CN107828567B

CN107828567B - Piece for washing

Info

Publication number: CN107828567B
Application number: CN201711087720.6A
Authority: CN
Inventors: 沈愚先; 金胜镇; 宋俊烨; 金致会; 张硕胤
Original assignee: LG Household and Health Care Ltd
Current assignee: LG H&H Co Ltd
Priority date: 2011-05-13
Filing date: 2012-04-17
Publication date: 2019-06-14
Anticipated expiration: 2032-04-17
Also published as: CN107881043B9; CN103608448A; CN113004991A; CN108559679B; CN108559679A; WO2012157851A9; CN107828567A; CN107881043B; CN103608448B; CN107881043A; WO2012157851A3; CN106978264B; CN108085146A; WO2012157851A2; CN108085146B; CN106978264A

Abstract

The present invention is provided to the piece of washing, can completely dissolve in water and after wash without removal.In addition, the piece for washing has good clean-up performance, using simply, will not bring inconvenience in use with determining storage stability and to user.The piece for washing of the invention is prepared by using polyvinyl alcohol polymer/copolymer, specific principal surfactant and optional cosurfactant (preferred nonionic surfactants, more preferable LA7/LA9).

Description

Piece for washing

The application is the divisional application of the Chinese patent application application No. is 201280029267.2, and original application is 2012 PCT International Application Serial No. PCT/the KR2012/002916 submitted April 17 enters the Shen of National Phase in China on December 13rd, 2013 Please.

Technical field

This disclosure relates to be placed in washing machine and in the detergent wherein used.More particularly, present disclosure It is related to piece type or membranous type detergent, is formulated different from general powder or liquid detergent.

This application claims the South Korea patent application No.10-2011- submitted on May 13rd, 2011 in Republic of Korea 0045255, the South Korea patent application No.10-2011-0045256 that is submitted on May 13rd, 2011 in Republic of Korea, in 2011 The South Korea patent application No.10-2011-0045257 that is submitted in Republic of Korea on May 13, on December 9th, 2011 in great Han The South Korea patent application No.10-2011-0132080 of the Republic of China's submission, the South Korea submitted on December 9th, 2011 in Republic of Korea The priority of patent application No.10-2011-0132083, during the disclosure is incorporated herein by reference.

Background technique

Use powder detergent or liquid detergent as being placed in washing machine and wash what is wherein used always so far Wash agent.However, they the shortcomings that are, liquid detergent is relatively heavy, and powder detergent is easy to spread.Therefore, to novel The demand of detergent constantly increases.

In order to solve these problems, United States Patent (USP) No.4,605,509 disclose liquid-type detergent component and fabric is soft Agent is encapsulated in the technology in water-solubility membrane sealer.However, when using water-soluble polymer films to encapsulate them respectively When, during storage or in transport, sealer may rupture and product leakage content.In addition, table of the active component from film Face exudation, causes the storage stability of product to substantially reduce.In addition, although devise the water-solubility membrane as potting object with Ensure that content resists the stability and persistence of moisture in air, but needs the considerable time at low temperature to dissolve this Water-solubility membrane, and the water-solubility membrane even endless fully dissolved, lead to the residual of film residue.

In addition, although developed by adsorbed on water-insoluble suction sheet liquid detergent come using for washing The piece washed, still, this shortcomings that is to have to remove the water-insoluble suction sheet after washing.

Summary of the invention

Technical problem

Therefore, this disclosure relates to provide for the laundry sheet used in washing machine, in washing process completely Dissolution, with excellent clean-up performance, easily fabricated and ensure storage stability.

Technical solution

In order to realize the purpose of present disclosure, provides by using piece formation polymer, lives for the surface of washing Property the manufactures such as agent the piece for washing,

Wherein i) piece forms polymer is polyvinyl alcohol or the copolymer based on polyvinyl alcohol, and

It ii is) the non-aromatic surface work for not conforming to ethylene oxide group in the structure for the surfactant of cleaning action Property agent, it is therefore preferable to the alkyl sulfate with 8 to 18 carbon atoms, more preferably lauryl sulfate.

The salt of alkyl sulfate including lauryl sulfate is metal alkyl salt, preferably sodium salt or sylvite, most preferably For sodium salt.

Present disclosure is based on following unexpected surprising discovery: when using polyvinyl alcohol or being total to based on polyvinyl alcohol Polymers as washing piece substrate when, astoundingly, numerous surfactants (nonionic surfactant, from Sub- surfactant, amphoteric surfactant etc.) among, in the purpose of present disclosure, film forming, clean-up performance, stability Etc., the surfactant of specific structure is preferred, and among them, particularly, in fact it is highly preferred that has 8 to 18 The alkali metal alkyl sulfates of carbon atom, more preferable lauryl sulfate alkali metal salt (most preferably NaLS).

Having the feature that (1) according to the piece for washing of present disclosure, it is easy to dissolve in water at low temperature, thus Excellent clean-up performance is provided, (2) prevent liquid-type active component from oozing out from piece, and until being put into washing machine, (3) have foot With the tensile strength for preventing it from rupturing when in use, and flexibility is shown, the absorption of (4) due to resisting ambient moisture, With distributional stability, and (5) show excellent clean-up performance.

According in piece of the present disclosure for washing, in multiple polymers it is highly preferred using polyvinyl alcohol or Based on the copolymer of polyvinyl alcohol as the substrate for being used to form the piece for washing, the multiple polymers are for example, gelatin, fruit Glue, glucan, hyaluronic acid, ossein, agar, acacia gum, Acacia rubber, alginic acid, sodium alginate, Methyl cellulose Element, ethyl cellulose, hydroxyethyl cellulose, sodium carboxymethylcellulose, starch, dextrin, carboxymethyl starch, polyvinylpyrrolidine Ketone, polyethylene methacrylate, polyacrylic acid, polyethylene oxide etc..

That is, being different from other film-forming components, polyvinyl alcohol or the copolymer based on polyvinyl alcohol can maintain material property, Such as tensile strength of film etc., even if having been embedded in the matrix formed by polyvinyl alcohol or the copolymer based on polyvinyl alcohol big The active component (for example, surfactant) of amount is also such.The present inventors have additionally discovered that polyvinyl alcohol or being total to based on polyvinyl alcohol Polymers shows excellent clean-up performance, or even with standard-sized aqueous tissue also in this way, because the poly- second of per unit area Enol is a large amount of based on that can accommodate within the limitation of the copolymer of polyvinyl alcohol material property required for detergent flakes Surfactant.

In the piece for washing of present disclosure, particularly, polyvinyl alcohol or the copolymer tool based on polyvinyl alcohol There are many molecular weight and saponification degree, when comprehensively consider film forming, dissolubility, easily fabricated property, storage stability, clean-up performance, , it is preferable to use the copolymer that number-average molecular weight is 10,000 to 100,000, more excellent whens program efficiency (viscosity of mixed solution) etc. Choosing using number-average molecular weight be 20,000 to 50,000 copolymer, even more preferably using number-average molecular weight be 20,000 to 30,000 copolymer.

In addition, the preferred saponification degree of polyvinyl alcohol or the copolymer based on polyvinyl alcohol according to the purpose of present disclosure, Whether it is copolymer based on polymer, whether uses alkaline auxiliary lotion etc. and changes.More specifically, when polymer is polyvinyl alcohol And when alkaline auxiliary lotion is not used, preferred saponification degree is 80% to 90%.In addition, when polymer preferably includes according to this The following formula 1 of disclosure or 2 comonomer specific copolymer and when using alkaline auxiliary lotion, saponification degree is preferred It is 60% to 90%, more preferably 70% to 85%, even more preferably 70% to 82%.

Present disclosure also provides the piece for washing comprising polymer, surfactant and alkaline auxiliary lotion,

Wherein, i) polymer be comprising with carboxyl anionic monomer unit the copolymer based on polyvinyl alcohol, with And

Ii) surfactant is the non-aromatic surfactant for being free of ethylene oxide group in the structure, is preferably had There are the alkyl sulfate of 8 to 18 carbon atoms, more preferably lauryl sulfate.

As copolymer, preferably comprises following formula 1 or 2 vinyl alcohol monomer units and anionic monomer unit are total to Polymers, the copolymer being more preferably made of the vinyl alcohol monomer units and anionic monomer unit of following formula 1 or 2.At this It particularly preferably include copolymer of the 0.5mol% to 5mol% anionic monomer unit in the case of kind.

In chemical formula 1 and 2, R₁、R₂And R₃Each independently be H or methyl, and n independently 0 to 3 it is whole Number.

When using polyvinyl alcohol (PVA) as main preparaton, problem is that it may be by as cleaning action component One of alkaline auxiliary lotion solidification.It, can be simultaneously when using the copolymer based on polyvinyl alcohol to replace PVA as at film base material Film forming, the dissolubility of film and the cleaning efficiency of the piece for washing are improved, or even in the presence of alkaline auxiliary lotion also such as This.However, astoundingly, all anionic monomers are all not suitable as the monomer of the copolymer, and only comprising having carboxylic The copolymer of the anionic monomer of base is suitable for the purpose of present disclosure.For example, comprising having-SO₃The anionic monomer of H PVA copolymer is easy to by alkaline auxiliary lotion gelation, as a result, described is difficult to dissolve after being manufactured.

In addition, quite particularly, being used to wash comprising metal alkyl sulfate, alkaline auxiliary lotion and PVA copolymer In the piece washed, the saponification degree of PVA copolymer is preferably 60% to 90%, and more preferably 70% to 85%, even more preferably 70% to 82%.Specifically, when saponification degree is excessively high (for example, being greater than 90%), the piece after manufacturing will appear dissolubility significantly The phenomenon that reduction, and when saponification degree too low (for example, being lower than 60%), the water-soluble of copolymer reduces.It is worth noting that, this A result is different from the result of preferred saponification degree of PVA previously discussed.

Present disclosure is based on following unexpected surprising discovery: using polyvinyl alcohol or being total to based on polyvinyl alcohol In the case where substrate of the polymers as the piece for washing, quite particularly, in various surfactant (non-ionic surface actives Agent, ionic surface active agent, amphoteric surfactant etc.) among, according to the purpose of present disclosure, in film forming, spatter property Can, stability etc. highly preferable use be free of in the structure the non-aromatic surfactant of ethylene oxide group as Principal surfactant.In the structure in the non-aromatic surfactant without ethylene oxide group, particularly, more preferably have There are the alkali metal alkyl sulfates of 8 to 18 carbon atoms, even more preferably lauryl sulfate alkali metal salt, most preferably lauryl sulphur Sour sodium.

Preferably, by the total weight of surfactant, the content of principal surfactant is 50 weight % or more, more Preferably 60 weight % or more, even more preferably 70 weight % or more.

It in the structure include the surfactant of a large amount of ethylene oxide groups (for example, sodium laureth sulfate when using (SLES) or be added to the nonionic surfactant of EO) as main surfactant when, filming performance will be greatly reduced. The attraction structure of water molecules performance of ethylene oxide is considered as that the dissolubility of polyvinyl alcohol in water reduces and for washing Piece material property deterioration the reason of；However, present disclosure is not limited to the theoretical hypothesis.

In addition, in the feelings using the surfactant (for example, linear alkyl benzene sulfonate (LAS)) with aromatic group Under condition, when manufacturing described together with polyvinyl alcohol with the surfactant, filming performance, storage stability etc. drop significantly It is low.When using the surfactant with aromatic group as principal surfactant, and as the poly- second at film base material The poor compatibility of enol or polyvinyl alcohol copolymer, and cannot ensure good film properties.

Therefore, it is highly preferred that in the piece for washing comprising polyvinyl alcohol polymer/copolymer and surfactant In, present disclosure includes being free of the non-aromatic surfactant of ethylene oxide group in the structure as surfactant. In addition, it is highly preferred that the non-aromatic surfactant without ethylene oxide group is to be considered as always containing by surfactant Meter preferably comprises from 50 weight % or more, more preferable 60 weight % or more, the even more preferably master of 70 weight % or more Want surfactant.

The non-aromatic surfactant without ethylene oxide group as principal surfactant can be alkyl sulfide Hydrochlorate RSO₄ ^-M⁺(M is alkali metal, preferably sodium or potassium, more preferably sodium), alpha-alkene sulfonate, alkanesulfonic acid alkali metal salt (preferably sylvite), aliphatic sulfonic methyl esters alkali metal salt (aliphatic ethyl ester sulfonate alkali Metal salt) (preferably sylvite), fatty acid, alkylglycoside etc., in this case, according to multiple mesh of present disclosure , particularly preferred alkyl sulfate, especially astoundingly, according to multiple purposes (including film forming etc.) of present disclosure, More preferable NaLS.Included in the alkyl in the structure of the non-aromatic surfactant without ethylene oxide group Or the carbon atom number of alkane is preferably C8 to C18, the carbon atom number of fatty acid is preferably C8 to C18.

Although not limited to theory, it is recommended that particularly preferably comprising C8 to C22, (preferably C8 to C18, more preferable C12 is extremely C16 the alkyl sulfate surfactant of saturated hydrocarbons), because it can improvement while making tablet preparation have good strength Clean-up performance, this is because its with as polyvinyl alcohol polymer/copolymer superior compatibility at film base material, even if surface The content height of activating agent is also such；However, present disclosure is not limited to the theoretical hypothesis.

If used using according to polyvinyl alcohol polymer/copolymer of present disclosure and the manufacture of specific surfactant In the piece of washing, then the total content of all surface activating agent is preferably based on 30 weight % to 80 of the total weight of piece after drying Weight % (more preferable 40 weight % to 70 weight %), after polyvinyl alcohol polymer/copolymer content is preferably based on drying Piece total weight 20 weight % to 50 weight % (more preferable 30 weight % to 50 weight %, even more preferably 35 weight % To 50 weight %).

As shown in following experimental results, when polyvinyl alcohol polymer/copolymer content is less than 35 weight %, described Material properties (that is, intensity) well, but be based on condition of storage, surface active agent composition be possible to smear (smear) come out, And when polyvinyl alcohol polymer/copolymer content is less than 30 weight %, on described intensity significantly reduces while having Problem is stated, allows to occur using defect.

When the content of surfactant is less than above range, clean-up performance is reduced, and when the content is more than above range When, polyvinyl alcohol polymer/copolymer content relative reduction, therefore, tablet preparation is difficult to manufacture.

Other than polyvinyl alcohol polymer/copolymer and surfactant, the piece for washing can also be comprising hereafter The additive, for example, fluorescent dye, enzyme etc..

Preferably, present disclosure provide comprising polyvinyl alcohol polymer/copolymer and surfactant for washing Piece, wherein the surfactant includes:

(a) principal surfactant, not conform to the non-aromatic surfactant of ethylene oxide group in the structure (more Preferably by chemical formula RSO₄ ^-M⁺What (M is alkali metal, preferably sodium or potassium, most preferably sodium) indicated has 8 to 18 The alkyl sulfate of carbon atom, even more preferably sodium alkyl sulfate, most preferably NaLS), and

(b) cosurfactant is oxygroup ethylization in heptan laruyl alcohol (LA7), nonyl epoxide ethylization alcohol (LA9) or it is mixed Close object.

Present disclosure is also based on following surprising discovery: using polyvinyl alcohol or copolymer based on polyvinyl alcohol and In the piece for washing that surfactant as cleaning action component manufactures, when using in the structure without Oxyranyle The non-aromatic surfactant of group is (more preferably with the alkyl sulfate of 8 to 18 carbon atoms, even more preferably alkylsurfuric acid Sodium, most preferably NaLS) it is used as principal surfactant and uses nonionic surfactant LA7 or LA9 (preferably When LA7) being used as cosurfactant, clean-up performance can be greatly improved while maintaining film forming.When other are with excellent clear When the surfactant of clean performance is mixed with polyvinyl alcohol polymer/copolymer and lauryl sulfate salt system, astoundingly, LA7 or LA9 only reduces film forming and is excellent in low degree or in terms of improving clean-up performance.

Therefore, it is highly preferred that present disclosure offer uses only comprising the lauryl sulphur of (a) as principal surfactant The piece for washing of the surfactant of hydrochlorate (most preferably sodium salt) and (b) LA7 and/or LA9 (preferably LA7) manufacture.

Moreover it is preferred that present disclosure provide for washing piece, it is characterised in that (a) and (b) between mixing ratio Rate (a: b) is 90: 10 to 60: 40, more preferable 80: 20 to 70: 30.

As too many LA7 or LA9 as cosurfactant of mixing, described is penetrated through, and deteriorate piece Property, this can make it be difficult to operate, and as very little LA7 or LA9 as cosurfactant of mixing, clean-up performance It improves not significant.

Therefore, present disclosure, which is provided, use polyvinyl alcohol or copolymer based on polyvinyl alcohol, as major surfaces work Property the alkyl sulfate of the agent and piece for washing of or mixtures thereof LA7, LA9 as cosurfactant manufacture, The alkyl sulfate is by RSO₄ ^-M⁺(M is alkali metal, preferably sodium or potassium, most preferably sodium) (preferably sodium alkyl sulfate, More preferably NaLS) indicate the alkyl with 8 to 18 carbon atoms, wherein by dry after piece total weight, The content of polyvinyl alcohol or the copolymer based on polyvinyl alcohol is 30 weight % to 50 weight %, as principal surfactant The content of sodium alkyl sulfate is 30 weight to 60 weight %, and the content of cosurfactant is 10 weight % to 20 weight %.

In the preparation according to present disclosure, present disclosure be also based on it is following it is surprisingly found that: it is preferably basic The upper starch that do not use is as preparaton (at film base material).When mixing starch and be used as preparaton when (that is, comprising starch as structure One of component at described), the solution suction phenomenon (poor compatibility) of surfactant occurs after the drying, and as starch contains Amount increases, and the intensity of piece decreases.In addition, dissolubility also decreases as content of starch increases.

In this disclosure, " not using " expression substantially, " the dry weight meter of press piece includes 5 weight % or less, preferably 3 weight % or less, more preferable 1 weight % or less, even more preferably zero ".

It can be also comprising following substance not deteriorate film forming, storage surely according to the piece for washing of present disclosure Clean-up performance or filming performance are improved in the range of qualitative, easily fabricated property etc.: fluorescent brightening enzyme is (for example, cellulase, albumen Enzyme etc.), alkaline auxiliary lotion is (for example, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium metasilicate, alkaline sodium silicate, neutral silicic acid Sodium, sodium tripolyphosphate, sodium pyrophosphate, Boratex, zeolite (sodium aluminosilicate), sesquicarbonate, MEA, TEA), disintegrating agent/disintegration Auxiliary agent (for example, starch, cellulose derivative, sodium chloride, citric acid, glycerol, propylene glycol), fabric softener are (for example, quaternary ammonium chlorine Cationic surfactant, the silicone fabric softening component of compound group), bleaching agent (for example, perborate, percarbonate, Superphosphate (superphosphate), two acyls, four acyl peroxide)；Dispersing agent/emulsifier is (for example, polyoxyalkylene Alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene polyoxypropylene block polymer), fungicide/disinfectant (for example, Sodium hypochlorite, hydrogen peroxide, urea peroxide)；Fragrance, preservative, dyestuff, antibacterial agent etc..

It for the thickness of the piece of washing is preferably 1 μm to 1cm, more preferably 5 μm to 0.5cm according to present disclosure, Most preferably 50 μm to 1mm.When the thickness of the dried piece for washing is less than 1 μm, the bearing of active component is not filled Point, film strength is low, it is difficult to desired performance is obtained, and when the thickness of the dried piece for washing is greater than 1cm, dissolution It is slack-off, and clean-up performance deterioration becomes to cause to pay close attention to.

It is highly preferred that by the total weight of piece after drying, present disclosure provides (excellent to 50 weight % comprising 20 weight % Select SLS, the 10 weight % to 20 weight % of PVA, the 30 weight % to 50 weight % of 30 weight % to 50 weight %) LA7/9, The piece type of the enzyme of the fluorescent whitening agent of optionally 1 weight % to 5 weight % and optionally 1 weight % to 5 weight % is water-soluble Laundry detergent compositions.When present disclosure piece type laundry detergent compositions and clothing be put into togerther washing machine and wherein in use, its It is completely dissolved, the process without removal.

In addition to polyvinyl alcohol or the copolymer based on polyvinyl alcohol, principal surfactant and cosurfactant it It outside, can be also comprising so that not interfering the close limit amount of present disclosure purpose according to the piece for washing of present disclosure Another cosurfactant.It can be also comprising containing the surfactant of ethylene oxide group in the structure as another Kind cosurfactant, and laureth sodium sulphate can be used as in the structure containing the table of ethylene oxide group Face activating agent.

Other than polyvinyl alcohol or copolymer and principal surfactant based on polyvinyl alcohol, according to present disclosure The piece for washing can be also comprising so that the aromatic surfactants of the range of present disclosure purpose not be interfered to make For cosurfactant, and alkylbenzene sulfonate can be used as the aromatic surfactants, and preferably, The alkyl of the alkyl benzene sulphonate is the linear alkyl with 8 to 18 carbon atoms.

The piece for washing of present disclosure can be at least to divide two layers of state to use, wherein a synusia is according to this public affairs Content is opened, another synusia is stacked thereon and integrated.

The piece for washing according to present disclosure can be manufactured by following steps: being dissolved in the water of appropriate amount Polyvinyl alcohol or based on the copolymer of polyvinyl alcohol to prepare polyvinyl alcohol polymer/copolymer solution, by the solution with comprising The other components of surfactant etc. mix, and gains are molded as to the piece of uniform thickness, and dry.In addition, according to the disclosure The piece for washing of content is not limited to previous building methods, for example, manufacturing method may include polyethylene dissolving alcohol in water Or before the copolymer based on polyvinyl alcohol, dissolve other components (for example, surfactant).

Present disclosure also based on the fact that it is preferred that further include bubbling process to improve in the disclosure in a manufacturing method The dissolubility of the piece of appearance in water can be provided preferably and be used for when specific gravity is adjusted to 0.6 to 0.9 by bubbling process The piece of washing it is water-soluble, in terms of many advantages.Therefore, present disclosure provides the system included the following steps The method for making the piece for washing: preparation is molten comprising polyvinyl alcohol or copolymer based on polyvinyl alcohol and surfactant Liquid, blistering, and it is dry.That is, present disclosure provides the piece for washing in multiple holes comprising being formed by bubbling process.

Therefore, the additional features that it is 0.6 to 0.9 with above-mentioned technical characteristic and specific gravity that present disclosure, which is also provided, are used for The piece of washing.

Advantageous effect

Present disclosure provides the piece for washing, is completely dissolved and there is no need to remove after wash, has Excellent clean-up performance is simple and easy to use, it is ensured that storage stability, and will not be related in use or cause not Just.

Detailed description of the invention

Fig. 1 is that explanation is stretched based on the piece of polyvinyl alcohol (PVA) molecular weight, PVA content and the water content based on solid The figure for the experimental result that intensity changes.For example, in the value " 03-40-170 " of X-axis, first value indicate the degree of polymerization/100 (that is, 03 indicates that the degree of polymerization is that 300), second value indicates PVA content (weight %), and third value indicates the water content based on solid (weight %).PVA molecular weight is about 50 times of the degree of polymerization.The value of Y-axis indicates tensile strength, unit be kilogram/centimetre² (kgf/cm²)。

Fig. 2 is the change for illustrating to be used as by being replaced with starch tensile strength caused by a part of the PVA of preparaton As a result figure.In the figure, the value of Y-axis indicates tensile strength, unit kgf/cm².In Fig. 2, red boundary line shows Minimum tensile strength required when using piece is 5kgf/cm out²(if it is less than the minimum tensile strength, then piece is easy to tear Or rupture).

Fig. 3 is the figure for illustrating viscosity and changing under conditions of concrete content with the increase of PVA molecular weight.In this feelings Under condition, for every kind of mixed solution, water content is 240% based on solid.

Specific embodiment

Hereinafter, it will be described in the embodiment of present disclosure to help to understand present disclosure.However, it is possible to A variety of changes and variation are made to the embodiment of present disclosure, and it will be understood that scope of the present disclosure be not limited to Following embodiments.The embodiment of present disclosure is that more completely retouching for present disclosure is provided for those skilled in the art It states.

The selection of<embodiment 1>for the suitable polymer of the piece of washing

Using the piece manufactured according to the different polymer of table 1 for washing, the film forming of polymer, dissolubility and It is evaluated in terms of storage stability.As a result it shows in table 1 below.

It is prepared by the dissolution in the distilled water or ethyl alcohol (about 400g) of appropriate amount or the corresponding polymer of suspension 100g Polymer solution or suspension.Polymer solution or suspension are applied with scheduled thickness by using Elcometer film applicator In release film (release film), in 115 DEG C of drying oven dry 10 minutes come manufacture for washing piece (thickness: 0.01cm).Using in the fabrication process with the piece after manufacture in three levels (excellent, good and poor) come evaluate film forming Property.

Following evaluation dissolubility.Manufactured diaphragm is cut into 5cm × 5cm, is then put into about 300ml15 DEG C of pure water In 500ml beaker, at the uniform velocity stir.The time spent in film is decomposed and dissolved completely length is measured, is evaluated in three levels Dissolubility: excellent (be equal to or less than 3 minutes), good (3 minutes to 5 minutes) and poor (greater than 10 minutes).

Table 1

In table 1, ATC indicates [2- (acryloyl group oxygroup) ethyl] trimethyl ammonium chloride；DMAEMA indicates metering system Sour dimethylamino ethyl ester；HEA indicates Hydroxyethyl Acrylate, and HEC indicates hydroxyethyl cellulose；And HPMC indicates hydroxypropyl Methylcellulose.

As shown in table 1, steady for the film forming and obtained sheet dissolubility of the piece of washing, easily fabricated property, storage in manufacture Qualitative aspect, most preferably polyvinyl alcohol are as the polymer for manufacturing the piece for washing.

The evaluation of<embodiment 2>to the effect of the content and molecular weight of PVA

In addition, as using with the polyvinyl alcohol of various molecular weights and saponification degree evaluation film forming, dissolubility, being easy to make The property made, storage stability, clean-up performance and program efficiency (viscosity of mixed solution) as a result, according to present disclosure mesh , when considering the relationship with content used, the polyvinyl alcohol or polyethylene of preferred number average molecular weight 10,000 to 100,000 Alcohol copolymer, the polymer that more preferable molecular weight is 20,000 to 50,000, even more preferably molecular weight are 20,000 to 30, 000 PVA or its copolymer.In addition, about saponification degree, when unmixed alkaline auxiliary lotion, preferably saponification degree be 80% to 90% polymer, and when using PVA copolymer and mixed-alkali builder, be particularly preferred saponification degree be 60% to The polymer of 90% (more preferable 70% to 85%, even more preferably 70% to 82%).When use saponification degree is than above-mentioned saponification When spending the polymer of lower range, water solubility is reduced, and when the gathering in range more higher than above-mentioned saponification degree using saponification degree When closing object, gel phenomenon occurs.

The experimental result for confirming above disclosure is shown in the following table 3 and 4.Described manufacture and evaluation with implementation The similar mode of example 1 carries out.In this case, casting condition is 1100 μm (coating thickness of mixed solution), and dry Condition is 115 DEG C and 15 minutes.Membrane material characteristic (" surface after dry ") including shift index etc. is scored and commented Valence.For example, 1 point indicates in addition to there is situation no abnormal on the external film of residual on surface, and 3 points indicate on the surface of the film Phenomenon of phase separation has occurred, and still there are also remain on surface.The evaluation criterion of dissolubility and tensile strength such as the following table 2 Shown in.

Table 2

In the case where change has occurred in the content of polymer, by supplement or reduce surfactant (SLS, LA7) come Total solid (PVA, SLS, LA7 and other) content is adjusted to 100%, other components (fluorescent whitening agent, enzyme, fragrance etc.) Content is fixed as 5 weight %.Use the PVA of 40 weight %, the SLS of 45 weight %, the LA7 of 10 weight % and 5 weight % Other components are as basic recipe (formula No.1).In table 3, the content of PVA indicates that PVA accounts for total solid in addition to water Weight %, water content are indicated as the weight % for preparing mixed solution Shi Shuizhan total weight of solids.That is, in formula No.1,40% PVA content indicate in total solid include 40 weight % PVA because 63% water content means for manufacturing piece It include 37% solid and 63% water in mixed solution, it is assumed that solid content is 100, then water content is about 170.

Table 3

Table 4

* in formula No.13, drying time increases by two minutes.

As Table 3 and Table 4, in the case where the number-average molecular weight of PVA is less than or equal to about 15 000, described Intensity is low, and the solution suction phenomenon (poor compatibility) of surfactant occurs after drying.In order to solve this problem, increase in piece The content of PVA is to improve the formability and intensity of piece, but the content due to reducing active component, so clean-up performance It reduces.

Meanwhile as the increase of molecular weight, the surface stabilization (compatibility improvement) of piece and the intensity of piece improve.Cause This, molecular weight is higher, more it is advantageously ensured that guaranteeing the formability of piece under low PVA content；However, sticking due to mixed solution Du Taigao, so being substantially difficult to ensure the program efficiency suitable for mass production.Meanwhile the content of water can be increased to change Into this problem (that is, reducing viscosity), but this can be related to the significant decrease of yield.

Therefore, as a result, considering piece intensity and the compatibility with cleaning action component, PVA's or its copolymer used Number-average molecular weight is preferably 20,000 or higher.In addition, with predetermined PVA content (about 30%) and predetermined water content (base In 240 weight % of solid) in the case where, it is contemplated that manufacturing process, 5,000cps or lower be it is appropriate, therefore, PVA or it is total The number-average molecular weight of polymers is preferably 5,000 or smaller, more preferably 30,000 or smaller.

It is related to this, when its for using the PVA of 30 weight %, the SLS of 52 weight %, the LA7 of 13 weight % and 5 weight % His component, and based on the solid piece of 100 parts by weight, using the water of 240 parts by weight come when manufacturing piece, measurement with PVA point Son amount increases and the viscosity of the polymer solution of variation, result are shown in table 3.Polymer used is molten in the fabrication process The viscosity of liquid is too high or too low to be all not preferred, the viscosity of polymer solution of the discovery comprising component described in present disclosure from About 50,000 molecular weight starts to improve rapidly.

As reference, the piece tensile strength based on molecular weight, PVA content and the water content based on solid is shown in Fig. 1 The measurement result of change.According to the purposes of piece, 5kgf/cm is needed²Or it is bigger (when tensile strength is 5kgf/cm²Or more hour, it Be easy to tear or rupture) minimum, by 10kgf/cm²Or it is determined as good level more greatly, according to tensile strength, such as preferably 05-40-170 formula, 10-40-170 formula, 15-30-200 formula, 10-40-200 formula, 15-40-240 formula, 10-30- 200 formulas and 10-35-200 formula.

<the evaluation of the selection of embodiment 3>principal surfactant

Piece according to component and the content manufacture listed in table 5 for washing, film forming and cleaning to manufactured piece Performance is compared evaluation

Table 5

Number	Component	Content (unit: %)
			1	Polyvinyl alcohol (PVA)	40%
2	The surfactant of table 3	55%
			3	Fluorescent whitening agent	2%
4	Enzyme	1.5%
			5	Fragrance and other	1.5%

Specifically, prepare PVA solution by following: be put into 630g distilled water 145g PVA (saponification degree: 86.5%, average degree of polymerization: 500), 80 DEG C at dissolve 2 hour.It is molten that the other components of table 5 are added to prepared PVA Liquid is mixed with mechanical agitator.Mixed solution is applied to scheduled thickness by release by using Elcometer film applicator Film, the dry 10 minutes PVA films using manufacture comprising the surfactant as cleaning component in 115 DEG C of drying oven.

The evaluation result of film forming and clean-up performance based on surfactant types is shown in table 6.With with 1 phase of embodiment Same method is based on (excellent, good and poor) the evaluation film forming of three levels.Clean-up performance is evaluated by method identified below, 60% or higher cleaning capacity based on the fabric (Japan) made dirty are determined as it is excellent, 50% to 59% be it is good, 50% Or lower is poor.

Specifically, cleaning capacity is evaluated using the washing machine of the same terms, in this case, is carried out using tap water Rinsing.In addition, wash temperature is cold water identical with the condition used at home, using the wet fabric artificially made dirty (by day This laundry scientific institution manufacture) and fabric (EMPA 116) through protein contamination as being used for making dirty for detergency evaluation Fabric.Furthermore, it is possible to be evaluated under conditions of the fabric made dirty belongs to cotton T-shirt.In addition, using 16 having a size of 5cm The fabric of × 5cm made dirty is compared evaluation by statistical method.In this case, using colour difference meter before washing The WB value of the whitness index of the fabric made dirty is indicated with measurement after washing.It is used to wash by what is manufactured in the embodiment above Piece be cut into the size of 20cm × 15cm, the detergent for using two panels to cut.It, will in embodiment when starting to wash clothing The piece for washing of manufacture is put into togerther in washing machine with the fabric made dirty respectively, in the standardization program (washing 20 of washing machine Minute, rinsing twice) and medium water level under conditions of washed, after dewatering by the fabric made dirty have stabilization Temperature and humidity room (25 DEG C, 20%RH) in a dry week, ironing uses same colorimeter measurement WB value.It will As a result the Kubelka-Munk equation that acquired results substitution is expressed as formula 2 is shown in table 6 with calculating cleaning capacity.

Equation 1

In equation 1, Rs indicates that the surface reflectivity for the fabric made dirty, Rc indicate the fabric made dirty after the washing process Surface reflectivity and Ro indicate White cotton fabric surface reflectivity.

Table 6

As shown in table 6, very astoundingly, when using polyvinyl alcohol as polymeric substrate, only lauryl Sodium sulphate (SLS) is excellent in terms of film forming, and other for washing surfactants be in terms of film forming it is good or Difference.For example, surfactant LAS, SLES and MEA are subjected to mutually separating in the fabrication process, there is low and PVA compatibility, institute The piece of manufacture has stickiness or frangible, therefore improper in terms of the storage stability of manufactured piece and easily operated property.

<the evaluation of the selection of embodiment 4>cosurfactant

NaLS is used as principal surfactant and uses a variety of nonionic surfactants as auxiliary Cosurfactant manufactures a variety of pieces for washing according to the formula of table 7, and evaluates these pieces.By with implementation Piece of the similar method of example 3 manufacture for washing.

Table 7

In table 7, PVA⁽¹⁾Indicate the polyvinyl alcohol that saponification degree is 86.5% and average degree of polymerization is 500, SLS⁽²⁾It is right Tinopal CBS-X (Ciba Specialty Chemical) should be used as fluorescent dye in NaLS⁽³⁾。

The above piece for washing manufactured is tested by method identical with embodiment 1 or embodiment 3, based on table 8 Standard evaluates these pieces, is as a result shown in table 9.

The tensile strength of film is evaluated as follows.Test method defers to the test method of ISO 527-3 standard, uses general survey Zwick 1120 is set in trial assembly.Each sample is manufactured with uniform thickness 0.2mm, and is cut into 2 × 10 (cm²), it is held with screw cramp Firmly sample, the distance between clamp maintain 50mm, carry out extension test with 20mm/ minutes speed.It will cannot be born in film The point of time when pulling force and breakage is set as tensile strength, it is contemplated that and it is easy to use, standard is set by the value of table 8.

Table 8

Table 9

As shown in table 9, LA7 and LA9 is comprehensively more living than other non-ionic surfaces in terms of cleaning capacity and material properties Property agent is more preferable, and LA7 is more preferable than LA9 in terms of cleaning capacity.

The effect of the content of the SLS of<embodiment 5>as the principal surfactant and LA7 as cosurfactant Evaluation.

Piece of the manufacture for washing, changes together with the component of table 10 and content be used as principal surfactant at the same time SLS and the LA7 as cosurfactant content.Manufacturing method is same as Example 4.

Table 10

Film forming and the cleaning of the piece for washing thus manufactured are evaluated by evaluation method same as Example 4 As a result performance is shown in table 11.

Table 11

As shown in table 11, when considering film forming and when clean-up performance, the total weight of press piece, preferred SLS content is excellent 40 weight % to 50 weight % are selected as, and are 5 weight % to 15 weights preferably as the LA7 content of nonionic surfactant Measure %.

<embodiment 6>overall merit

Water-soluble piece is manufactured according to the formula of table 12 and content, and is evaluated in many aspects.Manufacturing method and implementation Example 4 is identical.

Table 12

In table 12, uses the PVA that saponification degree is 86.5% and average degree of polymerization is 500 as PVA, use polyoxy second Allylic alkylation ether LA7 indicates alpha-alkene sulfonate, uses Tinopal CBS-X (Ciba as nonionic surfactant, AOS Specialty Chemical) it is used as fluorescent dye.

The evaluation of flakiness

Based on following standard, the water-soluble piece manufactured in above-described embodiment and comparative example is evaluated by macroscopic observation and is washed The formability of agent is washed, is as a result shown in table 13.

◎: tablet preparation is flexible and excellent, no smear phenomenon.

Zero: tablet preparation is flexible, but has liquid component slightly smear comes out.

△: piece is flexible insufficient, and has slight smear phenomenon.

×: not formed tablet preparation, and there are a large amount of liquid component smear to come out.

Table 13

As shown in table 13, it is found that the flakiness of embodiment a, b, c, d, k and l are excellent, with non-ionic surface active The content of agent and SLES increase, and film forming significantly reduces.

The evaluation of dissolubility and tensile strength

Tested by method same as Example 4 manufactured in above-described embodiment and comparative example for washing Piece, and evaluate its dissolubility and tensile strength.As a result it is shown in table 14.

Table 14

In the case where comparative example a and c, not formed tablet preparation, therefore it is unable to measure dissolubility and tensile strength.

As shown in table 14, embodiment a, b, c, d, k and l is especially excellent in dissolubility and two aspect of tensile strength.

The evaluation of cleaning capacity

The cleaning capacity of the piece for washing manufactured in above-described embodiment and comparative example is evaluated, described can pass through Following methods manufacture (replaces water soluble detergent piece to come evaluation comparison example a and c) using same amount of active component mixed solution.

Specifically, cleaning capacity is evaluated using the washing machine of the same terms, in this case, is carried out using tap water Rinsing.In addition, wash temperature is cold water identical with the condition used at home, the wet fabric (Japan artificially made dirty is used The manufacture of laundry scientific institution) and fabric (EMPA 116) through protein contamination as evaluating making dirty for detergency evaluation Fabric.In addition, being evaluated under conditions of the fabric made dirty belongs to cotton T-shirt.In addition, using 16 having a size of 5cm × The fabric of 5cm made dirty is compared evaluation by statistical method.In this case, using colour difference meter before washing and Measurement indicates the WB value of the whitness index of the fabric made dirty after washing.By manufacture in the embodiment above be used for wash Piece cuts into the size of 20cm × 15cm, the detergent cut using two panels.When starting to wash clothing, by be used to wash Piece and detergent are put into togerther in washing machine with the fabric made dirty, in standardization program (washing 20 minutes, the rinsing two of washing machine It is secondary) and medium water level under conditions of washed, and after dewatering, in the room (25 with stable temperature and humidity DEG C, 20%RH) in a dry week, then ironing uses same colorimeter measurement W_BValue.Acquired results are substituted into and implemented As a result the identical Kubelka-Munk equation of example 3 is shown with calculating cleaning capacity in table 15.

Table 15

As shown in table 15, embodiment a, b, c, d, k with flakiness appropriate, dissolubility and tensile strength with And in l, the polyoxyethylene alkyl ether comprising 15 weight % shows best clear as the embodiment d of nonionic surfactant Clean performance.

<the evaluation (hygroscopicity) of embodiment 7>stability

The stability for evaluating the piece for washing manufactured in the embodiment d of embodiment 6, as a result shows in table 16.

Table 16

The initial dried residue of piece is 95 weight %, and water content is 5 weight %, and drying makes after ten minutes at 105 DEG C With the residue that the measurement of Halogen moisture analyser is dry.

As shown in table 16, although product is water-soluble piece detergent, (it is included in high temperature and height under numerous conditions Under the conditions of the rainy season of humidity) ensure stability as product.

The evaluation used of<embodiment 8>PVA copolymer

Piece according to the formula manufacture of table 17 for washing, manufacturing method are same as Example 4.

Table 17

In table 17, PVA⁽¹⁾It indicates the polyvinyl alcohol that saponification degree is 86.5% and average degree of polymerization is 500, uses second Enol (98mol%, saponification degree: about 77mol%)-methacrylic acid (2mol%) copolymer is as PVA copolymer⁽²⁾, SLS⁽³⁾ Corresponding to NaLS, use sodium carbonate (soda) as builder⁽⁴⁾, use Tinopal CBS-X (Ciba Specialty Chemical) it is used as fluorescent dye⁽⁵⁾。

By the manufactured piece for washing of method evaluation same as Example 4, as a result shown in table 18.

Table 18

As shown in Table 18, when adding builder to PVA, PVA solidification, so that dissolubility and material property are significantly bad Change, due to this insoluble component, clean-up performance is also without the effect of generation builder.However, when using PVA copolymer, There is no solidification being added to builder, and clean-up performance is improved due to builder, be greater than when viscosity or Equal to it is scheduled horizontal when, the effect due to caused by the amount of surfactant is with respect to reduction clean-up performance reduce due to It offsets.In addition, the intensity of piece is reduced due to a large amount of builders in film when the amount of builder is greater than or equal to 7.5%.

<embodiment 9>adds the evaluation of the effect of starch

Piece is manufactured according to the formula of table 19, uses or mixtures thereof PVA, starch as preparaton to evaluate addition starch Effect.It is evaluated with method identical with the experiment of embodiment 2, synthesis result is shown in table 20, and table 20 is shown in FIG. 2 Result in tensile strength.

Table 19

	Raw material	Content
			1	Preparaton	40%
2	SLS	45%
			3	LA7	10%
4	Other	5%
				Water	170 (the piece solids relative to 100)

Table 20

As shown in table 20 and Fig. 2, when mixing starch and together as preparaton (including component of the starch as piece) When, solution suction phenomenon (poor compatibility) occurs for surfactant after the drying, and as content of starch increases, and the intensity of piece drops It is low.In addition, with the increase of content of starch, dissolubility is also reduced.Thus, it is found that in manufacture according to present disclosure for washing Starch is not preferably used when the piece washed.In order to overcome the problems, such as compatibility and tensile strength, exists to have to increase in piece and prepare The defect of agent content (being greater than or equal to 50%), in order to improve dissolubility, have the defects that have to gelling starches first.

The following contents corresponds to the original claims in parent application, is now incorporated to this as part of the specification Place:

1. a kind of piece for washing, uses polyvinyl alcohol or made based on the copolymer of polyvinyl alcohol as polymer It makes and it includes surfactant, wherein the surfactant is free of ethylene oxide group in the structure and is non-aromatic Race.

2. the piece according to item 1 for washing, wherein described be free of ethylene oxide group in the structure and be non- Aromatic surfactant is by RSO₄ ^-M⁺Alkyl sulfate, the alpha-alkene sulfonate, alkanesulfonic acid of (M is alkali metal) expression Or mixtures thereof alkali metal salt, aliphatic methyl esters sulfonic acid alkali metal salts, fatty acid, alkylglycoside.

3. the piece according to item 1 for washing, wherein the surfactant includes having 8 to 18 carbon atoms Alkali metal alkyl sulfates.

4. the piece according to item 3 for washing, wherein the alkali metal alkyl sulfates are NaLSs.

5. the piece according to item 1 for washing, wherein described be free of ethylene oxide group in the structure and be non- Aromatic surfactant is the main table of 50 weight % that content is the total content based on the surfactant or more Face activating agent.

6. the piece according to item 3 for washing, wherein it is based on described that the alkali metal alkyl sulfates, which are contents, The principal surfactant of 50 weight % of the total content of surfactant or more.

7. the piece according to item 5 or 6 for washing, wherein the content of the principal surfactant is based on described 60 weight % of the total content of surfactant or more.

8. the piece according to item 1 for washing, wherein the total content of the surfactant is based on described The 40 weight % to 70 weight % of total weight, and the total content of the polyvinyl alcohol or the copolymer based on polyvinyl alcohol For the 30 weight % to 50 weight % of the total weight based on described.

9. the piece according to item 1 for washing, wherein the polyvinyl alcohol or the copolymerization based on polyvinyl alcohol The number-average molecular weight of object is 20,000 to 50,000.

10. the piece according to item 1 for washing, wherein the polymer is polyvinyl alcohol, the polyvinyl alcohol Saponification degree is 80% to 90%.

11. the piece according to item 1 for washing, wherein described also other than the principal surfactant Cosurfactant is used as comprising or mixtures thereof oxygroup ethylization in heptan laruyl alcohol (LA7), nonyl epoxide ethylization laruyl alcohol (LA9) Agent.

12. the piece according to item 11 for washing, wherein the principal surfactant and the auxiliary surface are living Property agent mixed weight ratio (principal surfactant: the cosurfactant) be 90: 10 to 60: 40.

13. the piece according to item 11 for washing, wherein the polyvinyl alcohol described in described or described based on poly- The total content of the copolymer of vinyl alcohol is the 30 weight % to 50 weight % based on described total weight after drying, includes the moon For osmanthus base alkali metal persulfates as the principal surfactant, content is 30 weight % to 60 weight %, the supplementary table The total content of face activating agent is 10 weight % to 20 weight %.

14. the piece according to item 1 for washing, wherein the piece for washing is by the inclusion of via bubbling process The hole of formation and have improved water solubility.

15. the piece according to item 14 for washing, wherein the specific gravity of the piece for washing is 0.6 to 0.9.

16. a kind of piece for washing includes polymer, surfactant and alkaline auxiliary lotion, wherein the polymer It is the copolymer based on polyvinyl alcohol comprising the monomeric unit with carboxyl, the surfactant is free of epoxy in the structure Ethane group and for non-aromatic.

17. the piece according to item 16 for washing, wherein the copolymer includes the ethylene of following formula 1 or 2 The content of alcohol unit and anionic monomer unit, the anionic monomer unit is 0.5mol% to 5mol%:

Wherein, R₁、R₂And R₃Each independently be H or methyl, and n is independently 0 to 3 integer.

18. the piece according to item 16 for washing, wherein described be free of ethylene oxide group in the structure and be The surfactant of non-aromatic is by RSO₄ ^-M⁺Alkyl sulfate, the alpha-alkene sulfonate, alkane sulphur of (M is alkali metal) expression Or mixtures thereof acid alkali metal salt, aliphatic methyl esters sulfonic acid alkali metal salts, fatty acid, alkylglycoside.

19. the piece according to item 16 for washing, wherein the surfactant includes having 8 to 18 carbon atoms Alkali metal alkyl sulfates.

20. the piece according to item 19 for washing, wherein the alkali metal alkyl sulfates are NaLSs.

21. the piece according to item 19 for washing, wherein the alkali metal alkyl sulfates are contents for based on institute State the principal surfactant of 60 weight % of the total content of surfactant or more.

22. the piece according to item 16 for washing, wherein the total content of the surfactant is based on described Total weight the weight % of 40 weight % to 70, the total content of the copolymer based on polyvinyl alcohol is total based on described The 30 weight % to 50 weight % of weight.

23. the piece according to item 16 for washing, wherein the equal molecule of number of the copolymer based on polyvinyl alcohol Amount is 20,000 to 50,000.

24. the piece according to item 16 for washing, wherein the saponification degree of the copolymer based on polyvinyl alcohol is 60% to 85%.

25. the piece according to item 16 for washing, wherein described also other than the principal surfactant Cosurfactant is used as comprising or mixtures thereof oxygroup ethylization in heptan laruyl alcohol (LA7), nonyl epoxide ethylization laruyl alcohol (LA9) Agent.

26. the piece according to item 16 for washing, wherein the piece for washing was by the inclusion of via blistering Journey formed hole and have improved water solubility.

27. the piece according to item 26 for washing, wherein the specific gravity of the piece for washing is 0.6 to 0.9.

28. the piece according to item 1 or 16 for washing, wherein not starch-containing in the chip base sheet.

29. a kind of method of piece of manufacture for washing, comprising:

Solution of the preparation comprising polyvinyl alcohol or copolymer and surfactant based on polyvinyl alcohol；

It blisters to the solution；And

The dry solution.

30. according to method described in item 29, wherein the surfactant includes the alkyl sulfide with 8 to 18 carbon atoms Acid alkali metal salt.

Claims

1. a kind of piece for washing, uses polyvinyl alcohol or manufactured simultaneously based on the copolymer of polyvinyl alcohol as polymer And it includes surfactants, wherein the surfactant includes the alkali metal alkyl sulfates with 8 to 18 carbon atoms, And other than the alkali metal alkyl sulfates as surfactant, described also includes oxygroup in heptan ethylization laurel Or mixtures thereof alcohol (LA7), nonyl epoxide ethylization laruyl alcohol (LA9) are used as cosurfactant,

Wherein the piece for washing includes the surfactant of embedding in the polymer matrix, by by the polymerization Object and the surfactant mix to be formed.

2. the piece according to claim 1 for washing, wherein the alkali metal alkyl sulfates are NaLSs.

3. the piece according to claim 1 for washing, wherein the alkali metal alkyl sulfates are contents for based on institute State the principal surfactant of 50 weight % of the total content of surfactant or more.

4. the piece according to claim 3 for washing, wherein the content of the principal surfactant is based on described 60 weight % of the total content of surfactant or more.

5. the piece according to claim 1 for washing, wherein the total content of the surfactant is based on described Total weight 40 weight % to 70 weight %, and the polyvinyl alcohol or the copolymer based on polyvinyl alcohol always contain Amount is the 30 weight % to 50 weight % of the total weight based on described.

6. the piece according to claim 1 for washing, wherein the polyvinyl alcohol or being total to based on polyvinyl alcohol The number-average molecular weight of polymers is 20,000 to 50,000.

7. the piece according to claim 6 for washing, wherein the polyvinyl alcohol or being total to based on polyvinyl alcohol The number-average molecular weight of polymers is 20,000 to 30,000.

8. the piece according to claim 1 for washing, wherein the polymer is polyvinyl alcohol, the polyvinyl alcohol Saponification degree is 80% to 90%.

9. the piece according to claim 1 for washing, wherein the cosurfactant is oxygroup in the heptan ethylization moon Cinnamic alcohol (LA7).

10. the piece according to claim 1 for washing, wherein the alkali metal alkyl sulfates and the auxiliary surface The mixed weight ratio of activating agent is 90:10 to 60:40.

11. the piece according to claim 5 for washing, wherein the polyvinyl alcohol described in described or described based on poly- The total content of the copolymer of vinyl alcohol is the 30 weight % based on described total weight after drying to 50 weight %, as master Want the content of the alkali metal alkyl sulfates of surfactant for 30 weight % to 60 weight %, the cosurfactant The total content of agent is 10 weight % to 20 weight %.

12. the piece according to any one of claim 1 to 11 for washing, wherein the piece for washing includes Bubble.

13. the piece according to any one of claim 1 to 11 for washing, wherein the specific gravity of the piece for washing It is 0.6 to 0.9.

14. a kind of piece for washing includes polymer, surfactant and alkaline auxiliary lotion, wherein the polymer is packet The copolymer based on polyvinyl alcohol containing the monomeric unit with carboxyl, the surfactant include having 8 to 18 carbon originals The alkali metal alkyl sulfates of son, and other than the alkali metal alkyl sulfates as surfactant, described It is also living as auxiliary surface comprising or mixtures thereof oxygroup in heptan ethylization laruyl alcohol (LA7), nonyl epoxide ethylization laruyl alcohol (LA9) Property agent,

15. the piece according to claim 14 for washing, wherein the copolymer includes the second of following formula 1 or 2 The content of alcohol units and anionic monomer unit, the anionic monomer unit is 0.5mol% to 5mol%:

Wherein in the chemical formula 1 and 2, R₁、R₂And R₃Each independently be H or methyl, and n is independently 0 to 3 Integer.

16. the piece according to claim 14 for washing, wherein the alkali metal alkyl sulfates are lauryl sulfates Sodium.

17. it is according to claim 14 for washing piece, wherein the alkali metal alkyl sulfates be content be based on The principal surfactant of 60 weight % of the total content of the surfactant or more.

18. the piece according to claim 14 for washing, wherein the total content of the surfactant is based on described The weight % of 40 weight % to 70 of the total weight of piece, the total content of the copolymer based on polyvinyl alcohol are based on described The 30 weight % to 50 weight % of total weight.

19. the piece according to claim 14 for washing, wherein the number of the copolymer based on polyvinyl alcohol is divided equally Son amount is 20,000 to 50,000.

20. the piece according to claim 14 for washing, wherein the saponification degree of the copolymer of the polyvinyl alcohol is 60% to 85%.

21. the piece described in any one of 4 to 20 for washing according to claim 1, wherein the piece for washing includes Bubble.

22. the piece described in any one of 4 to 20 for washing according to claim 1, wherein the ratio of the piece for washing Weight is 0.6 to 0.9.

23. according to claim 1 to the piece described in any one of 11 and 14 to 20 for washing, wherein described includes to press institute State the starch of the 0 weight % of dry weight meter to 5 weight % of piece.

24. a kind of method of piece of manufacture for washing, comprising:

It blisters to the solution；And

The dry solution,

Wherein the surfactant includes the alkali metal alkyl sulfates with 8 to 18 carbon atoms, and as supplementary table Or mixtures thereof oxygroup ethylization in the heptan laruyl alcohol (LA7) of face activating agent, nonyl epoxide ethylization laruyl alcohol (LA9),