CN103608448B - For the piece of washing - Google Patents
For the piece of washing Download PDFInfo
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- CN103608448B CN103608448B CN201280029267.2A CN201280029267A CN103608448B CN 103608448 B CN103608448 B CN 103608448B CN 201280029267 A CN201280029267 A CN 201280029267A CN 103608448 B CN103608448 B CN 103608448B
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- polyvinyl alcohol
- surfactant
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0086—Laundry tablets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/044—Solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/008—Polymeric surface-active agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
Abstract
The present invention is provided to the pieces of washing, can be dissolved completely in water and after wash without removal.In addition, the piece for washing with good clean-up performance, using it is simple, will not bring inconvenience in use with the storage stability determined and to user.The piece for washing of the present invention is prepared by using polyvinyl alcohol polymer/copolymer, specific principal surfactant and optional cosurfactant (preferred nonionic surfactants, more preferable LA7/LA9).
Description
Technical field
Present disclosure is related to being placed on the detergent used in washing machine and wherein.More particularly, present disclosure
It is related to piece type or membranous type detergent, formula is 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
0045255th, 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 technology
So far always using powder detergent or liquid detergent as being placed in washing machine and what is used wherein washes
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 being encapsulated respectively to them using water-soluble polymer films
When, during storage or in transport, sealer may rupture and product leakage content.In addition, table of the active component from film
Face is oozed out, and the storage stability of product is caused 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 the considerable time is needed to dissolve this at low temperature
Water-solubility membrane, and the water-solubility membrane is not completely dissolved even, leads to the residual of film residue.
In addition, it uses to wash by adsorbing liquid detergent on water-insoluble suction sheet although having developed
The piece washed, still, this shortcomings that is to have to remove the water-insoluble suction sheet after washing.
Disclosure
Technical problem
Therefore, present disclosure is related to providing the laundry sheet for being used in washing machine, in washing process completely
Dissolving has excellent clean-up performance, is easily fabricated and ensure storage stability.
Technical solution
In order to realize purpose in the present disclosure, provide and polymer is formed by using piece, live for the surface of washing
Property the manufactures such as agent the piece for washing,
Wherein i) piece formed polymer be polyvinyl alcohol or copolymer based on polyvinyl alcohol and
Ii it is) that the non-aromatic surface without ethylene oxide group is lived in the structure for the surfactant of cleaning action
Property agent, it is therefore preferable to there is the alkyl sulfate of 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 base material when, astoundingly, numerous surfactants (nonionic surfactant, from
Sub- surfactant, amphoteric surfactant etc.) among, in purpose in the 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).
Following characteristics are had according to the piece in the present disclosure for washing：(1) it is easy to dissolve in water at low temperature, so as to
Excellent clean-up performance is provided, (2) prevent liquid-type active component from being oozed 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,
Excellent clean-up performance is shown with distributional stability and (5).
According in the piece in 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 base material 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, 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 can be accommodated based on the copolymer of polyvinyl alcohol within the limitation of detergent flakes required material property a large amount of
Surfactant.
In the present disclosure in the piece of washing, particularly, polyvinyl alcohol or the copolymer based on polyvinyl alcohol to have
There are many molecular weight and saponification degree, when consider film forming, dissolubility, easily fabricated property, storage stability, clean-up performance,
It is more excellent, it is preferable to use number-average molecular weight is 10,000 to 100,000 copolymer durings 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 for 20,000 to
30,000 copolymer.
In addition, the preferred saponification degree of polyvinyl alcohol or the copolymer based on polyvinyl alcohol according to purpose in the 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 is preferably included according to this
When the formula 1 below of disclosure or the specific copolymer of 2 comonomer and use 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, 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 of formula 1 below or 2 vinyl alcohol monomer units and anionic monomer unit.At this
In the case of kind, the copolymer of 0.5mol% to 5mol% anionic monomer units is particularly preferably included.
<Chemical formula 1>
<Chemical formula 2>
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 curing.It, can be simultaneously when using the copolymer based on polyvinyl alcohol that PVA is replaced to be used as into film base material
Improve film forming, film dissolubility and for washing piece cleaning efficiency in addition 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 for purpose in the present disclosure.For example, comprising with-SO3The anionic monomer of H
PVA copolymers are easy to by alkaline auxiliary lotion gelation, as a result, described is difficult to dissolve after being manufactured.
In addition, it quite particularly, is used to wash comprising metal alkyl sulfate, alkaline auxiliary lotion and PVA copolymers
In the piece washed, the saponification degree of PVA copolymers 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, more than 90%), the piece after manufacturing will appear dissolubility significantly
The phenomenon that reduction, and when saponification degree too low (for example, less than 60%), the water-soluble of copolymer reduces.It is worth noting that, this
A result is different from the result of the 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 of base material 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 purpose in the present disclosure, in film forming, spatter property
Energy, stability etc. highly preferable use the non-aromatic surfactant conduct for being free of ethylene oxide group in the structure
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.
The surfactant of a large amount of ethylene oxide groups is included in the structure (for example, sodium laureth sulfate when using
(SLES) or be added to the nonionic surfactant of EO) as main surfactant when, filming performance can substantially reduce.
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 theory hypothesis.
In addition, in the feelings for 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 in the piece for washing for including 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
Gauge 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), aliphatic acid, alkylglycoside etc., in this case, according to multiple mesh in the present disclosure
, particularly preferred alkyl sulfate, especially astoundingly, according to multiple purposes (including film forming etc.) in the 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 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 preferable C12 is extremely
C16 the alkyl sulfate surfactant of saturated hydrocarbons), because it can be such that tablet preparation is improved while having good strength
Clean-up performance, this is because itself and the superior compatibility as polyvinyl alcohol polymer/copolymer into film base material, even if surface
The content height of activating agent is also such；However, present disclosure is not limited to the theory hypothesis.
If it is used using according to polyvinyl alcohol polymer/copolymer in the present disclosure and the manufacture of specific surfactant
In the piece of washing, then the total content of all surface activating agent be preferably based on it is dry after piece total weight 30 weight % to 80
Weight % (more preferable 40 weight % to 70 weight %), the content of polyvinyl alcohol polymer/copolymer be preferably based on it is dry after
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 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) out,
And when the content of polyvinyl alcohol polymer/copolymer is less than 30 weight %, on the intensity of described is significantly reduced while is had
State problem so that can occur to use defect.
When the content of surfactant is less than above range, clean-up performance reduces, and when the content is more than above range
When, the content relative reduction of polyvinyl alcohol polymer/copolymer, therefore, tablet preparation is difficult to manufacture.
Other than polyvinyl alcohol polymer/copolymer and surfactant, it can also be included hereafter for the piece of washing
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, for the non-aromatic surfactant in the structure without ethylene oxide group (more
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 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：Use polyvinyl alcohol or copolymer based on polyvinyl alcohol and
In the piece for washing that surfactant as cleaning action component manufactures, Oxyranyle is free of in the structure when using
The non-aromatic surfactant of group (more preferably has the alkyl sulfate of 8 to 18 carbon atoms, even more preferably alkylsurfuric acid
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 and maintain film forming simultaneously.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 reduce film forming showed to low degree or in terms of clean-up performance is improved it is excellent.
Therefore, it is highly preferred that present disclosure offer is used only comprising the lauryl sulphur (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 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 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 notable.
Therefore, present disclosure offer use polyvinyl alcohol or copolymer based on polyvinyl alcohol, as major surfaces work
Property agent alkyl sulfate and the piece for washing 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) (preferably sodium alkyl sulfate,
More preferably NaLS) what is represented has the alkyl of 8 to 18 carbon atoms, wherein by the total weight 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 %.
According in preparation in the present disclosure, present disclosure also based on following it is surprisingly found that：It is it is preferred that basic
The upper starch that do not use is as preparaton (into film base material).When mixing starch and as preparaton when (that is, comprising starch as structure
Into one of described component), the solution suction phenomenon (poor compatibility) of generation surfactant, and as starch contains after the drying
Amount increases, and the intensity of piece decreases.In addition, as content of starch increases, dissolubility also decreases.
In this disclosure, " do not use substantially " expression " the dry weight meter of press piece, comprising 5 weight % or less, preferably
3 weight % or less, more preferable 1 weight % or less, even more preferably zero ".
Film forming, storage can also not deteriorated surely comprising following substance according to the piece in the present disclosure for washing
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), disintegrant/disintegration
Auxiliary agent (for example, starch, cellulose derivative, sodium chloride, citric acid, glycerine, 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)；Dispersant/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, antiseptic etc..
Thickness according to the piece in the present disclosure for washing be preferably 1 μm to 1cm, more preferably 5 μm to 0.5cm,
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 more than 1cm, dissolving
It is slack-off, and clean-up performance deterioration becomes to cause concern.
It is highly preferred that by the total weight 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 the fluorescent whitening agent of optionally 1 weight % to 5 weight % and optionally 1 weight % to the enzyme of 5 weight % is water-soluble
Laundry detergent compositions.When in the present disclosure 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
Outside, it can also be included according to the piece in the present disclosure for washing so that not interfering the close limit amount of present disclosure purpose
Another cosurfactant.The surfactant for containing ethylene oxide group in the structure can also be included as another
It plants cosurfactant and laureth sodium sulphate can be used as the table in the structure containing ethylene oxide group
Face activating agent.
Other than polyvinyl alcohol or copolymer and principal surfactant based on polyvinyl alcohol, according to present disclosure
For washing piece can also include so that the aromatic surfactants of the range of present disclosure purpose is not interfered to 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.
Piece in the present disclosure for washing 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.
It can be manufactured by following steps according to the piece in the present disclosure for washing：It is 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
Gains are molded as the piece of uniform thickness, and dry by the other components mixing of surfactant etc..In addition, according to the disclosure
The piece for washing of content is not limited to previous building methods, for example, manufacturing method can include polyethylene dissolving alcohol in water
Or before the copolymer based on polyvinyl alcohol, other components (for example, surfactant) are dissolved.
Present disclosure also based on the fact that：It is preferred that bubbling process is further included in a manufacturing method to improve in the disclosure
The dissolubility of the piece of appearance in water when proportion is adjusted to 0.6 to 0.9 by bubbling process, can be provided preferably and be used for
The piece of washing is in many advantages of water-soluble, water-soluble speed etc..Therefore, the system that present disclosure offer includes the following steps
The method for making the piece for washing：It prepares molten comprising polyvinyl alcohol or copolymer based on polyvinyl alcohol and surfactant
Liquid, blistering and drying.That is, present disclosure provides the piece for washing comprising the multiple holes formed by bubbling process.
Therefore, present disclosure is also provided is used for above-mentioned technical characteristic and proportion for 0.6 to 0.9 additional features
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.
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 stretches
The figure for the experimental result that intensity changes.For example, in the value " 03-40-170 " of X-axis, first value represent the degree of polymerization/100 (that is,
03 represents the degree of polymerization for 300), second value expression PVA content (weight %), third 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, unit for kilogram/centimetre2
(kgf/cm2)。
Fig. 2 is the change illustrated by using tensile strength caused by a part of PVA of the starch substitution as preparaton
As a result figure.In the figure, the value of Y-axis represents tensile strength, unit kgf/cm2.In fig. 2, red boundary line shows
Go out the minimum tensile strength required when using piece for 5kgf/cm2(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 each mixed solution, water content is 240% based on solid.
Specific embodiment
Hereinafter, embodiment in the present disclosure is will be described in help to understand present disclosure.However, it is possible to
A variety of change and variations are made to embodiment in the present disclosure, and it will be understood that scope of the present disclosure be not limited to
Following embodiments.Embodiment in the present disclosure is to provide in the present disclosure more completely to retouch for those skilled in the art
It states.
<Embodiment 1>For the selection of 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
It is evaluated in terms of storage stability.As a result it shows in table 1 below.
It is prepared by the dissolving 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 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 poor) forms a film to evaluate in three levels with the piece after manufacture in the fabrication process
Property.
Following evaluation dissolubility.Manufactured diaphragm is cut into 5cm × 5cm, is then put into about 300ml15 DEG C of pure water
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 oxygroup) 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 as the polymer for manufacture for the piece of washing.
<Embodiment 2>The evaluation of the effect of content and molecular weight to PVA
In addition, as evaluating film forming, dissolubility using the polyvinyl alcohol with various molecular weights and saponification degree, 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, more preferable 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, about saponification degree, when unmixed alkaline auxiliary lotion, preferably saponification degree for 80% to
90% polymer, and when using PVA copolymers and mixed-alkali builder, be particularly preferred saponification degree for 60% to
The polymer of 90% (more preferable 70% to 85%, even more preferably 70% to 82%).When using saponification degree than above-mentioned saponification
During the polymer of the lower range of degree, water solubility reduces, and works as and use saponification degree in the poly- of range more higher than above-mentioned saponification degree
When closing object, gel phenomenon occurs.
The experimental result of confirmation above disclosure is shown in the following table 3 and 4.The manufacture of described 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.The membrane material characteristic (" dried surface ") for including shift index etc. is scored and commented
Valency.For example, 1 point represents in addition to there is situation no abnormal on the external film of residual on surface, and 3 points represent on the surface of the film
Phenomenon of phase separation has occurred, and still also has remaining situation 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 represents that PVA accounts for total solid in addition to water
Weight %, water content represent that when preparing mixed solution water accounts for the weight % of total weight of solids.That is, in No.1 is formulated, 40%
The expression of PVA contents the PVA of 40 weight % is included in total solid because 63% water content means for manufacturing piece
37% solid and 63% water is included in mixed solution, it is assumed that solid content is 100, then water content is about 170.
Table 3
Table 4
* in No.13 is formulated, 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 of piece and intensity, but due to reducing the content of 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 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 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 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 240 weight % of solid) 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, and 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, point with PVA when manufacturing piece, is measured using the water of 240 parts by weight
The viscosity of polymer solution that son amount increases and changes, 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, find comprising the polymer solution of component described in present disclosure viscosity from
About 50,000 molecular weight starts to improve rapidly.
As reference, the piece tensile strength based on molecular weight, PVA contents and 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 bigger is (when tensile strength is 5kgf/cm2Or during smaller, it
Easily tear or rupture) minimum, by 10kgf/cm2Or bigger is determined as good level, according to tensile strength, such as 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
According to component and the content manufacture listed in table 5 for the piece of 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, PVA solution is prepared by following：145g PVA (saponification degrees are put into 630g distilled water：
86.5%, average degree of polymerization：500) it, is dissolved 2 hours at 80 DEG C.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 by release with scheduled thickness by using Elcometer films applicator
Film, the dry 10 minutes PVA films that the surfactant as cleaning component is included to manufacture 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,
The 60% or higher cleaning capacity based on the fabric (Japan) made dirty is 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 the 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 it is evaluated under conditions of the fabric made dirty belongs to cotton T-shirt.In addition, the use of 16 sizes is 5cm
The fabric made dirty of × 5cm is compared evaluation by statistical method.In this case, using colour difference meter before washing
With the WB values that the whitness index for representing the fabric made dirty is measured 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 that two panels is used to cut.It, will in embodiment when starting to wash clothing
The piece for washing of manufacture is put into togerther with the fabric made dirty in washing machine 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 stabilization
Temperature and humidity room (25 DEG C, 20%RH) in a dry week, ironing uses same colorimeter measurement WB values.It 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 of fabric made dirty, and the fabric that Rc expressions are made dirty is after the washing process
Surface reflectivity and Ro represent 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 being separated in the fabrication process, there is 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
As principal surfactant and a variety of nonionic surfactants are used as auxiliary using NaLS
Cosurfactant manufactures a variety of pieces for washing according to the formula of table 7, and these pieces are evaluated.By with implementation
The similar method manufacture of example 3 is used for the piece of washing.
Table 7
In table 7, PVA(1)Represent the polyvinyl alcohol that saponification degree is 86.5% and average degree of polymerization is 500, SLS(2)It is right
It should be in NaLS, using Tinopal CBS-X (Ciba Specialty Chemical) as fluorescent dye(3)。
By the method test above piece for washing that manufactures 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 standards, uses general survey
Zwick 1120 is put in trial assembly.Each sample is manufactured, and be cut into 2 × 10 (cm with uniform thickness 0.2mm2), it is held with screw cramp
The distance between firmly sample, clamp maintains 50mm, and extension test is carried out with the speed of 20mm/ minutes.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, the value of table 8 is set as 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 is more preferable, and LA7 is more preferable than LA9 in terms of cleaning capacity.
<Embodiment 5>The effect of the content of SLS as the principal surfactant and LA7 as cosurfactant
Evaluation.
At the same time manufacture changes with together with the component and content of table 10 as principal surfactant for the piece of washing
SLS and LA7 as cosurfactant content.Manufacturing method is same as Example 4.
Table 10
Thus the film forming of the piece for washing manufactured and cleaning 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 during clean-up performance, the total weight of press piece, preferred SLS contents are excellent
40 weight % are selected 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.Manufacturing method is with implementing
Example 4 is identical.
Table 12
In table 12, the PVA that using saponification degree be 86.5% and average degree of polymerization is 500 uses polyoxy second as PVA
Allylic alkylation ether LA7 represents alpha-alkene sulfonate, uses Tinopal CBS-X (Ciba as nonionic surfactant, AOS
Specialty Chemical) as fluorescent dye.
The evaluation of flakiness
Based on following standard, washed by macroscopic observation to evaluate the water-soluble piece manufactured in above-described embodiment and comparative example
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 insufficient, 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 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
By method same as Example 4 come test 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 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 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 (coming evaluation comparison example a and c instead of water soluble detergent piece 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 the 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, it is evaluated under conditions of the fabric made dirty belongs to cotton T-shirt.In addition, using 16 sizes for 5cm ×
The fabric made dirty of 5cm is compared evaluation by statistical method.In this case, using colour difference meter before washing and
The WB values for the whitness index for representing the fabric made dirty are measured after washing.It is used for what is washed by what is manufactured in the embodiment above
Piece cuts into the size of 20cm × 15cm, the detergent cut using two panels.It, will be for washing when starting to wash clothing
Piece and detergent and the fabric made dirty are put into togerther in washing machine, 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, ironing, then using same colorimeter measurement WBValue.Acquired results are substituted into and implemented
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 washing 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 %, dry at 105 DEG C to make after ten minutes
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) ensure stability as product.
<Embodiment 8>The evaluation used of PVA copolymers
The piece of washing is used for according to the formula manufacture of table 17, manufacturing method is same as Example 4.
Table 17
In table 17, PVA(1)It represents 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 copolymers(2), SLS(3)
Corresponding to NaLS, using sodium carbonate (soda) as builder(4), use Tinopal CBS-X (Ciba
Specialty Chemical) 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 curings 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 copolymers,
Be not cured, and clean-up performance is improved due to builder even if be added to builder, be more than when viscosity or
Equal to it is scheduled horizontal when, the effect due to the amount because surfactant it is relatively reduced caused by clean-up performance reduce due to
It offsets.In addition, when the amount of builder is greater 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.The method identical with the experiment with embodiment 2 is evaluated, and 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, it is used as when mixing starch and together preparaton (i.e. comprising component 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 also reduces.Thus, it is found that it is used to wash according in the present disclosure in manufacture
Starch is not preferably used during the piece washed.In order to overcome the problems, such as compatibility and tensile strength, exist to have to increase and be prepared in piece
The defects of agent content (being greater than or equal to 50%), in order to improve dissolubility, there is the defects of having to gelling starches first.
Claims (15)
1. a kind of piece for washing is manufactured simultaneously using polyvinyl alcohol or based on the copolymer of polyvinyl alcohol as polymer
And it includes surfactant, wherein the surfactant includes the alkali metal alkyl sulfates with 8 to 18 carbon atoms；
The total content of wherein described surfactant be based on 40 weight % of the total weight of dried described to 70 weight %, and
And the total content of the polyvinyl alcohol or the copolymer based on polyvinyl alcohol is based on the total weight of dried described
30 weight % to 50 weight %；The wherein described alkali metal alkyl sulfates with 8 to 18 carbon atoms are lived for major surfaces
Property agent, the 60 weight % of the content of the principal surfactant for the total content based on the surfactant or more；And
And the number-average molecular weight of wherein described polyvinyl alcohol or the copolymer based on polyvinyl alcohol is 20,000 to 50,000；
Wherein other than the principal surfactant, described also comprising oxygroup ethylization in heptan laruyl alcohol, nonyl epoxide ethyl
Change laruyl alcohol or its mixture as cosurfactant；And
The vinyl alcohol and concentration that the wherein described copolymer based on polyvinyl alcohol is a concentration of 98mol%, saponification degree is 77mol%
Methacrylic acid copolymer for 2mol%.
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 polymer is polyvinyl alcohol, the polyvinyl alcohol
Saponification degree is 80% to 90%.
4. the piece according to claim 1 for washing, wherein the principal surfactant is lived with the auxiliary surface
Property agent mixed weight ratio be 90: 10 to 60: 40.
5. the piece according to claim 1 for washing, wherein the polyvinyl alcohol described in described or described based on poly-
The total content of the copolymer of vinyl alcohol is to include the moon to 50 weight % based on 30 weight % of the total weight of dried described
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 %.
6. the piece according to claim 1 for washing, wherein the piece for washing passes through comprising via blistering
Hole that journey is formed and with improved water solubility.
7. the piece according to claim 6 for washing, wherein the proportion of the piece for washing is 0.6 to 0.9.
8. a kind of piece for washing, comprising polymer, surfactant and alkaline auxiliary lotion, wherein the polymer is to include
The copolymer based on polyvinyl alcohol of monomeric unit with carboxyl, the surfactant include having 8 to 18 carbon atoms
Alkali metal alkyl sulfates；The total content of wherein described surfactant is 40 based on the total weight of dried described
Weight % to 70 weight %, the total content of the copolymer based on polyvinyl alcohol is based on the total weight of dried described
30 weight % to 50 weight %；Wherein described alkali metal alkyl sulfates are that content is always containing based on the surfactant
The principal surfactant of 60 weight % of amount or more；And the equal molecule of number of the wherein described copolymer based on polyvinyl alcohol
Measure is 20,000 to 50,000；
The vinyl alcohol and concentration that the wherein described copolymer based on polyvinyl alcohol is a concentration of 98mol%, saponification degree is 77mol%
Methacrylic acid copolymer for 2mol%.
9. the piece according to claim 8 for washing, wherein the alkali metal alkyl sulfates are NaLSs.
10. the piece according to claim 8 for washing, wherein the saponification degree of the copolymer based on polyvinyl alcohol is
60% to 85%.
11. the piece according to claim 8 for washing, wherein other than the principal surfactant, described
Also comprising oxygroup ethylization in heptan laruyl alcohol, nonyl epoxide ethylization laruyl alcohol or its mixture as cosurfactant.
12. the piece according to claim 8 for washing, wherein the piece for washing passes through comprising via blistering
Hole that journey is formed and with improved water solubility.
13. the piece according to claim 12 for washing, wherein the proportion of the piece for washing is 0.6 to 0.9.
14. the piece for washing according to claim 1 or 8, wherein not starch-containing in the chip base sheet.
15. a kind of method for manufacturing the piece for washing, including：
It prepares comprising polyvinyl alcohol or copolymer and the solution of surfactant based on polyvinyl alcohol；
It blisters to the solution；And
The dry solution；
The total content of wherein described surfactant is the 40 weight % to 70 weights based on the total weight of dried described
% is measured, and the total content of the polyvinyl alcohol or the copolymer based on polyvinyl alcohol is based on dried described
30 weight % of total weight to 50 weight %；
Wherein described surfactant includes the alkali metal alkyl sulfates with 8 to 18 carbon atoms, and the alkyl sulfide
Acid alkali metal salt is principal surfactant, 60 weight %s or more of the content for the total content based on the surfactant
It is more；
The number-average molecular weight of wherein described polyvinyl alcohol or the copolymer based on polyvinyl alcohol is 20,000 to 50,000；
Wherein other than the principal surfactant, described also comprising oxygroup ethylization in heptan laruyl alcohol, nonyl epoxide ethyl
Change laruyl alcohol or its mixture as cosurfactant；And
The vinyl alcohol and concentration that the wherein described copolymer based on polyvinyl alcohol is a concentration of 98mol%, saponification degree is 77mol%
Methacrylic acid copolymer for 2mol%.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610879699.2A CN106978264B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201810024649.5A CN108085146B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201810511711.3A CN108559679B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201711087720.6A CN107828567B (en) | 2011-05-13 | 2012-04-17 | Piece for washing |
| CN202110242566.5A CN113004991A (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201711087875.XA CN107881043B9 (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20110045255 | 2011-05-13 | ||
| KR10-2011-0045255 | 2011-05-13 | ||
| KR20110045256 | 2011-05-13 | ||
| KR1020110045257A KR101146292B1 (en) | 2011-05-13 | 2011-05-13 | Laundry sheet comprising lauryl sulfate salt |
| KR10-2011-0045257 | 2011-05-13 | ||
| KR10-2011-0045256 | 2011-05-13 | ||
| KR1020110132083A KR101787652B1 (en) | 2011-05-13 | 2011-12-09 | Sheet for laundry |
| KR10-2011-0132080 | 2011-12-09 | ||
| KR1020110132080A KR101358923B1 (en) | 2011-05-13 | 2011-12-09 | Sheet for laundry |
| KR10-2011-0132083 | 2011-12-09 | ||
| PCT/KR2012/002916 WO2012157851A2 (en) | 2011-05-13 | 2012-04-17 | Sheet for washing |
Related Child Applications (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711087720.6A Division CN107828567B (en) | 2011-05-13 | 2012-04-17 | Piece for washing |
| CN201610879699.2A Division CN106978264B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201810024649.5A Division CN108085146B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201810511711.3A Division CN108559679B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201711087875.XA Division CN107881043B9 (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN202110242566.5A Division CN113004991A (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103608448A CN103608448A (en) | 2014-02-26 |
| CN103608448B true CN103608448B (en) | 2018-06-26 |
Family
ID=47177419
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711087720.6A Active CN107828567B (en) | 2011-05-13 | 2012-04-17 | Piece for washing |
| CN201810511711.3A Active CN108559679B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201810024649.5A Active CN108085146B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201280029267.2A Active CN103608448B (en) | 2011-05-13 | 2012-04-17 | For the piece of washing |
| CN201610879699.2A Active CN106978264B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN202110242566.5A Pending CN113004991A (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201711087875.XA Active CN107881043B9 (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
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| CN201711087720.6A Active CN107828567B (en) | 2011-05-13 | 2012-04-17 | Piece for washing |
| CN201810511711.3A Active CN108559679B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201810024649.5A Active CN108085146B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
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| CN202110242566.5A Pending CN113004991A (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
| CN201711087875.XA Active CN107881043B9 (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
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| WO2017111498A1 (en) * | 2015-12-22 | 2017-06-29 | 주식회사 엘지생활건강 | Sheet for washing |
| KR101772195B1 (en) * | 2015-12-22 | 2017-08-28 | 주식회사 엘지생활건강 | Sheet for laundry |
| CN105586165A (en) * | 2016-01-29 | 2016-05-18 | 广州康钰生物科技有限公司 | Laundry sheet with color protecting function and preparation method thereof |
| CN105969546B (en) * | 2016-05-31 | 2018-12-14 | 杨晶晶 | A kind of laundry sheet and preparation method thereof |
| CN106118916A (en) * | 2016-08-15 | 2016-11-16 | 邓国政 | A kind of Superconcentrated washing sheet and production technology thereof |
| CN106367222A (en) * | 2016-08-27 | 2017-02-01 | 朱耀灯 | Multifunctional laundry sheet and preparing method thereof |
| CN106381235A (en) * | 2016-08-27 | 2017-02-08 | 朱耀灯 | Ultra-concentrated multifunctional laundry sheet and preparation method thereof |
| CN106726905A (en) * | 2016-12-09 | 2017-05-31 | 广州市福美生物科技有限公司 | A kind of natural tea seed hair washing piece and preparation method thereof |
| CN106635572B (en) * | 2016-12-12 | 2020-09-22 | 广州立白企业集团有限公司 | Detergent composition in tablet form and process for producing the same |
| CN106590986A (en) * | 2016-12-26 | 2017-04-26 | 佛山市芊茹化妆品有限公司 | Laundry sheets with clothing softening effect |
| JP6882496B2 (en) | 2017-02-06 | 2021-06-02 | ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ | Laundry detergent sheet with microcapsules |
| CN107034039A (en) * | 2017-05-03 | 2017-08-11 | 诺圆环保科技（苏州）有限公司 | A kind of preparation method of compound laundry sheet |
| WO2019050341A1 (en) * | 2017-09-08 | 2019-03-14 | 주식회사 엘지생활건강 | Laundry sheet |
| WO2019056336A1 (en) | 2017-09-25 | 2019-03-28 | The Procter & Gamble Company | Unitary laundry detergent article |
| US11584903B2 (en) * | 2017-10-05 | 2023-02-21 | Lubrizol Advanced Materials, Inc. | Structured unit dose cleansing product |
| CN112041418A (en) * | 2018-05-02 | 2020-12-04 | 奈克斯特阿普有限公司 | Laundry sheet |
| JP7101671B2 (en) * | 2019-01-15 | 2022-07-15 | ザ プロクター アンド ギャンブル カンパニー | Flexible and soluble solid sheet article |
| CN114867452A (en) | 2020-02-20 | 2022-08-05 | 宝洁公司 | Flexible porous dissolvable solid sheet article comprising cationic surfactant |
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| CN1009113B (en) * | 1986-06-06 | 1990-08-08 | 西北大学 | Prepn. of solid antilithic and deoderant for urinal |
| JP3126675B2 (en) * | 1997-01-23 | 2001-01-22 | 花王株式会社 | Sheet detergent |
| KR19980052351A (en) * | 1996-12-24 | 1998-09-25 | 유병언 | Thin film soap with air bubbles attached to cellulose film |
| ES2245819T3 (en) * | 1998-07-10 | 2006-01-16 | THE PROCTER & GAMBLE COMPANY | TENSIOACTIVE AGLOMERATES. |
| EP0971030A1 (en) * | 1998-07-10 | 2000-01-12 | The Procter & Gamble Company | Surfactant agglomerates |
| GB9826105D0 (en) * | 1998-11-27 | 1999-01-20 | Unilever Plc | Detergent compositions |
| CN2352536Y (en) * | 1998-11-30 | 1999-12-08 | 顾一平 | Detergent |
| CN1421519A (en) * | 2001-11-23 | 2003-06-04 | 吕秀娟 | Lamelliform sanitory washing article and its making process and use |
| CN1142264C (en) * | 2002-01-15 | 2004-03-17 | 北京博恒新材料研究有限责任公司 | Completely water-soluble hand-washing film |
| CN1445353A (en) * | 2002-03-19 | 2003-10-01 | 上海白猫有限公司 | Multi-functional quick dissolving filmy cleanser and its manufacturing methods |
| CN1528268A (en) * | 2003-10-14 | 2004-09-15 | 吴广权 | Skin-care washing article |
| CN1621507A (en) * | 2003-11-27 | 2005-06-01 | 漳州艾妮沐浴用品有限公司 | Quick dissolving soap flake and processing technology thereof |
| KR20050075064A (en) * | 2004-01-15 | 2005-07-20 | 케이씨더블류 주식회사 | Cleaning compositions for hard surfaces |
| CN1888042A (en) * | 2005-06-27 | 2007-01-03 | 顾仁安 | Water soluble detergent film |
| KR101222402B1 (en) * | 2009-02-05 | 2013-01-16 | 주식회사 엘지생활건강 | Laundry sheet |
| KR101259425B1 (en) * | 2009-02-24 | 2013-04-30 | 주식회사 엘지생활건강 | Sheet type detergent, detergent composition and preparation method thereof |
| KR101014889B1 (en) * | 2009-03-25 | 2011-02-15 | 오씨아이 주식회사 | Sheet-type Detergent Containing Eco-friendly Non-Aqueous Composition and Method for Producing thereof |
| CN106635572B (en) * | 2016-12-12 | 2020-09-22 | 广州立白企业集团有限公司 | Detergent composition in tablet form and process for producing the same |
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2012
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- 2012-04-17 CN CN201810511711.3A patent/CN108559679B/en active Active
- 2012-04-17 CN CN201810024649.5A patent/CN108085146B/en active Active
- 2012-04-17 CN CN201280029267.2A patent/CN103608448B/en active Active
- 2012-04-17 WO PCT/KR2012/002916 patent/WO2012157851A2/en active Application Filing
- 2012-04-17 CN CN201610879699.2A patent/CN106978264B/en active Active
- 2012-04-17 CN CN202110242566.5A patent/CN113004991A/en active Pending
- 2012-04-17 CN CN201711087875.XA patent/CN107881043B9/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107881043B9 (en) | 2020-11-24 |
| CN103608448A (en) | 2014-02-26 |
| CN113004991A (en) | 2021-06-22 |
| CN107828567B (en) | 2019-06-14 |
| CN108559679B (en) | 2021-03-26 |
| CN108559679A (en) | 2018-09-21 |
| WO2012157851A9 (en) | 2013-04-04 |
| CN107828567A (en) | 2018-03-23 |
| CN107881043B (en) | 2020-08-18 |
| CN107881043A (en) | 2018-04-06 |
| WO2012157851A3 (en) | 2013-01-24 |
| CN106978264B (en) | 2020-11-03 |
| CN108085146A (en) | 2018-05-29 |
| WO2012157851A2 (en) | 2012-11-22 |
| CN108085146B (en) | 2020-10-16 |
| CN106978264A (en) | 2017-07-25 |
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