CN106978264A

CN106978264A - Piece for washing

Info

Publication number: CN106978264A
Application number: CN201610879699.2A
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: 2017-07-25
Anticipated expiration: 2032-04-17
Also published as: CN107881043B; CN108085146B; CN107881043A; CN107828567A; CN103608448B; WO2012157851A2; WO2012157851A9; CN107881043B9; CN108559679A; CN107828567B; WO2012157851A3; CN108559679B; CN106978264B; CN113004991A; CN103608448A; CN108085146A

Abstract

The present invention is provided to the piece of washing, it can be dissolved completely in water and after wash without removing.In addition, the piece for being used to wash has good clean-up performance, will not brought inconvenience in use using the simple, storage stability with determination and to user.The piece for being used to wash of the present invention is prepared by using polyvinyl alcohol polymer/copolymer, specific principal surfactant and optional cosurfactant (preferred nonionic surfactants, more preferably LA7/LA9).

Description

Piece for washing

The application is Application No. 201280029267.2, the division Shen of the application of entitled " being used for the piece washed " Please, the parent application is that the PCT application PCT/KR2012/002916 submitted on April 17th, 2012 enters National Phase in China Application.

Technical field

Present disclosure is related to the detergent for being placed in washing machine and using wherein.More particularly, present disclosure It is related to piece type or membranous type detergent, its formula is different from general powder or liquid detergent.

This application claims the korean patent application No.10-2011- submitted on May 13rd, 2011 in Republic of Korea 0045255th, the korean patent application No.10-2011-0045256 that is submitted on May 13rd, 2011 in Republic of Korea, in 2011 The korean patent application No.10-2011-0045257 that is submitted in Republic of Korea on May 13, on December 9th, 2011 in great Han The korean 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 Patent application No.10-2011-0132083 priority, the disclosure of which is herein incorporated by reference.

Background technology

So far always using powder detergent or liquid detergent as being placed in washing machine and washing of using wherein Wash agent.However, they the disadvantage is that, liquid detergent is relatively heavy, and powder detergent is easy to spread.Therefore, to new The demand of detergent constantly increases.

In order to solve these problems, United States Patent (USP) No.4,605,509 disclose that liquid-type detergent component and fabric is soft Agent is encapsulated in the technology in water-solubility membrane sealer.They are encapsulated respectively using water-soluble polymer films however, working as When, during storing or in transport, sealer may rupture and product leakage content.In addition, table of the active component from film Face is oozed out, and causes the storage stability of product to substantially reduce.Although in addition, devise the water-solubility membrane as potting thing with Ensure that content resists the stability and persistence of moisture in air, but need the considerable time to dissolve this at low temperature Water-solubility membrane, and the water-solubility membrane is not completely dissolved even, causes the residual of film residue.

Although in addition, developed by water-insoluble suction sheet adsorptive liquid detergent come use be used for wash The piece washed, still, the shortcoming of this are to have to remove the water-insoluble suction sheet after washing.

The content of the invention

Technical problem

Therefore, present disclosure is related to the laundry sheet for providing and being used for being used in washing machine, and it is complete in washing process Dissolving, with excellent clean-up performance, easily fabricated and ensure storage stability.

Technical solution

In order to realize the purpose of present disclosure, there is provided by using piece formation polymer, the surface work for washing Property the manufacture such as agent the piece for being used to wash,

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

Ii) surfactant for cleaning action is that the non-aromatic surface without ethylene oxide group is lived in the structure 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 being total to using polyvinyl alcohol or based on polyvinyl alcohol When polymers is as base material for the piece of washing, astoundingly, numerous surfactants (nonionic surfactant, from Sub- surfactant, amphoteric surfactant etc.) among, in the purpose of present disclosure, film forming, clean-up performance, stability In terms of, the surfactant of specific structure is preferred, and among them, especially, in fact it is highly preferred that with 8 to 18 The alkali metal alkyl sulfates of carbon atom, more preferably lauryl sulfate alkali metal salt (most preferably NaLS).

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

According to present disclosure be used for wash piece in, in multiple polymers highly preferred use polyvinyl alcohol or Copolymer based on polyvinyl alcohol is as the base material for forming the piece for washing, and 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, CMS, polyvinylpyrrolidine Ketone, polyethylene methacrylate, polyacrylic acid, PEO etc..

That is, the copolymer different from other film-forming components, polyvinyl alcohol or based on polyvinyl alcohol can maintain material property, It is big even in having been embedded by polyvinyl alcohol or in matrix that the copolymer based on polyvinyl alcohol is formed such as the tensile strength of film 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 It is a large amount of that enol or copolymer based on polyvinyl alcohol can be accommodated within the material property limitation required for detergent flakes Surfactant.

In the piece for being used to wash of present disclosure, especially, polyvinyl alcohol or the copolymer tool based on polyvinyl alcohol Have various molecular weights and saponification number, when consider film forming, dissolubility, easily fabricated property, storage stability, clean-up performance, During program efficiency (viscosity of mixed solution) etc., the copolymer that number-average molecular weight is 10,000 to 100,000 is preferably used, it is more excellent 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 number 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 is changed using alkaline auxiliary lotion etc..More specifically, when polymer is polyvinyl alcohol And when alkaline auxiliary lotion is not used, saponification number preferably is 80% to 90%.In addition, when polymer is preferably to include according to this When the formula 1 below of disclosure or the specific copolymer of 2 comonomer and use alkaline auxiliary lotion, saponification number is preferred For 60% to 90%, more preferably 70% to 85%, even more preferably 70% to 82%.

Present disclosure also provides the piece for being used to wash comprising polymer, surfactant and alkaline auxiliary lotion,

Wherein, i) polymer is the copolymer based on polyvinyl alcohol for including the anionic monomer unit with carboxyl, 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, being total to for formula 1 below or 2 vinyl alcohol monomer units and anionic monomer unit is preferably comprised Polymers, the copolymer being more preferably made up of formula 1 below or 2 vinyl alcohol monomer units and anionic monomer unit.At this In the case of kind, 0.5mol% to 5mol% anionic monomer units copolymer is particularly preferably included.

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., can be simultaneously when using the copolymer based on polyvinyl alcohol to replace PVA as into film base material Improve the cleaning efficiency of film forming, the dissolubility of film and the piece for washing, 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 including has carboxylic The copolymer of the anionic monomer of base is suitable to the purpose of present disclosure.For example, comprising with-SO₃H anionic monomer PVA copolymers are easy to by alkaline auxiliary lotion gelation, as a result, described is difficult to dissolve after being manufactured.

In addition, quite especially, being washed in being used for comprising metal alkyl sulfate, alkaline auxiliary lotion and PVA copolymers In the piece washed, the saponification number of PVA copolymers is preferably 60% to 90%, and more preferably 70% to 85%, even more preferably 70% to 82%.Specifically, when saponification number is too high (for example, more than 90%), the piece after manufacture occurs dissolubility significantly The phenomenon of reduction, and when saponification number too low (for example, less than 60%), the water-soluble reduction of copolymer.It is worth noting that, this Individual result is different from the result of PVA previously discussed preferred saponification number.

Present disclosure is based on following unexpected surprising discovery：In being total to using polyvinyl alcohol or based on polyvinyl alcohol In the case that polymers is as the base material for the piece of washing, quite especially, 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 The non-aromatic surfactant conduct for being free of ethylene oxide group in the structure is highly preferable used in terms of energy, stability Principal surfactant.In the structure in the non-aromatic surfactant without ethylene oxide group, especially, 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 gross weight meter 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.

The surfactant of a large amount of ethylene oxide groups is included in the structure (for example, sodium laureth sulfate when using (SLES) or with the addition of EO nonionic surfactant) as main surfactant when, filming performance can be substantially reduced. The structural behaviour of the attraction hydrone of oxirane is considered as that dissolubility of the polyvinyl alcohol in water is reduced and for washing The material property of piece the reason for deteriorate；However, present disclosure is not restricted to the theory 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 into film base material The poor compatibility of enol or polyvinyl alcohol copolymer, and cannot ensure good film properties.

Therefore, it is highly preferred that including the piece for being used to wash of polyvinyl alcohol polymer/copolymer and surfactant In, present disclosure includes the non-aromatic surfactant without ethylene oxide group in the structure and is used 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 Gauge, preferably comprises from 50 weight % or more, more preferably 60 weight % or more, even more preferably 70 weight % or more master 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 (being preferably sylvite), aliphatic sulfonic methyl esters alkali metal salt (aliphatic ethyl ester sulfonate alkali Metal salt) (be preferably sylvite), aliphatic 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 preferably NaLS.Included in the alkyl in the structure of the non-aromatic surfactant without ethylene oxide group Or the carbon number of alkane is preferably C8 to C18, the carbon number of aliphatic 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 preferably C12 are extremely C16 the alkyl sulfate surfactant of saturated hydrocarbons), because it can be improved while making tablet preparation have good strength Clean-up performance, this is due to itself and the superior compatibility as polyvinyl alcohol polymer/copolymer into film base material, even if surface The content of activating agent is high also such；However, present disclosure is not limited to the theory hypothesis.

If used using polyvinyl alcohol polymer/copolymer according to 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 gross weight of piece after drying Weight % (more preferably 40 weight % to 70 weight %), the content of polyvinyl alcohol polymer/copolymer is preferably based on after drying Piece gross weight 20 weight % to 50 weight % (more preferably 30 weight % to 50 weight %, even more preferably 35 weight % To 50 weight %).

As shown in following experimental results, when the content of polyvinyl alcohol polymer/copolymer is less than 35 weight %, described Material character (that is, intensity) well, but based on condition of storage, surface active agent composition is possible to smear (smear) and come out, And when the content of polyvinyl alcohol polymer/copolymer is less than 30 weight %, the intensity of described is significantly reduced on while having State problem so that defect can be used.

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

In addition to 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 provides being used for comprising polyvinyl alcohol polymer/copolymer and surfactant and washed Piece, wherein the surfactant is included：

(a) principal surfactant, it is to be free of the non-aromatic surfactant of ethylene oxide group (more in the structure Preferably by chemical formula RSO₄ ^-M⁺What (M is alkali metal, preferably sodium or potassium, most preferably sodium) represented has 8 to 18 The alkyl sulfate of carbon atom, even more preferably sodium alkyl sulfate, most preferably NaLS), and

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

Present disclosure is also based on following surprising discovery：Using polyvinyl alcohol or copolymer based on polyvinyl alcohol and In the piece for being used to wash manufactured as the surfactant of cleaning action component, when using in the structure without Oxyranyle Non-aromatic surfactant (alkyl sulfate more preferably with 8 to 18 carbon atoms, even more preferably alkylsurfuric acid of group Sodium, most preferably NaLS) as principal surfactant and using nonionic surfactant LA7 or LA9 (preferably When LA7) as cosurfactant, clean-up performance can be greatly improved while maintaining film forming.When other have it is 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 reduce film forming and show excellent to low degree or in terms of clean-up performance is improved.

Therefore, it is highly preferred that present disclosure, which provides to use, only includes (a) as the lauryl sulphur of principal surfactant The piece for being used to wash of hydrochlorate (most preferably sodium salt) and (b) LA7 and/or LA9 (preferably LA7) surfactant manufacture.

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

As too many LA7 or LA9 as cosurfactant of mixing, it penetrates through described, and deteriorates piece Property, this can make it be difficult to operate, and when mixing very little as LA7 or LA9 of cosurfactant, clean-up performance Improve not notable.

Therefore, present disclosure is provided using polyvinyl alcohol or the copolymer based on polyvinyl alcohol, lived as major surfaces Property agent alkyl sulfate and the piece for being used to wash that is manufactured as LA7, LA9 of cosurfactant or its mixture, The alkyl sulfate is by RSO₄ ^-M⁺(M is alkali metal, preferably sodium or potassium, most preferably sodium) (it is preferably sodium alkyl sulfate, More preferably NaLS) what is represented has the alkyl of 8 to 18 carbon atoms, wherein by the gross weight meter of piece after drying, The content of polyvinyl alcohol or 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 also based on following it is surprisingly found that：It is preferred that basic On be used as preparaton without using starch (into film base material).When mixing starch and as preparaton when (that is, be used as structure comprising starch Into one of described component), the solution suction phenomenon (poor compatibility) of surfactant occurs after the drying, and as starch contains Amount increase, the intensity of piece is decreased.In addition, as content of starch increases, dissolubility is also decreased.

In this disclosure, " substantially without using " expression is " based on the dry weight of piece, comprising 5 weight % or less, preferably 3 weight % or less, more preferably 1 weight % or less, even more preferably zero ".

Film forming, storage can not also deteriorated surely comprising following material according to the piece for being used to wash 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 acid carbonate, sodium metasilicate, alkaline sodium silicate, neutral silicic acid Sodium, sodium tripolyphosphate, sodium pyrophosphate, Boratex, zeolite (sodium aluminosilicate), sesquicarbonate, MEA, TEA), disintegrant/disintegration Auxiliary agent (for example, starch, cellulose derivative, sodium chloride, citric acid, glycerine, propane diols), 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)；Dispersant/emulsifying agent is (for example, polyoxyalkylene Alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene polyoxypropylene block polymer), bactericide/disinfectant (for example, Sodium hypochlorite, hydrogen peroxide, urea peroxide)；Spices, preservative, dyestuff, antiseptic etc..

According to present disclosure be used for wash piece thickness be preferably 1 μm to 1cm, more preferably 5 μm to 0.5cm, Most preferably 50 μm to 1mm.When the thickness through the dry piece for being used to wash is less than 1 μm, the supporting to active component is not filled Point, film strength is low, it is difficult to obtain desired performance, and when the thickness through the dry piece for being used to wash is more than 1cm, dissolving It is slack-off, and clean-up performance deterioration become to cause concern.

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

Except polyvinyl alcohol or the copolymer based on polyvinyl alcohol, principal surfactant and cosurfactant it Outside, can also it be included according to the piece for being used to wash of present disclosure to cause the close limit amount of without prejudice to present disclosure purpose Another cosurfactant.The surfactant for containing ethylene oxide group in the structure can also be included as another Cosurfactant is planted, and laureth sodium sulphate can be used as the table containing ethylene oxide group in the structure Face activating agent.

In addition to polyvinyl alcohol or copolymer and principal surfactant based on polyvinyl alcohol, according to present disclosure Be used for wash piece can also include with cause without prejudice to present disclosure purpose scope aromatic surfactants make For cosurfactant, and alkylbenzenesulfonate 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 being used to wash 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 being used to wash according to present disclosure can be manufactured by following steps：Dissolved in the water of appropriate amount Polyvinyl alcohol or copolymer based on polyvinyl alcohol to prepare polyvinyl alcohol polymer/copolymer solution, by the solution with comprising The other components mixing of surfactant etc., gains is molded as the piece of uniform thickness, and dry.In addition, according to the disclosure The piece for being used to wash of content is not limited to previous building methods, for example, manufacture method can be included in 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 also including bubbling process in a manufacturing method to improve in the disclosure Dissolubility of the piece of appearance in water, when proportion is adjusted into 0.6 to 0.9 by bubbling process, can preferably provide is used for Many advantages of the piece of washing in terms of water-soluble, water-soluble speed.Therefore, present disclosure provides the system comprised the following steps The method for making the piece for washing：Prepare molten comprising polyvinyl alcohol or copolymer based on polyvinyl alcohol and surfactant Liquid, foaming, and dry.That is, present disclosure provides the piece for being used to wash for including multiple holes by bubbling process formation.

Therefore, present disclosure also provides being used for for 0.6 to 0.9 additional features with above-mentioned technical characteristic and proportion The piece of washing.

Favourable effect

Present disclosure provides the piece for washing, and it is completely dissolved and therefore without removing after wash, had Excellent clean-up performance, it is simple and easy to use, it is ensured that storage stability, and will not be related to or cause not in use Just.

Brief description of the drawings

Fig. 1 is that piece of the explanation based on polyvinyl alcohol (PVA) molecular weight, PVA contents and the water content based on solid is stretched The figure for the experimental result that intensity changes.For example, in the value " 03-40-170 " of X-axis, first value represents the degree of polymerization/100 (i.e., 03 represents the degree of polymerization for 300), second value represents PVA contents (weight %), and the 3rd value represents the water content based on solid (weight %).PVA molecular weight is about 50 times of the degree of polymerization.The value of Y-axis represents tensile strength, its unit be kilogram/centimetre² (kgf/cm²)。

Fig. 2 is the change for illustrating to replace by using starch tensile strength caused by a part of the PVA as preparaton As a result figure.In the figure, the value of Y-axis represents tensile strength, and its unit is kgf/cm².In fig. 2, red boundary line shows It is 5kgf/cm to go out required minimum tensile strength when using piece²(if less than the minimum tensile strength, then piece is easily torn Or rupture).

Fig. 3 is to illustrate the figure that viscosity changes 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.

Embodiment

Hereinafter, the embodiment of present disclosure is will be described in help to understand present disclosure.However, it is possible to Embodiment to present disclosure makes a variety of changes and change, and it will be understood that scope of the present disclosure be not limited to Following embodiments.The embodiment of present disclosure is to provide more completely retouching for present disclosure for those skilled in the art State.

<Embodiment 1>Selection for the suitable polymer of the piece of washing

Manufacture the piece for washing using the different polymer according to table 1, the film forming of polymer, dissolubility and Evaluated in terms of storage stability.As a result show in table 1 below.

Prepared by dissolving in the distilled water in appropriate amount or ethanol (about 400g) or the corresponding polymer of suspension 100g Polymer solution or suspension.Polymer solution or suspension are applied with predetermined thickness by using Elcometer films applicator In release film (release film), 10 minutes are dried in 115 DEG C of drying oven to manufacture the piece (thickness for washing： 0.01cm).Using (excellent, good and difference) evaluates film forming in three levels with the piece after manufacture in the fabrication process Property.

It is following to evaluate dissolubility.The diaphragm being made is cut into 5cm × 5cm, then about 300ml15 DEG C of pure water is put into In 500ml beakers, 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 (more than 10 minutes).

Table 1

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

As shown in table 1, it is 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 used as the polymer for manufacturing the piece for washing.

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

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

Show to confirm the experimental result of above disclosure in table 3 below and 4.The manufacture of described and evaluate with implementation The similar mode of example 1 is carried out.In this case, casting condition is 1100 μm (coating thickness of mixed solution), and is dried Condition is 115 DEG C and 15 minutes.Membrane material characteristic (" dried surface ") including shift index etc. is scored and commented Valency.For example, 1 point represents except there is situation no abnormal on the external film of residual on surface, and 3 points represent on the surface of the film It there occurs still there be the situation of residual in phenomenon of phase separation, and surface.The evaluation criterion of dissolubility and tensile strength such as table 2 below Shown in.

Table 2

In the case where the content of polymer there occurs change, 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, spices etc.) Content is fixed as 5 weight %.Use 40 weight % PVA, 45 weight % SLS, 10 weight % LA7 and 5 weight % Other components are used as basic recipe (formula No.1).In table 3, PVA content represents that PVA accounts for total solid in addition to water Weight %, water content represents that when preparing mixed solution water accounts for the weight % of total weight of solids.That is, in formula No.1,40% PVA contents represent to include 40 weight % PVA in total solid because 63% water content means for manufacturing piece Included in mixed solution 37% solid and 63% water, it is assumed that solids content be 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 PVA number-average molecular weight is less than or equal to about 15,000, described Low intensity, the solution suction phenomenon (poor compatibility) that surfactant occurs after drying.In order to solve in the problem, increase piece PVA content is due to the content for reducing active component to improve the formability and intensity of piece, so clean-up performance Reduce.

Meanwhile, with the increase of molecular weight, the surface stabilization (compatibility improvement) of piece and the intensity raising of piece.Cause This, molecular weight is higher, more it is advantageously ensured that ensureing the formability of piece under low PVA contents；However, sticking due to mixed solution Du Taigao, so being substantially difficult to ensure that the program efficiency for being suitable for largely producing.Meanwhile, the content of water can be increased to change Enter this problem (that is, reducing viscosity), but this can be related to significantly reducing for yield.

Therefore, as a result, compatibility in view of piece intensity and 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 contents (about 30%) and predetermined water content (base In the weight % of solid 240) in the case of, it is contemplated that manufacturing process, 5,000cps or lower be it is appropriate, therefore, PVA or it is common 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 PVA, 52 weight % SLS, 13 weight % LA7 and the 5 weight % for using 30 weight % His component, and based on the solid piece of 100 parts by weight, manufactured using the water of 240 parts by weight during piece, measure point with PVA The viscosity for the polymer solution that son amount increases and changed, its result is 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, find comprising the polymer solution of component described in present disclosure viscosity from About 50,000 molecular weight starts rapid raising.

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

<Embodiment 3>The evaluation of the selection of principal surfactant

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

Table 5

Numbering	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	Spices and other	1.5%

Specifically, PVA solution is prepared by following：145g PVA (saponification numbers are put into 630g distilled water： 86.5%, average degree of polymerization：500), dissolved 2 hours at 80 DEG C.The other components of table 5 are added to prepared PVA molten Liquid, is mixed with mechanical agitator.Mixed solution is put on by release with predetermined thickness by using Elcometer films applicator Film, dries the PVA film for including the surfactant as cleaning component to manufacture in 10 minutes 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 the phase of embodiment 1 Same method is based on three levels (excellent, good and difference) and evaluates film formings.Clean-up performance is evaluated by method identified below, The 60% or higher cleaning capacity based on the fabric (Japan) made dirty is defined as it is excellent, 50% to 59% be it is good, 50% Or it is lower to be poor.

Specifically, cleaning capacity is evaluated using the washing machine of the same terms, in this case, is carried out using running water Rinsing.In addition, wash temperature is the condition identical cold water with using 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, the use of 16 sizes being 5cm × 5cm the fabric made dirty is compared evaluation by statistical method.In this case, using colour difference meter before washing The WB values of the whitness index of the fabric made dirty are represented with measurement after washing.It will manufacture in the embodiment above for washing Piece be cut into 20cm × 15cm size, the detergent cut using two panels., will be in embodiment when starting washing clothing The piece for being used to wash of manufacture is put into washing machine together 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 with stably Temperature and humidity room (25 DEG C, 20%RH) in dry a week, ironing, use same colorimeter measurement WB values.Will Acquired results substitute into the Kubelka-Munk equatioies for being expressed as formula 2, to calculate cleaning capacity, are as a result shown in table 6.

Equation 1

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

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 be used for wash surfactants be in terms of film forming it is good or Difference.For example, surfactant LAS, SLES and MEA are subjected to being separated in the fabrication process, with low and PVA compatibilities, institute The piece of manufacture has stickiness or frangible, therefore improper in terms of the storage stability and easily operated property of manufactured piece.

<Embodiment 4>The evaluation of the selection of cosurfactant

Using NaLS is as principal surfactant and uses a variety of nonionic surfactants as auxiliary Cosurfactant manufactures a variety of pieces for being used to wash according to the formula of table 7, and these pieces are evaluated.By with implementation The similar method of example 3 manufactures the piece for washing.

Table 7

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

By the piece for being used to wash with more than embodiment 1 or the test of the identical method of embodiment 3 manufacture, 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.Method of testing defers to the method for testing of ISO 527-3 standards, uses general survey Zwick 1120 is put in trial assembly.Each sample is manufactured with uniform thickness 0.2mm, and is cut into 2 × 10 (cm²), held with screw cramp Firmly sample, the distance between clamp maintains 50mm, and extension test is carried out with the speed of 20mm/ minutes.It will can not be born in film The point of time when pulling force and breakage is set to tensile strength, it is contemplated that easy to use, and the value of table 8 is set into standard.

Table 8

Table 9

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

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

The piece for washing is manufactured, is at the same time changed together with the component and content of table 10 as principal surfactant SLS and LA7 as cosurfactant content.Manufacture method is same as Example 4.

Table 10

Film forming and the cleaning of the piece for being used to wash thus manufactured are evaluated by evaluation method same as Example 4 Performance, as a result shows in table 11.

Table 11

As shown in table 11, when considering film forming and clean-up performance, by the gross weight meter of piece, SLS contents preferably are excellent 40 weight % are elected as to 50 weight %, and the LA7 contents preferably as nonionic surfactant are 5 weight % to 15 weights Measure %.

<Embodiment 6>Overall merit

According to the formula of table 12 and the water-soluble piece of content manufacture, and evaluated in many aspects.Manufacture method is with implementing Example 4 is identical.

Table 12

In table 12, the PVA that using saponification number be 86.5% and average degree of polymerization is 500 uses polyoxy second as PVA Allylic alkylation ether LA7 represents alpha-alkene sulfonate as nonionic surfactant, AOS, uses Tinopal CBS-X (Ciba 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.

○：Tablet preparation is flexible, but has liquid component slightly smear comes out.

△：Piece is flexible not enough, and has slight smear phenomenon.

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

Table 13

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

The evaluation of dissolubility and tensile strength

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

Table 14

In the case of comparative example a and c, tablet preparation is not formed, therefore can not measure dissolubility and tensile strength.

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

The evaluation of cleaning capacity

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

Specifically, cleaning capacity is evaluated using the washing machine of the same terms, in this case, is carried out using running water Rinsing.In addition, wash temperature is the condition identical cold water with using 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 being used to evaluate 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 sizes be 5cm × The 5cm fabric made dirty is compared evaluation by statistical method.In this case, using colour difference meter before washing and Measurement represents the WB values of the whitness index of the fabric made dirty after washing.It is used for what is washed by what is manufactured in the embodiment above Piece cuts into 20cm × 15cm size, the detergent cut using two panels.When starting washing clothing, by for washing Piece and detergent are put into washing machine together with the fabric made dirty, in standardization program (washing 20 minutes, 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 dry a week, ironing, then using same colorimeter measurement W_BValue.Acquired results are substituted into implementing The identical Kubelka-Munk equatioies of example 3, to calculate cleaning capacity, as a result show in table 15.

Table 15

As shown in table 15, embodiment a, b, c, d, k with appropriate flakiness, 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.

<Embodiment 7>The evaluation (hygroscopicity) of stability

The stability of the piece for being used to wash manufactured in the embodiment d of embodiment 6 is evaluated, is as a result shown in table 16.

Table 16

The initial dried residue of piece is 95 weight %, and water content is 5 weight %, is made after being dried 10 minutes at 105 DEG C Dry residue is measured with Halogen moisture analysers.

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) it ensure that stability as product.

<Embodiment 8>The evaluation used of PVA copolymers

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

Table 17

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

The manufactured piece for being used to wash is evaluated by method same as Example 4, is as a result shown in table 18.

Table 18

As shown in Table 18, when adding builder to PVA, PVA solidifications so that dissolubility and material property are significantly bad Change, due to this insoluble component, clean-up performance does not produce the effect of builder yet.However, when using PVA copolymers, Also do not solidify even if with the addition of builder, and clean-up performance is improved due to builder, be more than when viscosity or During equal to predetermined level, the effect is due to clean-up performance reduction caused by relatively reduced because of the amount of surfactant Offset.In addition, when the amount of builder is more than or equal to 7.5%, the intensity of piece is reduced due to a large amount of builders in film.

<Embodiment 9>Add the evaluation of the effect of starch

Piece is manufactured according to the formula of table 19, addition starch is evaluated using PVA, starch or its mixture as preparaton Effect.Evaluated with the experiment identical method with embodiment 2, synthesis result is shown in table 20, and figure 2 illustrates table 20 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, it is used as when mixing starch and together preparaton (i.e. comprising component of the starch as piece) When, solution suction phenomenon (poor compatibility) occurs for surfactant after the drying, and as content of starch increases, the intensity drop of piece 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 Preferably without using starch during the piece washed.The problem of in order to overcome compatibility and tensile strength, exist and have to prepare in increase piece , in order to improve dissolubility, there is the defect for the gelling starches first of having in the defect of agent content (be more than or equal to 50%).

Claims

1. a kind of piece for being used to wash, it is using polyvinyl alcohol or the copolymer based on polyvinyl alcohol is manufactured simultaneously as polymer And it includes surfactant, wherein the surfactant without ethylene oxide group and is in the structure non-aromatic 's.

2. the piece according to claim 1 for being used to wash, wherein described be free of ethylene oxide group and be in the structure The surfactant of non-aromatic is by RSO₄ ^-M⁺The alkyl sulfate, alpha-alkene sulfonate, alkane sulphur of (M is alkali metal) expression Acid alkali metal salt, aliphatic methyl esters sulfonic acid alkali metal salts, aliphatic acid, alkylglycoside or its mixture.

3. the piece according to claim 1 for being used to wash, wherein the surfactant includes having 8 to 18 carbon atoms Alkali metal alkyl sulfates.

4. the piece according to claim 3 for being used to wash, wherein the alkali metal alkyl sulfates are NaLSs.

5. the piece according to claim 1 for being used to wash, wherein described do not conform to ethylene oxide group and be in the structure The surfactant of non-aromatic is the main of the 50 weight % that content is the total content based on the surfactant or more Surfactant.

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

7. the piece for being used to wash according to claim 5 or 6, wherein the content of the principal surfactant is based on institute State 60 weight % of total content of surfactant or more.

8. the piece according to claim 1 for being used to wash, wherein the total content of the surfactant is based on described Gross weight 40 weight % to 70 weight %, and the polyvinyl alcohol or the copolymer based on polyvinyl alcohol always contain Measure the 30 weight % to 50 weight % for the gross weight based on described.

9. the piece according to claim 1 for being used to wash, 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.

10. the piece according to claim 1 for being used to wash, wherein the polymer is polyvinyl alcohol, the polyvinyl alcohol Saponification number be 80% to 90%.

11. the piece according to claim 1 for being used to wash, wherein in addition to the principal surfactant, described Also lived comprising epoxide ethylization in heptan laruyl alcohol (LA7), nonyl epoxide ethylization laruyl alcohol (LA9) or its mixture as auxiliary surface Property agent.

12. the piece according to claim 11 for being used to wash, wherein the principal surfactant and the auxiliary surface The mixed weight ratio (principal surfactant: the cosurfactant) of activating agent is 90: 10 to 60: 40.

13. the piece according to claim 11 for being used to wash, wherein the polyvinyl alcohol described in described or described being based on The total content of the copolymer of polyvinyl alcohol is the 30 weight % based on the gross weight of dried described to 50 weight %, comprising Lauryl sulfate alkali metal salt is as the principal surfactant, and its content is 30 weight % to 60 weight %, the auxiliary The total content of surfactant is 10 weight % to 20 weight %.

14. the piece according to claim 1 for being used to wash, wherein the piece for being used to wash passes through comprising via bubbling The hole of journey formation and with improved water solubility.

15. the piece according to claim 14 for being used to wash, wherein the proportion of the piece for being used to wash is 0.6 to 0.9.

16. a kind of piece for being used to wash, comprising polymer, surfactant and alkaline auxiliary lotion, wherein the polymer is bag The copolymer based on polyvinyl alcohol containing the monomeric unit with carboxyl, the surfactant is free of oxirane in the structure Group and for non-aromatic.

17. the piece according to claim 16 for being used to wash, wherein the copolymer includes formula 1 below or 2 second Alcohol units and anionic monomer unit, the content of 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 claim 16 for being used to wash, wherein it is described in the structure without ethylene oxide group and It is by RSO for the surfactant of non-aromatic₄ ^-M⁺The alkyl sulfate, alpha-alkene sulfonate, alkane of (M is alkali metal) expression Sulfonic acid alkali metal salts, aliphatic methyl esters sulfonic acid alkali metal salts, aliphatic acid, alkylglycoside or its mixture.

19. the piece according to claim 16 for being used to wash, wherein the surfactant includes having 8 to 18 carbon originals The alkali metal alkyl sulfates of son.

20. the piece according to claim 19 for being used to wash, wherein the alkali metal alkyl sulfates are lauryl sulfates Sodium.

21. it is according to claim 19 be used for wash piece, wherein the alkali metal alkyl sulfates be content be based on 60 weight % of the total content of the surfactant or more principal surfactant.

22. the piece according to claim 16 for being used to wash, wherein the total content of the surfactant is based on described 40 weight % of the gross weight of piece to 70 weight %, the total content of the copolymer based on polyvinyl alcohol is based on described 30 weight % of gross weight to 50 weight %.

23. the piece according to claim 16 for being used to wash, wherein the number of the copolymer based on polyvinyl alcohol is divided equally Son amount is 20,000 to 50,000.

24. the piece according to claim 16 for being used to wash, wherein the saponification number of the copolymer based on polyvinyl alcohol For 60% to 85%.

25. the piece according to claim 16 for being used to wash, wherein in addition to the principal surfactant, described Also lived comprising epoxide ethylization in heptan laruyl alcohol (LA7), nonyl epoxide ethylization laruyl alcohol (LA9) or its mixture as auxiliary surface Property agent.

26. the piece according to claim 16 for being used to wash, wherein the piece for being used to wash passes through comprising via foaming The hole of process formation and with improved water solubility.

27. the piece according to claim 26 for being used to wash, wherein the proportion of the piece for being used to wash is 0.6 to 0.9.

28. the piece for being used to wash according to claim 1 or 16, wherein not conforming to starch in the chip base sheet.

29. a kind of method for manufacturing the piece for washing, including：

Prepare and include polyvinyl alcohol or copolymer and the solution of surfactant based on polyvinyl alcohol；

The solution is bubbled；And

Dry the solution.

30. method according to claim 29, wherein the surfactant includes the alkyl with 8 to 18 carbon atoms Alkali metal persulfates.