nonionogenic tenside., this patent is only open wherein mixes the water-soluble polymeric compounds and with the mixture hot moulding embodiment in blocks that obtains with SYNTHETIC OPTICAL WHITNER and tensio-active agent.Therefore, be similar to above-mentioned soak type goods, this detergent component partly is exposed on the surface that obtains like this and adheres on hand and the container.That is to say the not concrete and open effectively technology that detergent composition is not processed into sheet and applies 2 surfaces of this sheet with water-solubility membrane etc. of this patent.

In addition, suppose that disclosed composition is used as washing composition in above-mentioned patent under the situation that other washing composition uses together.Therefore, these compositions neither contain alkaline reagents and do not contain sequestrant again, and these reagent are the basal components that are used for the washing composition of clothes.Therefore, when the such composition of independent use, can not reach enough detersive poweies.In addition, from angle convenient and that use with other washing composition economically, it is bad.It also be not suitable for by add the water-soluble polymeric compounds for example polyvinyl alcohol prepare these compositions.This be because: in this case, these water-soluble polymerss contact with alkaline reagents in large area and so usually be hydrolyzed.

Being used for the washing composition of clothes at great majority, owing to use tensio-active agent, sequestrant and alkaline reagents as basal component in large quantities, is very difficult so obtain that the sandwich type composition of these activated detergent components can be arranged with big loading gage.

In these cases, people are the such sheet-like composition of demand development urgently, said composition contains the washing assistant as phosphatic quid pro quo, present in an amount at least sufficient to the detersive power that reaches fabulous, even also be that so it is fabulous aspect accessibility and can be loaded with a large amount of relatively activated detergent components so that prevent wherein dispersing or seepage of material when using separately.On the other hand, in fabric softener and SYNTHETIC OPTICAL WHITNER field, also require development to be used for the sheet-like article of clothes, it does not have dispersing of powder, have the Environmental compatibility height, contain the fabric softener or the active bleaching agent of q.s, have high flexibility and can dissolve fully in the step in laundry.

Disclosure of an invention

Thereby the inventor has carried out extensive studies has obtained the goods that are used to do washing, and in fact it can use easily, reduced wherein dispersing or seepage of material considerably.The result, have been found that, compare extremely thin sheet-like article by the washing composition etc. that the thin layer that provides a kind of support to contain the thin layer of Powdered or granular composition or to contain dough shape composition can obtain with a package-type of routine, and when contacting with wet hand, the goods that obtain like this have improved weather resistance, not because therefore the seepage of the wherein material that fracture causes is convenient at random adjust usage quantity, and use easily, need not to remove this sheet after the washing.Finished the present invention based on this discovery.

Therefore, the invention provides the sheet-like article that is used to do washing, it has the parts that contain one or more thin layers that are selected from the detergent composition, fabric softener composition and the whitener composition that are used for clothes and this thin layer of support.

At the sheet-like article that is used for doing washing that has the thin layer that contains composition and support the parts of this thin layer of the present invention, can be continuously or form this thin layer discontinuously.In addition, the parts that are used to support can be configured in the outside or the inside of this thin layer.Fig. 1 has illustrated an example according to the sheet-like article that is used to do washing of the present invention.In Fig. 1,1 expression contains the thin layer of composition, and the parts that 2 and 2 ' expression is used to support.In this case, use be arranged in these thin layer both sides water-soluble as support component.In Fig. 2,3 expressions contain the thin layer of detergent composition, and 4,4 ' and 4 " the expression water-soluble substrate of sheet (water-soluble).

In the present invention, support the parts of thin layer, when itself and other material (another thin layer, pass through to reduce the thin layer tackiness when or user) contacting, help to support this thin layer so that alleviate the infringement that causes by contact, powder or the particle keeping the shape of this thin layer and prevent to be contained in this thin layer disperse, and keep the shape of this thin layer.Such parts also can have other additional function.The parts that use water-soluble conduct to be used to support in the present invention are suitable.

Water-soluble

At first, illustrate water-soluble that is preferred among the present invention.Use-testing method I carries out the mensuration of example I-1 to I-12.

The water-soluble preferred example that is used for the present invention comprises: non-woven fabrics of being made by water-solubility membrane, water-soluble polymer fibers or yarn fabric and the non-woven fabrics of being made by water-solubility membrane and water-soluble polymer fibers or the laminate of yarn fabric.These water-soluble is made of water-soluble polymers, for example polyvinyl alcohol, Polyvinylpyrolidone (PVP), pullulan, polyacrylamide, polyacrylic acid, polymethyl acrylic acid, poly-methylene-succinic acid, polyethylene oxide, polyvinyl methylene ether, xanthan gum, cyamoposis glue, collagen, carboxymethyl cellulose, hydroxypropylcellulose and Natvosol.In the middle of them, preferably use polyvinyl alcohol, or with toxilic acid or methylene-succinic acid modified polyethylene alcohol.

In these water-soluble, the example of water-soluble fabric or non-woven fabrics comprises: by the non-woven fabrics that water-soluble polyvinyl alcohol fibers is made, it is disclosed in JP-A8-127919, JP-A8-3848, JP-A5-321105, JP-A7-42019, JP-A3-86530, JP-A3-279410, JP-A3-199408, JP-A2-112406 and JP-A61-75862; The non-woven fabrics that fiber from be described in JP-A1-229805, JP-A64-33209, JP-A3-199408, JP-A2-112406, JP-A3-27112 and JP-A56-306 obtains; With the supports fabrics and the non-woven fabrics that are described among JP-A61-75862, JP-A60-162850, JP-A3-25539 and the JP-A58-98464.The example of yarn fabric is by using those that above-mentioned various water-soluble polymer fibers obtains.The diameter that constitutes the water-soluble polymer fibers of these non-woven fabrics or fabric is preferably 5-200 μ m, more preferably 5-50 μ m.

The example of water-solubility membrane comprises and is described in US-A3186869, US-A3198740, US-A3280037, US-A3322674, JP-U48-33837, JP-U48-88343, JP-U50-140958, JP-U51-150, JP-U52-77961, JP-U55-151853, JP-U57-1851, JP-A59-180085, JP-A61-57700, JP-A61-97348, JP-A61-98752, JP-A61-200146, JP-A61-200147, JP-A61-204254, JP-A61-228057, JP-A62-57492, JP-A62-156112, JP-A62-275145, JP-A63-8496, JP-A63-8497, JP-A63-12466, JP-A63-12467, JP-A 64-29408, JP-A64-29438, JP-A2-60906, JP-A2-108534, JP-A2-163149, JP-A3-59059, JP-A4-53900, JP-A4-57989, JP-A4-63899, JP-A4-72180, JP-A4-147000, JP-A4-164998, among JP-A4-174792 and the JP-A4-202600 those.As water-soluble of the present invention, also can use the above-mentioned laminate that comprises that the non-woven fabrics made by water-soluble polymer fibers or woven and water-solubility membrane are made.On a surface that water-solubility membrane is placed on non-woven fabrics etc., then heat-seal bond can obtain these laminate.In addition, also water-soluble polymers can be coated on the surface of non-woven fabrics etc., then film forming.When using such laminate, preferably water-solubility membrane is contacted and is arranged in the outside of non-woven fabrics etc. with composition layer.

Fig. 3 has illustrated the detergent tablet of the laminate of the above-mentioned type used according to the invention.Be shown in that this detergent tablet among Fig. 3 is made up of the thin layer that contains detergent composition and laminate.The water-solubility membrane 6 and 6 ' of this laminate is arranged in contacts with the thin layer 5 that contains detergent composition and soluble non-woven fabrics 7 and 7 ' is positioned at its outside.

In above-mentioned water-soluble, consider preferred non-woven fabrics or the yarn fabric of making by water-soluble polymer fibers that use from adjusting the angle that usage quantity etc. tears.More preferably use with partly-hydrolysed polyvinyl alcohol, carboxyl acid modified polyvinyl alcohol, non-woven fabrics or yarn fabric that the fiber made from modified polyethylene alcohol such as tensio-active agents obtains.The also preferred laminate of using those non-woven fabrics or yarn fabric of being made by water-soluble polymer fibers and the water-solubility membrane that is laminated to the inboard to form, water-solubility membrane is made with toxilic acid or methylene-succinic acid modified polyethylene alcohol by polyvinyl alcohol.

Water-soluble that is used for the present invention preferably is dissolved in water at 50 ℃.Term used herein " dissolving " referred in 10 minutes, and in preferred 7 minutes, water-soluble of 0.5g is dissolved in 50 ℃ the 1L water, and the solution that obtains is by No. 8.6 sieve (Japanese Pharmacopoeia: do not have resistates 2000 μ m).

Composition

The sheet-like article that is used to do washing of the present invention has and contains the thin layer that one or more are selected from the detergent composition, fabric softener composition and the whitener composition that are used for clothes.Next, the composition that is used to form thin layer is described.

The detergent composition that is used for clothes

The detergent composition that is used for clothes that can be used among the present invention can comprise the component that is generally used for this field, anion surfactant for example, nonionogenic tenside, amphoterics, cats product, water-soluble inorganic salt, washing assistant, sequestrant, anti-deposition agent, enzyme, sulphite, dirt release agent, dye transfer inhibitor, fluorescence dye, spices, antifoams such as clay and siloxanes, percarbonate, perborate, bleach-activating agent, granulation aid such as macromolecule polyethylene glycol, or the like, but be not limited to these components.When 2 sides that are arranged in the detergent composition layer with water-soluble, preferably this detergent composition contains and is less than 15%, the moisture more preferably less than 9%.Under powder or particulate situation, can easily regulate moisture content by being controlled at the water yield or the exsiccant degree used in the granulation step.On the other hand, in order to prepare dough shape composition, preferably with an organic solvent, nonionogenic tenside or molecular weight be 2000 or lower poly-dihydric alcohol for example polyoxyethylene glycol or polypropylene glycol so that obtain doughy composition.As optional components, in order to increase the solubleness of high density detergent, detergent composition of the present invention preferably contains the hydrotropic agent that is generally used in this area, for example urea, low alkyl group Phenylsulfonic acid or low alkyl group benzene carboxylic acid such as cumene sulfonate, tosylate, benzoate etc.

The preferred version of the sheet-like article that the present invention is used to do washing comprises that by non-phosphoric acid be the thin layer that the dough shape composition of detergent composition is made, this dough shape composition comprises at least a nonionogenic tenside, at least a alkaline agent and at least a sequestrant, and this dough shape composition demonstrates 0.1-10kg/cm at 25 ℃ ²Pin to go into hardness and above-mentioned parts be to be arranged in water-soluble of this thin layer both sides.

The detergent composition that is used for the sheet-like article of this laundry usefulness is a dough-like, and it is 0.1-10kg/cm that its pin at 25 ℃ is gone into hardness ², preferred 0.5-10kg/cm ², more preferably 1-10kg/cm ²Term used herein " dough " is meant by for example liquid, lotion or gel are mediated the material that obtains with powdered composition and fluid.This fluid comprises by heating or apply the reagent of power fluidify.Owing to be dough, there be not observed dispersing under the powdered composition situation so be used for the present invention's detergent composition.In addition, this detergent composition has low flowability, i.e. 0.1-10kg/cm ²Pin go into hardness.When because when for example causing when contact with wet hand this water soluble matrix for example to be used to the water-soluble of sheet-like article of doing washing to rupture, perhaps when in order to regulate dosage and to be torn by hand this water-soluble, the wherein seepage of material does not take place.Go into hardness when pin and be lower than 0.1kg/cm ²The time, so have high flowability owing to cross soft said composition.As a result, this detergent composition becomes and is difficult to obtain sheet-like article or causes the wherein seepage of material.When pin is gone into hardness ratio 10kg/cm ²Or when bigger, this detergent composition becomes fragile and therefore almost can not be processed into sheet-like article.High brittleness also causes the wherein seepage of material.

The detergent composition that is used for the preferred embodiment of the invention is the detergent composition of no phosphoric acid salt, and it comprises at least a nonionogenic tenside, at least a alkaline reagents and at least a sequestrant.In addition, the detergent composition that is used for the present invention can comprise the component that is generally used in this field, anion surfactant for example, amphoterics, cats product, water-soluble inorganic salt, washing assistant, anti-deposition agent, enzyme, sulphite, dirt release agent, dye transfer inhibitor, fluorescence dye, spices, antifoams such as clay and siloxanes, percarbonate, perborate, bleach-activating agent, granulation aid such as macromolecule polyethylene glycol, or the like, but be not limited to these components.When the both sides that are arranged in dough shape detergent composition layer with water-soluble, preferably this detergent composition contains and is less than 10%, the moisture more preferably less than 5%.Preparation dough shape composition under such water content, preferred with an organic solvent, nonionogenic tenside or molecular weight be 2000 or lower poly-dihydric alcohol for example polyoxyethylene glycol or polypropylene glycol so that obtain doughy composition.As optional components, in order to increase the solubleness of high density detergent, detergent composition of the present invention preferably contains the hydrotropic agent that is generally used in this area, for example urea, low alkyl group Phenylsulfonic acid or low alkyl group benzene carboxylic acid such as cumene sulfonate, tosylate, benzoate etc.

The example that can be used for the nonionogenic tenside in the detergent composition of the present invention comprises: polyoxyalkylene alkyl, the polyoxyalkylene alkyl phenyl ether, Vykamol Sorbitol 8B, Polyoxyethylene Sorbitol Fatty Acid Esters, cithrol, the polyoxyethylene fatty acid alkyl ester, polyoxyethylene polyoxy-propylene, the polyoxyethylene polyoxypropylene fatty acid alkyl ester, polyoxyethylene alkyl amine, glycerol fatty acid ester, the polyoxyethylene high-grade aliphatic ester, the higher fatty acid alkylolamide, polyoxyethylene higher fatty acid alkylolamide, polyol esters of fatty acids, sucrose fatty ester, alkyl amine oxide, alkyl glycoside and alkyl glucose amide.Can use one or more of these nonionogenic tensides.Especially, the preferred use by alkylene oxide such as oxyethane or propylene oxide being added on uncle with 10-18 carbon atom or the secondary straight or branched alcohol and regulating HLB (method by Grrifin is calculated) to 10.5-15.0, preferably the polyoxyalkylene alkyl for preparing of 11.0-14.5 is as this nonionogenic tenside.

In addition, use 25 ℃ as liquid or slurries form be its fusing point not to be higher than 25 ℃ nonionogenic tenside be suitable because this nonionogenic tenside is being fabulous aspect detersive power, foaming property, froth breaking character and the solubleness.

In the present invention, the content of the nonionogenic tenside in detergent composition is in the scope of 5-50% weight, preferred 10-30% weight.

If necessary, this detergent composition can also contain other tensio-active agent for example anion surfactant, amphoterics and cats product.The preferred anion surfactant that uses.

The preferred example of anion surfactant comprises: have the uncle of 10-18 carbon atom or sulfuric acid, the sulfuric acid with ethoxylate of 8-20 carbon atom alcohol, alkylbenzene sulfonate, paraffin sulfonate, sulfonated, alpha-sulfo-fatty acid salt, alpha-sulfo-fatty acid alkyl ester salt or the soap of the straight or branched alcohol of the second month in a season.Preferred especially linear alkylbenzene sulfonate with 12-14 carbon atom alkyl and the alkyl-sulphate of using with 12-18 carbon atom.As counter ion, preferably use basic metal, particularly, one or more are selected from the counter ion of sodium, potassium and alkanolamine.

As the alkaline reagents that is used for detergent composition of the present invention, can use to be generally used for any in the clothes washing composition.Its example comprises: yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, S-WAT, potassium sulfite, concentrated crystal soda, according to JIS No.1, the amorphous silicic salt of No.2 and crystalline silicate etc. and alkanolamine such as monoethanolamine and diethanolamine.Can use a kind of these alkaline reagentss or multiple.Especially preferably use yellow soda ash, salt of wormwood, amorphous silicic salt and crystalline silicate.

Now, at length narrate crystalline silicate.It is suitable that use in the present invention has the crystalline silicate of forming below:

x(M ₂O).y(SiO ₂).z(Me _mO _n).w(H ₂O) (I)

Wherein M represents the Ia family element in the periodic table of elements; Me represents a kind or the multiple element that is selected among IIa in the periodic table of elements, IIb, IIIa, IVa and the VIII; Y/x is 0.5-2.6; Z/x is 0.01-1.0; W is 0-20; With n/m be 0.5-2.0.

In following formula (I), preferably y/x is in the scope of 0.5-2.6, preferred 1.5-2.2.When y/x was lower than 0.5, this crystalline silicate can not demonstrate enough water-fast dissolubilities, and this all presents very unfavorable effect to the caking character of this silicate itself and the stability in storage of solvability and this detergent composition.On the other hand, when y/x surpassed 2.6, therefore the reduction of the alkalescence of this silicate also became and is not suitable as alkaline reagents.In addition, in this case, its ion-exchange capacity also be damaged and therefore this silicate become and also be not suitable as ion-exchanger.In formula (I), z/x is in the scope of 0.01-0.9, preferred 0.02-0.9.When z/x less than 0.1 the time, this silicate can not demonstrate enough water-fast dissolubilities.When z/x surpasses 0.9, its ion-exchange capacity be damaged and therefore this silicate become and be not suitable as ion-exchanger.The not special restriction of the value of x, y and z is as long as the ratio of y/x and z/x satisfies the requirement that limits above by the crystalline silicate of formula (I) expression.

Usually, can obtain these silicate by make unformed glass water glass crystallization 200-1000 ℃ of calcination.

M ₂O.x’(SiO ₂).y’(H ₂O) (II)

Wherein M represents basic metal; X ' is 1.5-2.6; Y ' is 0-20.

JP-A60-227895 discloses the method for the crystalline silicate of a kind of preparation formula (II) expression.Usually, can be by obtaining these silicate at the 200-1000 ℃ of unformed glass water glass post crystallization of calcination.The method of synthetic these silicate is described in, for example, Phys.Chem.Glasses, 7,127-138 (1966) and Z.Kristallogr., 129, among the 396-404 (1969).By this crystalline silicate of formula (II) expression can be used as Powdered or granulated product from Hoechst for example with trade name " Na-SKS-6 " (δ-Na ₂Si ₂O ₅) buy.The ion-exchange capacity of these crystalline silicates is at least 100CaCO ₃More than the mg/g, preferred 200-600CaCO ₃Mg/g plays the sequestrant that uses among the present invention thus.

As mentioned above, crystalline silicate has alkalescence and alkalescence-shock absorption and ion-exchange capacity.Therefore,, the effect that it needs can be reached, the detersive power of needed flaked product can be reached thus by suitably controlling its content.

The median size of crystalline silicate is in the scope of 0.1-100 μ m, more preferably 1-60 μ m.When its median size surpassed 100 μ m, therefore the superfacial velocity that can hinder ion-exchange can damage detersive power.On the other hand, when its median size during less than 0.1 μ m, the specific surface area of increase causes the water adsorption and the CO that increase ₂Adsorb, therefore damaged the quality of detergent composition significantly.Term used herein " median size " is meant the mid-diameter in the particle size dispersion.

Can be by the crystalline silicate of institute's median size on for example oscillating mill, hammer mill, ball mill or roller press grinding preparation have with shredder and size distribution.

In the present invention, the content of the alkaline reagents in the detergent composition is in the scope of 5-60% weight, preferred 10-50% weight.

As the sequestrant that is used for detergent composition of the present invention, can use normally used material in the clothes washing composition.Its example comprises: above-mentioned crystalline silicate, crystal aluminosilicate be zeolite A, zeolite P and X zeolite for example, and amorphous silicon aluminium hydrochlorate, organic sequestering agent be multi-carboxylate and amino polyacetic acid salt and carboxylic acid based polymer for example.Can use one or more of these sequestrants.Although above-mentioned crystalline silicate plays alkaline reagents and sequestrant, preferably also use additional alkaline reagents or sequestrant.

Can easily obtain the amorphous silicon aluminium hydrochlorate with reference to JP-A6-179899.

The example of carboxylate salt polymkeric substance comprises: polyacrylic acid or its salt, poly-methylene-succinic acid or its salt, poly-alpha-hydroxy vinylformic acid or its salt, (methyl) vinylformic acid/toxilic acid (acid anhydride) multipolymer or its salt and the metaldehyde hydrochlorate that is described among the JP-A54-52196.

Other example of carboxylate salt polymkeric substance comprises for example polyaspartic acid salts of aminocarboxylate polymkeric substance.

In the present invention, the content of sequestrant is in the scope of 5-60% weight, preferred 10-50% weight.

Except said components, detergent composition can also contain: dissolution aids is sodium sulfate, tosic acid, xylenesulfonate, talcum, thin silica powder and clay for example; Organic washing-assisting detergent is polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and carboxymethyl cellulose for example; SYNTHETIC OPTICAL WHITNER; Enzyme; Bluing agent; Fluorescence dye; Antifoams/suds suppressor and spices.Especially, preferably use molecular weight to go into hardness so that control pin as the polyoxyethylene glycol of 200-30000.

The example of SYNTHETIC OPTICAL WHITNER is: SPC-D, Sodium peroxoborate (preferred monohydrate) or sodium sulfate/hydrogen peroxide affixture.SPC-D is preferred in the middle of them.When being used for washing composition, when particularly for example zeolite uses with silico-aluminate, preferably apply SPC-D with Sodium Tetraborate.

The detergent composition that is used for the present invention can contain 10% or lower, and preferred 5% or lower and more preferably 2% or lower moisture.When it contains greater than 10% moisture, be arranged in the dissolving of water-soluble substrate sections ground and the thickness that becomes of the both sides of the thin layer that comprises this detergent composition.As a result, cause that some problems cause these detergent tablet goods bonded to each other, perhaps when at low temperature for example when store winter, this detergent composition becomes and does and crisp, and therefore in fact can not keep the snappiness of sheet-like article.

The component that constitutes the detergent composition that uses among the present invention is divided into organism and inorganics.In total organism, the ratio of mixture of liquid ingredient and solid ingredient is preferably in the scope of 10/1-1/10 at normal temperatures, more preferably 10/2-2/10.When liquid ingredient surpasses above-mentioned scope, need to use a large amount of mineral compound that can adsorptive liquid so that preventing liquid ingredient oozes out from dough, see that from the viewpoint of economy this is unfavorable.On the other hand, it also is unfavorable using solid organic matters, when especially tensio-active agent surpasses the content of above-mentioned qualification, because can damage the solvability of composition in this case.

On the other hand, the ratio of mixture of regulating mineral compound and organic compound is effective keeping aspect the pliability of raw material.The content of mineral compound in whole composition (promptly comprising organic and mineral compound) is preferably 30-95%.When the content of mineral compound is lower than 30%, can easily process said composition by for example applying., when such composition is processed into the sheet that is clipped between two or more substrates, produced unfavorable phenomenon, promptly As time goes on the activated detergent component is passed through substrate seepage constantly.This problem is remarkable especially owing to use fluid organic material.When the content of mineral compound surpasses 95%, almost can not obtain uniform dough by stirring.In addition, when such composition is processed into the sheet that is clipped between the substrate, produced unfavorable phenomenon, promptly the activated detergent composition can seepage when fracture.

Fabric softener composition

As the fabric softener that is used for the present invention, can use the known softening agent of quaternary ammonium salt as softening agent.The specially suitable quaternary ammonium salt that is to use two (chain alkyl) type, its randomly in alkyl, can contain binding groups for example-COO-,-OCO-,-NHCO-or-CONH-.As optional component, also can use spices, tinting material, silicone compounds, antiseptic-germicide, solvent, water-soluble salt etc.

Bleaching composition

Have no particular limits the suitable oxygen bleaching agent that is to use although be used for the present invention's SYNTHETIC OPTICAL WHITNER.This oxygen bleaching agent contains the compound with superoxide, and this superoxide can form hydrogen peroxide in water.The example of these superoxide comprises: SPC-D, tripoly phosphate sodium STPP/hydrogen peroxide affixture, trisodium phosphate/hydrogen peroxide affixture, urea/hydrogen peroxide affixture, 4NaSO ₄.2H ₂O ₂.NaCl, Sodium peroxoborate monohydrate, sodium perborate tetrahydrate, mistake water glass, sodium peroxide and calcium peroxide.Preferred SPC-D, Sodium peroxoborate monohydrate or the sodium perborate tetrahydrate of using in the middle of them.If necessary; as bleach-activating agent; said composition can contain the compound with suitable leavings group; tetra acetyl ethylene diamine; the acetoxyl group benzene sulfonate, be described among JP-A59-22999, JP-A63-258447 and the JP-A6-316700 the organic peracid precursor or by stablize the metal catalyst that transition metal prepares with sequestrant.In addition, composition also can contain solubilizing agent for example tosilate, xylenesulfonate, alkenyl succinic salt and urea; Permeate agent; Suspension agent is clay for example; Friction agent; Sequestrant; Pigment; Dyestuff; Spices etc.

The sheet-like article that is used to do washing

The preparation method of the sheet-like article that is used to do washing of the present invention has no particular limits, and at first, being suitable for stirring very by use, for example general stirrer of stirrer and the kneader of thick substances can prepare doughy composition.When the component of using easy thermally denature for example when enzyme or SYNTHETIC OPTICAL WHITNER, preferably whipping temp is adjusted to 40 ℃ or lower.With the dough shape composite mold tablet forming that obtains like this, will comprise that then water-soluble of at least one layer is laminated on 2 surfaces of this dough shape composition.Another method comprises dough shape composition is fed between two or more water-soluble that this sheet for example is transferred under rotation with cylinder, and uses identical cylinder or other cylinder pressing mold simultaneously.Another method comprises dough shape composition is coated on water-soluble that comprises at least one layer, then another comprised that water-soluble of at least one layer is laminated on the composition of above-mentioned coating.In addition, also can soak into soluble non-woven fabrics or yarn fabric so that make this non-woven fabrics or yarn fabric have said composition, then will this water-soluble substrate be arranged in the both sides of the layer that forms thus with this dough shape composition.

Consider the accessibility of use, the sheet-like article that is used to do washing preferably of the present invention has the thickness of 0.1-5mm.That is to say that 5mm or littler thickness make tears this laundry sheet-like article easily, the feasible detergent composition that can the load q.s of while 0.1mm or thicker thickness.More preferably its thickness is in the scope of 0.25-3mm.

The sheet-like article that is used to do washing of the present invention preferably has 0.005-1.0g/cm ²Area density.When area density is in above-mentioned specified scope, detergent composition that can the load q.s on it and therefore can obtain fabulous detersive power.More preferably area density is at 0.02-0.5g/cm ²Scope.

It is desirable to: the sheet-like article that is used to do washing of the present invention the dispersing or flow out of material wherein not when tearing in actual use.Can easily check " wherein material disperses or flow out " by 2 kinds of following methods.

In one of these methods, obtain the sheet of a 5cm * 5cm around the sheet-like article that cutting is used to do washing.Cause the surface that it is all loaded on these goods with 200g weight in such method load then.Under 60% relative humidity, allow its level leave standstill 30 minutes, check whether material (being detergent composition) wherein flows out from this cross section at 25 ℃.Do not flow out and mean that these goods can use and do not make dirty hand or environment easily.

The purpose of another method is to measure the composition that flows out/leak out from innermost layer when tearing this sheet-like article.This method comprises: in the room that the relative humidity 60% is 20 ℃, with commercially available scissors sheet-like article partly is cut into 10cm * 20cm, then with the fixing 5mm slit edge not of clip, hung this sheet up cutting shoulder downward 30 minutes, in a vinyl disc, the washing composition that flows from this sheet/leak out is compiled in the vinyl disc simultaneously, then weigh.

Washing composition according to the present invention is when tearing or does not have wherein material seepage or effusive sheet-like article during use.Therefore, its can in all sorts of ways filling or use, and these methods can not be used for washing composition, softening agent or the SYNTHETIC OPTICAL WHITNER of conventional Powdered, sheet that is used to do washing or 1-package-type.The sheet-like article perforation that for example, this can be used to do washing is torn so that be convenient to.Also can be by printing last pattern or character thereon to improve the outward appearance of these goods.In addition, can also print operation instruction and notice thereon so that the user is noted.The method of said composition layer is feasible can easily to form the successive layer although prepare, and can certainly form discontinuous composition layer.

Thereby sheet-like article of the present invention can be packaged in and obtain laundry product very easily in the suitable containers.For example, the preparation multi-disc goods that are used to do washing of the present invention, and partially folded with every.With these sheets laminations and being packaged in the container in a zigzag, obtain to take out continuously easily the wrapped product that is used to do washing of sheet thus then.Fig. 4 has illustrated this product.Shown in Fig. 4 (a), partially folded sheet (41) to be to pile up in a zigzag, be then packed in the fixed container for example be shown among Fig. 4 (b) carton (42) thus in obtain the goods that are used to do washing thus, wherein can take out this sheet continuously.In this case, preferably this sheet has 9cm at least ²Area, more preferably 40-500cm ²Also can be by being that 4cm or wideer and length are that the sheet-like article that 30cm or longer the present invention are used to do washing rolls with width, the coil packing that will obtain like this obtains the goods that are used to do washing in the fixed container then.This series products sees it is good from angle convenient and that distribute arbitrarily easily.In addition, under the situation of scroll product, container (carton etc.) can be equipped with the sheet cutter made by metal and/or resin so that easy to use.In addition, this volume can with constant at interval on the direction parallel with minor axis perforation so that can the artificially or mechanically take out the inner sheet of more volume that limits size.Much less, this sheet can indicate scale so that indicate consumption.Simpler filling method also can be easily with the dosage that at every turn uses as the single filling of 5-20g activated detergent component sheet after, in loading container, arrange or do not arrange goods are packed with single filling morphology.In this mode, tear remaining of back for one and can refill in this container.

Washing composition according to the present invention is when tearing or does not have wherein material seepage or effusive sheet-like article during use.Therefore, its can in all sorts of ways filling or use, and these methods can not be used for the washing composition of the conventional Powdered or 1-package-type that is used to do washing.The sheet-like article perforation that for example, this can be used to do washing is torn so that be convenient to.Also can improve the outward appearance of these goods by last pattern of printing thereon or character.In addition, can also print operation instruction and notice thereon so that the user is noted.The method of said composition layer is feasible can easily to form the successive layer although prepare, and can certainly form discontinuous composition layer.

In order to illustrate in greater detail the present invention, provide following embodiment.Yet, should be appreciated that the present invention is not limited to these embodiment.

Test method 1

Now, the test method of using is described in experimental example.

Measure pin and go into the method I of hardness

Advance in the Dalton universal mixer (model 5DM-03-r) with every kind of component of the detergent composition of 1000g altogether with as tinting material (red No.106) feeding of marker.Temperature regulation after about 25 ℃, was mediated this mixture 1 minute down at low speed (about 100rpm) earlier, mediate down in high speed (about 200rpm) then.By using by Minolta Co., the colorimeter (CR-300) that Ltd. makes is measured the b value of mediating material, and continues to mediate till the b value reaches a steady state value at a high speed, obtains the detergent composition of uniformity thus.

Press the 3. (floorage: 1cm of adapter that is exclusively used in FUDOH RHEOMETER (RT-2010J-CW) on 25 ℃ the said detergent composition surface maintaining ²).When this adapter is absorbed in detergent composition 20mm with the speed of 30cm/min, measure stress.

The method I of evaluation composition seepage/outflow (going out property of anti-current) under load

5cm * 5cm the size and (weight: Wi) of weighing will be cut into around the detergent tablet.Next, the weight of 200g all being carried in the lip-deep mode of this detergent tablet with this weight is carried on this detergent tablet.It was left standstill 30 minutes 25 ℃ of levels under 60% relative humidity, scrape along the limit of being cut with cutter, and collect effusive material from this sheet (being detergent composition) thus, then weigh, weight is: W _aWith W _a/ W _iWeight percent represent rate of outflow.In this method, preferably rate of outflow is 5% or lower.

The method I of composition seepage/outflow (anti-current goes out) is down being torn in evaluation

25 ℃ of relative humidity 60% are cut into the sheet-like article of 10cm * 20cm with commercially available scissors at the centre portions of sheet-like article down, then with the fixing limit do not cut off of 5mm of clip.Simultaneously this sheet is cut edge and down hung up 30 minutes, the washing composition that flows out from this sheet/leak out collects in the vinyl disc and weighs.

Measure the method I of detersive power

The preparation of artificial dirty cloth

Prepare artificial dirty cloth sample by a piece of cloth being made dirty with the artificial dirty solution of forming below.By using the printing and dyeing of gravure roll shape applicator, this cloth is made dirty with artificial dirty solution.This is made dirty, and to operate in gravure roll mesh (cell) volume be 58cm ³/ m ²With coating speed be under the 1.0m/min, drying was carried out under 100 ℃ of temperature in 1 minute.Use cotton shirt 2003 (by valley head shop system) as this sample cloth.

The composition of artificial dirty solution

Lauric acid 0.44 weight %

Interior myristic acid 3.09 weight %

Pentadecylic acid 2.31 weight %

Palmitinic acid 6.18 weight %

Margaric acid 0.44 weight %

Stearic acid 1.57 weight %

Oleic acid 7.75 weight %

Triolein 13.06 weight %

Palmitinic acid n-hexadecyl ester 2.18 weight %

Squalene 6.53 weight %

Albumen Yelkin TTS liquid crystal thing 1.94 weight %

Deer natural pond laterite 8.11 weight %

Carbon black 0.01 weight %

The tap water surplus

Wash conditions and evaluation method

The artificial dirty cloth of the above-mentioned preparation of 5 10cm * 10cm is put in 1 liter the aqueous solution of the washing composition that will estimate and under 100rpm, in Terg-O-tometer, washs under the condition below.

Wash conditions:

Washing time 10 minutes

Detergent concentration 0.05%

4 ° of DH of the water hardness

20 ℃ of water temps

Rinsing is with washing from the beginning 5 minutes

Instrument (Shimadzu Seisakusho Ltd.'s manufacturing) by the service recorder color is estimated detersive power at the 550nm place mensuration beginning cloth (promptly unsoiled) and the reflectivity of dirty cloth before washing and afterwards, calculate soil removal efficiency (%) according to following formula then.The mean value of 5 cloth is represented detersive power.

Test routine I-1

The component feeding of listing in the table 1 of 1000g is altogether advanced in the Dalton universal mixer (model 5DM-03-r).Temperature regulation after about 25 ℃, is mediated this mixture 1 minute down at low speed (about 100rpm) earlier, mediate till this this powder mixture becomes the dough shape down in high speed (about 200rpm) then, obtain the detergent composition of uniformity thus.

Then, use noodle press " titania (registrar entitling) " (Industrial ProdottiStampati TORINO manufacturing) that this dough is processed into the thick thin layer of 2mm.Then, this thin layer is cut into the sheet of 50 * 100mm size.The weight in average of these synusia is 15g, and centre plane density is 0.3g/cm ²

Next, the fiber process that will prepare according to the embodiment 1 of JP-A8-3848 by the rotation Method for bonding becomes level ground amount (per unit weight) to be 20g/m ²Non-woven fabrics, and " Hi-selon (water-solubility membrane) " that will make by Japanese synthetic chemical industry (strain) lamination thereon.Be clipped between 2 laminate that obtain like this as the thin-layer tablet of outermost mode with non-woven fabrics above-mentioned cutting.Then, with around the composition sheet that obtains with FUJI IMPULSE AUTO SEALER (FA-600-5) thus heat seal obtains detergent tablet.Then with aforesaid method under load and tearing the discharge of estimating down the gained detergent tablet.Table 1 has provided the result.

In addition, by with perforation this detergent tablet being divided into 3 parts equably, when the eyelet hand tore, the result can easily tear the seepage or the outflow that only have seldom.Have, washing composition is bonded on hand hardly again.This detergent tablet is dissolved in obtains the concentration that limits in the ion exchanged water and estimate its detersive power with aforesaid method.The result has reached 58% detersive power.It is 2.63kg/cm that the pin of this dough shape detergent composition of measuring by aforesaid method is gone into hardness ²

Test routine I-2

By using the component of listing in the table 1 with ratio given in the table 1, use with test routine I-1 in identical method prepare dough shape detergent composition.

Long 70mm is advanced in this dough shape detergent composition mold pressing, obtain the thin-layer tablet identical in the mould of wide 70mm and dark 0.7mm with this mould.The weight in average that these sheets are one piece is 5.1g, and centre plane density is 0.10g/cm ²

Next, the fiber process that will prepare according to the embodiment 1 of JP-A8-3848 by the rotation Method for bonding becomes level ground amount (per unit weight) to be 20g/m ²Non-woven fabrics, and the above-mentioned thin-layer tablet of its clamping obtained the sheet lotion.Table 1 has provided under load and has torn discharge and the detersive power of estimating the gained detergent tablet down.Can easily tear the seepage or the outflow that only have seldom.In addition, washing composition is bonded on hand hardly.Table 1 gives the pin of this detergent composition of measuring by aforesaid method and goes into hardness.

Test routine I-3

With each composition of ratio given in the table 1 is that 300g sends among the BENCH KNEADER (PNV-1) of Irie Shokai (strain) manufacturing with the total amount.After being heated to 30 ℃, till obtaining dough shape mixture, obtain the detergent composition of uniformity thus with 4 grades of these powder mixtures of stirring.

Next, with 2 by Nippon Synthetic Chemical Industry, the water-solubility membrane " Hi-selon " that Co., Ltd. make is inserted in the stainless steel rider (diameter: 50mm) that can rotate relative to one another that three power are made manufacturing.When this roller of manual operation, above-mentioned dough is clipped between the water-solubility membrane, the composition material that obtains is cut into the sheet of 10cm * 10cm.Then, with around the sheet that obtains with FUJI IMPULSE AUTO SEALER (FA-600-5) thus heat seal obtains detergent tablet.The detergent tablet that obtains has the thick detergent composition layer of 4mm and weight in average is 60g.Its centre plane density is 0.6g/cm ²Table 1 has provided this detergent tablet under load and discharge under tearing and detersive power.In addition, by with perforation washing composition being divided into 3 parts equably, when the pin hole hand tore, the result can easily tear the seepage or the outflow that only have seldom.Have, washing composition is bonded on hand hardly again.Table 1 gives the pin of this detergent composition of measuring by aforesaid method and goes into hardness.

Test routine I-4

Advance Kurimoto with the component feeding that ratio given in the table 1 will be listed in the table 1, at room temperature obtain the thick dough shape detergent composition thin layer of 1.2mm in the KRC kneader (model S1) that 1.2 * 50mm slit is housed that Ltd. makes and therein with the 100rpm kneading.

Next, will become level ground amount (per unit weight) according to the fiber process of the test of JP-A1-229805 example I-1 preparation by the rotation Method for bonding is 40 or 20g/m ²Non-woven fabrics.Be clipped in above-mentioned thin layer between the two-layer nonwoven and make the roller of its noodle press by being used for testing routine I-1 obtain the thick thin layer of 3mm, wherein soak this soluble non-woven fabrics with this detergent composition.Then, this thin layer is cut into the sheet of 50 * 100mm size.The weight in average of these sheets is 18g, and centre plane density is 0.36g/cm ²

Next, to be clipped in 2 by between the laminated laminate by soaking this thick thin layer of 3mm that obtains with detergent composition, this laminate is according to the test of JP-A8-3848 example I-2, is that (per unit weight) measured on water miscible level ground is 20g/m to outermost mode with non-woven fabrics ²Non-woven fabrics and by Nippon Synthetic Chemical Industry, water-solubility membrane " Hi-selon " the lamination preparation that Co., Ltd. make.Then, with around the sheet that obtains with FUJIIMPULSE AUTO SEALER (FA-600-5) thus heat seal obtains detergent tablet.Table 1 has provided this detergent tablet under load and discharge under tearing and detersive power.In addition, by with perforation detergent tablet being divided into 3 parts equably, when the pin hole hand tore, the result can easily tear the seepage or the outflow that only have seldom.Have, washing composition is bonded on hand hardly again.Table 1 gives the pin of this detergent composition of measuring by aforesaid method and goes into hardness.

Test routine I-5 to I-9

By the method identical, use the component of listing in table 1 or 2 to prepare each dough shape detergent composition with the ratio that wherein provides with experimental example I-1.

Next, use the method identical to obtain detergent tablet with testing routine I-1.Use level ground amount (per unit weight) to be 25g/m ²Fiber as soluble non-woven fabrics.The weight in average of the detergent composition thin layer in each detergent tablet is 13-20g, and centre plane density is 0.26-0.4g/cm ²Table 1 and 2 has provided the detergent tablet that obtains like this under load and discharge under tearing and detersive power.In addition, by with perforation detergent tablet being divided into 3 parts equably, when the pin hole hand tore, the result can easily tear the seepage or the outflow that only have seldom.Have, washing composition is bonded on hand hardly again.Table 1 and 2 gives the pin of each detergent composition of measuring by aforesaid method and goes into hardness.

Test routine I-10 to I-12

By with test routine I-1 identical method, use the component of listing in the table 2 to prepare each dough shape detergent composition with the ratio that wherein provides.

In above-mentioned experimental example,, its high workability almost can not be processed to such thin layer because testing the detergent composition of routine I-10.Therefore, it is that 5cm is in the bag of 10cm deeply that this detergent composition is packaged in internal diameter with the ratio of 15g, and this bag is by making with the identical laminate that is used for testing routine I-1.

The routine I-11 of method preparation test, I-12 thin-layer tablet with identical with the routine I-2 of test use used laminate in the routine I-1 of test then, are processed into detergent tablet with the identical mode of the routine I-1 of use therein test.Table 2 has provided discharge and the detersive power of detergent tablet under tearing that obtains like this.In addition, by this detergent tablet being divided into 3 parts equably, tear along the pin hole hand with perforation.As a result, under each situation, all observe the seepage or the outflow of washing composition.Have, washing composition also is bonded on hand again.

Table 2 gives the pin of each detergent composition of measuring by aforesaid method and goes into hardness.

Table 1

Component			The group branch	Experimental example number
				Experimental example number					I-1	I-2	I-3	I-4	I-5	I-6
				Detergent composition (wt.%)	Nonionogenic tenside		^*1	12	I-1	I-2	I-3	I-4	I-5	I-6
Nonionogenic tenside		^*2	12		Nonionogenic tenside		^*1	12
Nonionogenic tenside		^*2	12		Nonionogenic tenside		^*3							25			20	25
Nonionogenic tenside		^*4			Nonionogenic tenside		^*3			17		10		25			20	25
Nonionogenic tenside		^*4			Nonionogenic tenside		^*5			17		10				20
Anion surfactant		^*6			Nonionogenic tenside		^*5		3	2	2	4				20
Anion surfactant		^*6			Anion surfactant		^*7		3	2	2	4				2		2
Anion surfactant		^*8			Anion surfactant		^*7			8						2		2
Anion surfactant		^*8			Anion surfactant		^*9			8					2
Anion surfactant		^*10			Anion surfactant		^*9		2	1	2				2
Anion surfactant		^*10			Carbonate		^*11	30	2	1	2			3	25	10	25	30
Saltcake					Carbonate		^*11	30						3	25	10	25	30
Saltcake					Crystalline silicate		^*12							32	2	20
Crystal aluminosilicate		^*13	30		Crystalline silicate		^*12		20	30	35	20	25	32	2	20
Crystal aluminosilicate		^*13	30		The amorphous silicon aluminium hydrochlorate		^*14	4	20	30	35	20	25	3			8	5
Organic sequestering agent		^*15	2		The amorphous silicon aluminium hydrochlorate		^*14	4						3			8	5
Organic sequestering agent		^*15	2		Organic sequestering agent		^*16								2
Polycarboxylic acid polymer		^*17	2		Organic sequestering agent		^*16					2			2
Polycarboxylic acid polymer		^*17	2		Polycarboxylic acid polymer		^*18					2		4	3		2	4
Polycarboxylic acid polymer		^*19			Polycarboxylic acid polymer		^*18				2			4	3		2	4
Polycarboxylic acid polymer		^*19			Dissolution aids		^*20				2				2			2
Dissolution aids		^*21	2		Dissolution aids		^*20				2	2			2			2
Dissolution aids		^*21	2		Organic washing-assisting detergent		^*22	2			2	2		2	2	1	1	1
Organic washing-assisting detergent		^*23			Organic washing-assisting detergent		^*22	2				4		2	2	1	1	1
Organic washing-assisting detergent		^*23			The bleaching component		^*24					4
The bleaching component		^*25			The bleaching component		^*24
The bleaching component		^*25			Common ingredients		^*26	4						6	4	4	2	6
The content of liquid active ingredient in the gross activity component under the normal temperature					Common ingredients		^*26	4	100％	83％	57％	77％	88％	6	4	4	2	6	93％
				The content of fluid organic material matter in total organic compound				29％	100％	83％	57％	77％	88％	40％	60％	39％	24％	38％	93％
Organic content in the total composition								29％	66％	58％	57％	67％	55％	40％	60％	39％	24％	38％	60％
Organic content in the total composition				Estimate		Pin is gone into hardness (kg/cm ²)		2.63	66％	58％	57％	67％	55％	0.47	2.53	5.04	0.17	0.17	60％
Going out property of anti-current	Under load (g)	0.4	0.8			Pin is gone into hardness (kg/cm ²)		2.63	0.2	0.3	0.5	0.6		0.47	2.53	5.04	0.17	0.17
	Under load (g)	0.4	0.8			When tearing (g)	0.01	0.05	0.2	0.3	0.5	0.6	0.01	0.1	0.2	0.1
	Detersive power (%)		58			When tearing (g)	0.01	0.05	66	61	64	59	0.01	0.1	0.2	0.1	61

Table 2

Component			The group branch	Experimental example number
				Experimental example number					I-7	I-8	I-9	I-10	I-11	I-12
				Detergent composition (wt.%)	Nonionogenic tenside	^*1		2	I-7	I-8	I-9	I-10	I-11	I-12		35	20
Nonionogenic tenside		^*2			Nonionogenic tenside	^*1		2		13						35	20
Nonionogenic tenside		^*2			Nonionogenic tenside	^*3				13							20
Nonionogenic tenside		^*4	10		Nonionogenic tenside	^*3			20								20
Nonionogenic tenside		^*4	10		Nonionogenic tenside	^*5			20					3		5
Anion surfactant		^*6	20		Nonionogenic tenside	^*5			1					3		5
Anion surfactant		^*6	20		Anion surfactant	^*7	5		1
Anion surfactant		^*8			Anion surfactant	^*7	5			5
Anion surfactant		^*8			Anion surfactant	^*9				5				2
Anion surfactant		^*10			Anion surfactant	^*9				1				2
Anion surfactant		^*10			Carbonate	^*11	25	25		1				25	15		30
Saltcake					Carbonate	^*11	25	25						25	15		30
Saltcake					Crystalline silicate	^*12		3						2	15
Crystal aluminosilicate		^*13	25		Crystalline silicate	^*12		3	25	20	25	45		2	15
Crystal aluminosilicate		^*13	25		The amorphous silicon aluminium hydrochlorate	^*14		4	25	20	25	45
Organic sequestering agent		^*15			The amorphous silicon aluminium hydrochlorate	^*14		4	2	2
Organic sequestering agent		^*15			Organic sequestering agent	^*16			2	2						5
Polycarboxylic acid polymer		^*17			Organic sequestering agent	^*16				2		5				5
Polycarboxylic acid polymer		^*17			Polycarboxylic acid polymer	^*18	5	3		2		5			4
Polycarboxylic acid polymer		^*19			Polycarboxylic acid polymer	^*18	5	3							4
Polycarboxylic acid polymer		^*19			Dissolution aids	^*20	3									4	2
Dissolution aids		^*21			Dissolution aids	^*20	3			5						4	2
Dissolution aids		^*21			Organic washing-assisting detergent	^*22	1	1		5				2	1	2	2
Organic washing-assisting detergent		^*23			Organic washing-assisting detergent	^*22	1	1					2	2	1	2	2
Organic washing-assisting detergent		^*23			The bleaching component	^*24		10					2
The bleaching component		^*25			The bleaching component	^*24		10		12
The bleaching component		^*25			Common ingredients	^*26	6	4		12				6	5	5	4
The content of liquid active ingredient in the gross activity component under the normal temperature					Common ingredients	^*26	6	4	29％	96％	67％	100％	100％	6	5	5	4	100％
				The content of fluid organic material matter in total organic compound			80％	37％	29％	96％	67％	100％	100％	67％	22％	46％	27％	100％
Organic content in the total composition							80％	37％	50％	65％	52％	55％	54％	67％	22％	46％	27％	70％
Organic content in the total composition				Estimate	Pin is gone into hardness (kg/cm ²)		2.50	0.18	50％	65％	52％	55％	54％	5.88	0.00	0.01	0.01	70％
Going out property of anti-current	Under load (g)		1.5		Pin is gone into hardness (kg/cm ²)		2.50	0.18	0.3	0.7	18.0	12.0	11.0	5.88	0.00	0.01	0.01
	Under load (g)		1.5		When tearing (g)	0	0.1	0.3	0.3	0.7	18.0	12.0	11.0	1.3	1	0.8
	Detersive power (%)				When tearing (g)	0	0.1	0.3	58	59	61	49	32	1.3	1	0.8	41

(notes)

* 1: the average 6 moles ethylene oxide adduct of lauryl alcohol.

* 2: the C that Mitsubishi Chemical makes _12-13The average 6.5 moles ethylene oxide adduct (Nonidet S-6.5) of alcohol.

* 3: the C that Japanese catalyst chemical industry (strain) is made _12-13The average 7 moles ethylene oxide adduct (Softanol 70) of secondary alcohol.

* 4:C ₁₂Alcohol/C ₁₄Average 3 moles of ethylene oxide of alcohol mixture (weight ratio 75/25)/average 2 moles of propylene oxide/average 3 moles of ethylene oxide are with the affixture of block arrangement.

* 5: the average 6 moles of ethylene oxide affixtures of the coconut oil fatty acid methyl ester (Exceparl MC) that flower king (strain) makes.

* 6: weight ratio is 1/1 straight chained alkyl (C _10-13) mixture of Phenylsulfonic acid sodium salt and sylvite.

* 7: weight ratio is 1/1 the alkylsurfuric acid ester sodium salt and the mixture (coconut oil fat acid constituents) of diethanolamine (coco-nut oil fatty acid composition).

* 8: the alpha-sulfo-fatty acid methyl ester sodium salt that in fatty acid residue, has 14-16 carbon atom.

* 9: alpha-olefin sodium sulfonate with 14-16 carbon atom.

* 10: the sodium salt of tallow fatty acids.

* 11: weight ratio is 7/3 the yellow soda ash and the mixture of salt of wormwood.

* 12:Hoechst " SKS-6 " that make.

* the synthetic zeolite " Toyobuilder " made of 13:Tosoh Corp..

* 14:Rhodia " Tixolex 25 " of making.

* 15: trisodium citrate.

* 16: sodium ethylene diamine tetracetate.

* the sodium polyacrylate " Sokalan PA40 " made of 17:BASF.

* the sodium salt " SokalanCP5 " of vinylformic acid/maleic acid of making of 18:BASF.

* 19: by the poly-glyoxime acid sodium (Mw: about 9000) of formula (X) expression

* 20: paratoluenesulfonic acid sodium salt.

* 21: wilkinite (reagent).

* 22: polyoxyethylene glycol (Mw: about 6000).

* the polymkeric substance that contains vinyl pyrrolidone " GAFQUAT 734 " made of 23:ISP (Japan) Ltd.

* 24: contain weight ratio and be 1/4 by the bleach-activating agent of formula (XI) expression and the bleaching components of SPC-D

* 25: contain weight ratio and be the tetra acetyl ethylene diamine that 1/4 Hoechst makes and the bleaching components of SPC-D.

* 26: enzyme 1% weight [comprising mixed weight] than " API-21H " as proteolytic enzyme that be 2/1/1/1 (clear and electrician's (strain) makes), as " Lipolase 100T " (Novo Nordisk manufacturing) of lipase, as " Cellzyme 0.1T " (Novo Nordisk manufacturing) of cellulase and as diastatic " Termamyl 60T " (Novo Nordisk manufacturing); The fluorescence dye of 0.5% weight [by mix " Whitex SA " and " Chinopal CBS " preparation of Ciba-GeigyLtd. manufacturing that Sumitomo Chemical society makes with 1/1 weight ratio]; Antifoams/the froth suppressor of 0.25% weight [silicone oil of aminoalkyl group modification]; The listing in the spices in the following table 3 and equilibrate to the saltcake of 100% weight of 0.25% weight.

		Content
		Content	Perfume composition	Linalool	5
Geraniol	5			Linalool	5
Geraniol	5	Geraniol		10
Phenylethyl alcohol	10	Geraniol		10
Phenylethyl alcohol	10	Meraneine		1
The acetate benzyl ester	2	Meraneine		1
The acetate benzyl ester	2	The acetate phenylethylester		1
Citral	1	The acetate phenylethylester		1
Citral	1	Limonene		2
Terpinolene	3	Limonene		2
Terpinolene	3	4-(4-hydroxy-4-methyl amyl group)-3-cyclohexylidene-1-carboxyl aldehyde		3
Jasmonal H	5			3
Jasmonal H	5	α-Yi Jiajiziluolantong		7
3,4-methylene radical titanium dioxide benzyl aldehyde	4	α-Yi Jiajiziluolantong		7
3,4-methylene radical titanium dioxide benzyl aldehyde	4	1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-six-methylcyclopentyl-γ-2-chromene		12
Sandenol	7			12
Sandenol	7	Acetate trichloromethyl phenyl methyl alcohol ester		1
1, the 2-benzopyrone	2	Acetate trichloromethyl phenyl methyl alcohol ester		1
1, the 2-benzopyrone	2	Ethyl-beta-phenyl acrylate		5
Woodyflor	5	Ethyl-beta-phenyl acrylate		5
Woodyflor	5	1-methyl-4-sec.-propyl-1-hexamethylene-8-alcohol		9

I as a result

Clearly show as top data, test routine I-1 to the washing composition of I-9 because so its dough state all demonstrates very little powder dustability, each detergent tablet is all by water-soluble substrate with have specific pin and go into the dough shape detergent composition that is clipped between the substrate of hardness and form.In addition, owing to have specific pin and go into hardness, so these goods are using or all demonstrating the leakage of very little wherein material and help the adjusting of usage quantity when tearing.In addition, owing to wherein contain at alkaline reagents and the sequestrant of removing the basal component of effective nonionogenic tenside and washing composition aspect the oily stain, so these detergent tablets have fabulous detersive power.

On the contrary, to go into aspect the hardness at pin to the product of I-12 be poor to experimental example I-10.In other words, in these embodiments, detergent composition is soft high flow, therefore almost can not obtain sheet-like article.Even can obtain sheet-like article, also can cause the leakage of detergent composition, this makes that its use is very inconvenient.In experimental example I-11 and I-12, because do not have alkaline reagents or sequestrant, so the detergent composition detersive power is low

Test method II

Now, the test method of using in an embodiment is described.In II-6, the method for use-testing example II is measured at the routine II-1 of test.

Estimate the method II that composition flows out/leaks when tearing

Measure by the identical method of method I that when tearing, flows out/leak with above-mentioned evaluation composition.

Experimental example II-1＜the be used for detergent tablet of clothes 〉

With 25g dewatered domiphen base oxide in microwave oven in advance; " Nonidet R-7 " [polyoxyethylene (7) alkyl (C that 10g is made by Mitsubishi Chemical's (strain) _12-15) ether] vitriol (sodium salt); 5g is by Nippon Shokubai Co., " SoftanolEP7045 " [C that Ltd. makes _12-14Secondary alcohol polyoxyethylene (7) polyoxypropylene (4.5) glycol]; The zeolite A4 type that 40g is made by TosohCorp.; The vinylformic acid of 4g/maleic acid sylvite (Mw:60000); 8g yellow soda ash; 2.5g polypropylene glycol (Mw:1000); " Tixolex 25 " that 3g is made by Kofran Chemical; 0.2g d-limonene; 0.9g " API-21 " as proteolytic enzyme by Showa Denko K.K. manufacturing; 0.9g " Celluzyme 1.0T " as cellulase by Novo Nordisk Industry manufacturing; 0.5g conduct diastatic " Termamyl 6.0T " by Novo Nordisk Industry manufacturing; 0.2g mixing with hand, the fluorescence dye " Chinopal CBS-X " that " Lipolase 100T " and the 0.2g as the lipase that are made by Novo Nordisk Industry are made by Ciba-Geigy obtains dough.

Next, (10cm * 20cm) make this non-woven fabrics in the middle of outermost layer is inserted in 2 stainless steel riders that diameter is 50mm, this laminate is by level ground amount (per unit weight) is 20g/m with 2 laminate ²The nonwoven layer that forms of the embodiment 2 according to JP-A 8-3848 be pressed in Nippon Synthetic Chemical Industry, Co., Ltd. the water-solubility membrane of Zhi Zaoing " Hi-selon " prepares, this roller is by can rotating relative to one another that Sanriki Seisakusyo makes, with this roller of manual operation, thereby and the dough that 7g obtains is inserted in the detergent tablet that obtains being used for clothes between 2 laminate.Repeat this process and obtain 50 detergent tablets that contain the 7g washing composition for 50 times thus, every 10cm * 20cm size.The centre plane density of these sheets is 0.047g/cm ², mean thickness is 1.2mm.Then, with the trellis arrangement that is shown among Fig. 3 all these sheets are overlaped, it is long to be then packed in 12cm, in the carton that 13cm is wide and 9cm is dark.Above the box, form the slot that is of a size of 6cm * 4.5cm at this.And from this box, take out a slice detergent body.As a result, following a slice is partly pulled out this box.This process can repeat 47 times.Confirm these sheets easily to take out thus and hand or finger need not be injected in this box.In addition, can these sheets be torn washing composition seepage or the outflow that only demonstrates simultaneously seldom with hand.It is almost tack-free.When measuring with aforesaid method, 0.00g washing composition seepage or outflow.

Experimental example II-2＜the be used for detergent tablet of clothes 〉

The mixture that obtains forming below.Be that said composition is: " Softanol 70 " [polyoxyethylene (7) alkyl (C of 5% weight by the NipponShokubai manufacturing _12-14) ether]; " the Nonidet R-7 " of Mitsubishi Chemical's system of 5% weight [polyoxyethylene (7) alkyl (C _12-15) ether]; The polyoxyethylene of 0.4% weight (6) alkyl (C ₁₂/ C ₁₄/ C ₁₆=70/25/5) ether; The coco-nut oil fatty acid sodium salt of 3.6% weight; Passing through of 10% weight with the alkyl benzene sulphonate (ABS) (Alken L) and the dry LAS-Na that obtains of 48%NaOH neutralization by Nisseki Senzai K.K. manufacturing; The AS-Na[Mitsubishi Chemical Corp. of 2% weight makes, " alkyl (Dobanol 25) vitriol " (C _12-15Vitriol)]; The zeolite A4 type by Tosoh Corp. manufacturing of 15.6% weight; The cellular silica compound " Tixolex 25 " by Kofran Chemical manufacturing of 3.6% weight; The crystalline silicate of 6% weight (by " SKS-6 " of Hoechst manufacturing); No. 1, the water glass of 4.4% weight; The yellow soda ash by Tosoh Corp. manufacturing of 8% weight; Vinylformic acid/the maleic acid of 0.8% weight (Mw:60000) sodium salt; The sodium polyacrylate of 2.4% weight (Mw:20000); The poly-ethanoyl carboxylic acid sodium salt (Mw:20000) of 1.2% weight; The polyoxyethylene glycol of 22.4% weight (Mw:6000); The salt of wormwood of 4.6% weight; The sodium sulfate of 1.4% weight; The ratio of mixture with 1: 1 of 1.6% weight contains the mixture of " Celluzyme 1.0T " that " API-21 " that made by ShowaDenko K.K. make as enzyme with by Novo Nordisk Industry; " Chinopal CBS-X " and the water of surplus by the Ciba-Geigy manufacturing of 0.4% weight.

Next, identical with the method among the experimental example II-1, with the long laminate of the wide 25cm of 2 15cm be inserted in the stainless steel rider that 2 identical diameters are 50mm (it be with the routine II-1 of test in identical roller) between, this laminate is to be 20g/cm by the level ground amount that will form according to the embodiment 3 of JP-A8-127919 ²Nonwoven layer is pressed in the Industry by Nippon SyntheticChemical, Co., Ltd. the water-solubility membrane of Zhi Zaoing " Hi-selon " is gone up preparation, when rotating this roller, obtain the long detergent tablet that is used for clothes of 10m between two laminate thereby just the mixture of above-mentioned preparation is clipped in constant speed with the speed of 1m/min.The centre plane density of this sheet is 0.053g/cm ², mean thickness is 1.3mm.Then, sheet that 20m is long twists on the fiber board roller of the wide 2.5cm diameter of 11cm and puts in the box that cutting knife is housed.Thus, use can easily be torn this sheet and the seldom seepage or the outflow of washing composition are only arranged with random length at the metal cutter on this box top.In addition, it is almost tack-free.When measuring with aforesaid method, 0.11g washing composition seepage or outflow.

Test routine II-3＜sheet SYNTHETIC OPTICAL WHITNER 〉

The level ground amount that 2 long embodiment 1 according to JP-B3-25539 of the wide 25m of 15cm are formed is 10g/m ²Non-woven fabrics to be inserted in diameter be that 50mm can be between the stainless steel rider of direction respect to one another with the rotation of the speed of 1m/min.When this roller of rotation; to contain 70% weight SPC-D; 5% weight is as the tetra acetyl ethylene diamine of bleach-activating agent; 5% weight Oleum Cocois chain triacontanol base oxygen benzene sulfonic acid sodium salt; 2% weight is with the fumaric acid of used as stabilizers, 10% weight polyoxyethylene glycol (Mw:2000) thereby and the composition of 8% weight sodium carbonate be transported to constant speed and obtain the long sheet SYNTHETIC OPTICAL WHITNER that is used for clothes of 10m between 2 non-woven fabrics.The centre plane density of this sheet is 0.050g/cm ², mean thickness 1.6mm.Then, sheet that 20m is long twists on the fiber board roller of the wide 2.5cm diameter of 11cm and puts in the box that cutting knife is housed.Thus, use can easily be torn this sheet and the seldom seepage or the outflow of washing composition are only arranged with random length at the metal cutter on this box top.In addition, it is almost tack-free.When measuring with aforesaid method, 0.07g washing composition seepage or outflow.

Experimental example II-4＜the be used for sheet softening agent of clothes 〉

By mixing the softening agent base-material that is expressed from the next of 42% weight, the dihydro tallow alkyl alkyl dimethyl ammonium chloride of 35% weight, the glycerine of 11% weight, two limonenes of the propylene glycol of 11% weight and 1% weight make composition.

Next, be 25g/m by the level ground amount that will form according to the embodiment 2 of JP-B3-25539 ²Nonwoven layer be pressed in Industry by Nippon Synthetic Chemical, the water-solubility membrane " Hi-selon " that Co., Ltd. make is gone up the laminate of 2 10cm * 20cm of preparation.Then, a laminate " Hi-Selon " is placed on up on the stainless steel plate of 13cm * 22cm and and spreads thereon equably the 7g above-mentioned composition.Then, put another sheet laminate thereon, then the stainless steel with another sheet 13cm * 22cm covers.Then, thus the pressing machine that uses AIKOEngineering to make applies the load of 400kgf on 15 points of this sheet obtain the sheet softening agent.Repeat this process and obtain 50 sheet softening agents for 50 times thus, each 10cm * 20cm's contains the 7g softening agent.The centre plane density of these sheets is 0.022g/cm ², mean thickness is 0.9mm.Then, with the trellis arrangement that is shown among Fig. 3 all these sheets are overlaped, it is long to be then packed in 12cm, in the carton that 13cm is wide and 9cm is dark.Above the box, form the slot that is of a size of 6cm * 4.5cm at this.Confirm that thus these sheets can take out continuously from the hole.In addition, can these sheets be torn washing composition seepage or the outflow that only demonstrates simultaneously seldom with hand.It is almost tack-free.When measuring with aforesaid method, 0.00g washing composition seepage or outflow.

Test routine II-5＜the be used for detergent tablet of clothes 〉

The zeolite A4 type that 5g is made by Tosoh Corp. joins in the dough shape composition that 30g prepares in the routine II-1 of test.Then, the noodle press made from Industria Prodotti StampatiTORINO " titania (registrar entitling) " thus the mixture of handling gained obtains the thin layer of thickness less than 1mm.Next, these thin layers are coated on equably according to the 0.8g fiber (3mm is long) of embodiment 2 preparation of JP-A8-3848 thus the surface and the inside on obtain the washing composition that is used for clothes of 2 17cm * 8.5cm.Repeat this process and obtain 40 detergent tablets for 20 times thus.The centre plane density of these sheets is 0.13g/cm ², mean thickness is 1.0mm.Then, all these sheets are converted into 2 overlap, long to be then packed in 10cm after stacking in a zigzag, in the carton that 10cm is wide and 10cm is dark.Above the box, form slot (6cm * 4.5cm) also therefrom take out 1 at this.As a result, following a slice is partly pulled out this box.This process can repeat 15 times.In addition, can these sheets be torn washing composition seepage or the outflow that only demonstrates simultaneously seldom with hand.It is almost tack-free.When cutting this sheet, find 0.01g washing composition seepage or outflow with aforesaid method with scissors.

Test routine II-6＜the be used for roll shape detergent tablet of clothes 〉

By mixing " NonidetR-7 " [polyoxyethylene (7) alkyl (C that 600g is made by Mitsubishi Chemical Corp. _12-15) ether], 300g is by Nippon Shokubai Co., " Softanol EP7045 " [C that Ltd. makes _12-14Secondary alcohol polyoxyethylene (7) polyoxypropylene (4.5) dibasic alcohol], " Nonidet R-7 " [polyoxyethylene (7) alkyl (C that 100g polypropylene glycol (Mw:1000) and 200g are made by MitsubishiChemical Corp. _12-15) ether] and vitriol, obtain liquid composition.

The level ground amount that the embodiment 3 according to JP-A8-127919 that the wide 5m of a slice 15cm is long forms is 15g/m ²Non-woven fabrics be immersed in this liquid composition 5 minutes.After enough wetting thus, this non-woven fabrics is inserted between the stainless steel rider that 2 identical diameters are 50mm (identical as what use in the routine II-1 of test), then before passing through this roller, composition with constant speed powdery, it contains the polyoxyethylene glycol (Mw:6000) of 20% weight, the vinylformic acid of 2% weight/maleic acid sylvite (Mw:60000), the yellow soda ash of 20% weight, " Tixolex 25 " by Kofran Chemical manufacturing of 40% weight, the d-limonene of 1% weight, " API-21 " by Showa Denko K.K. manufacturing of 0.5% weight, " the Celluzyme 1.0T " that make by Novo Industry of 0.5% weight, " Chinopal CBS-X " and the zeolite A4 type by Tosoh Corp. manufacturing of surplus made by Ciba-Geigy of 0.4% weight.Next, thus rotating this roller with the speed of 1m/min in direction respect to one another obtains detergent tablet with this powder coated.The centre plane density of this sheet is 0.083g/cm ², mean thickness is 0.7mm.Then, thus with the sheet perforation that 5m is long and roll and obtain the roller that internal diameter is the hollow of 2.5cm on width of the interval of 10cm.Then it is packaged in the dark garden cylindrical container of 15cm diameter 20cm and in the above on cover and have that cross slits is long to be the lid of 3cm otch.When this slit takes out this sheet, it is cut open at perforated portion, and a slice is partly pulled out from this container down.Can repeat this process 12 times.When tearing this sheet, demonstrate seldom washing composition seepage or outflow and tack-free at perforated portion.When cutting this sheet, find to have 0.10g washing composition seepage number or flow out with aforesaid method with scissors.

II as a result

Clearly show as these results, test routine II-1 to the sheet-like article that is used to do washing of II-6 during use or when tearing, demonstrate very little wherein material disperse and usage quantity is convenient at random regulate.Owing to being sheet and not having the wherein seepage of material (powder etc.), so such goods can fold and be packaged in the container in a zigzag.In addition, it also can roll and be then packed in the container.Obviously these characteristics provide the fabulous handling properties of these goods.

The simple description of accompanying drawing

Fig. 1 schematically illustrates the example according to sheet-like article of the present invention, and Fig. 2 schematically illustrates its another example, and Fig. 3 also schematically illustrates another example, and Fig. 4 schematically illustrates the example according to the goods that are used to do washing of the present invention.

Claims

1, be used to the sheet-like article that washs, it comprises that by going into hardness at 25 ℃ of hour hands be 0.1-10kg/cm ²The thin layer made of face dough and be configured in water-soluble of this thin layer both sides, this face dough contains and is selected from the detergent composition that is used for clothes, at least a composition of fabric softener composition and bleaching composition.

2, the sheet-like article that is used to wash as claimed in claim 1, wherein the thickness of this thin layer is 0.1-5mm, area density is 0.005-1.0g/cm ²

3, the sheet-like article that is used to wash as claimed in claim 1, it has by by using 1/5-1 time amount packing and being packaged in form in the box, and each amount of using is 5-20g activated detergent component.

4, the sheet-like article that is used to wash as claimed in claim 1, wherein above-mentioned thin layer are to be made by the face dough that the surface has viscosity, and water-soluble viscosity that reduces this thin layer surface.

5, the sheet-like article that is used to wash as claimed in claim 1, wherein said composition is to contain at least a nonionogenic tenside, the detergent composition that the non-phosphoric acid of at least a alkaline reagents and at least a metal ion chelation agent is.

6, being used to the goods that wash, is to obtain by a lot of sheets sheet-like article that is used for washing is as defined in claim 1 piled up in a zigzag and is packaged in given container.

7, be used to the goods that wash, thereby be to obtain more than the width 4cm by will the sheet-like article that is used to wash as defined in claim 1 rolling, the volume that length 30cm is above obtains this coil packing then in given container.