CN113004991A - Washing sheet - Google Patents
Washing sheet Download PDFInfo
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- CN113004991A CN113004991A CN202110242566.5A CN202110242566A CN113004991A CN 113004991 A CN113004991 A CN 113004991A CN 202110242566 A CN202110242566 A CN 202110242566A CN 113004991 A CN113004991 A CN 113004991A
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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 provides a tablet for washing, which can be completely dissolved in water and does not need to be removed after washing. In addition, the sheet for washing has good cleaning performance, is easy to use, has definite storage stability, and does not cause inconvenience to a user during use. The tablets for washing of the present invention are prepared by using a polyvinyl alcohol polymer/copolymer, a specific primary surfactant, and optionally a secondary surfactant (preferably a nonionic surfactant, more preferably LA7/LA 9).
Description
The present application is a divisional application for chinese patent application having application number 201810511711.3 entitled "tablet for washing", which was filed 24/5/2018. The application to which the present application is directed is a divisional application of chinese patent application having application number 201280029267.2 entitled "sheet for washing", and the parent application is an application of PCT international application PCT/KR2012/002916 filed 4/17/2012 to enter the chinese national phase at 12/13/2013.
Technical Field
The present disclosure relates to a detergent to be placed in a washing machine and used therein. More particularly, the present disclosure relates to tablet or film type detergents, which are formulated differently from general powder or liquid detergents.
The present application claims priority from korean patent application No. 10-2011-.
Background
Powder detergents or liquid detergents have hitherto been used as detergents to be put into and used in washing machines. However, they have a disadvantage in that liquid detergents are relatively heavy, whereas powder detergents are easily dispersed. Therefore, the demand for new detergents is increasing.
To solve these problems, U.S. patent No.4,605,509 discloses a technique of encapsulating a liquid type detergent component and a fabric softener in a water-soluble film sealer. However, when they are separately packaged using water-soluble polymer films, the seal may break and leak the product contents during storage or while in transport. In addition, the active ingredient bleeds out from the surface of the film, resulting in a great reduction in the storage stability of the product. In addition, although the water-soluble film used as a sealing sealant is designed to ensure stability and durability of the contents against moisture in the air, a considerable time is required to dissolve the water-soluble film at low temperature, and the water-soluble film is not even completely dissolved, resulting in residue of the film.
Further, although a tablet for washing used by adsorbing a liquid detergent on a water-insoluble absorbent tablet has been developed, such a tablet has a disadvantage in that the water-insoluble absorbent tablet has to be removed after washing.
Disclosure of Invention
Technical problem
Accordingly, the present disclosure is directed to providing laundry tablets for use in washing machines, which are completely dissolved in the washing process, have excellent cleaning performance, are easy to manufacture, and ensure storage stability.
Technical solution
To achieve the object of the present disclosure, there is provided a sheet for washing manufactured by using a sheet-forming polymer, a surfactant for washing, and the like,
wherein i) the sheet-forming polymer is polyvinyl alcohol or a copolymer based on polyvinyl alcohol, and
ii) the surfactant for cleaning action is a non-aromatic surfactant which does not contain an ethylene oxide group in the structure, preferably an alkyl sulphate having 8 to 18 carbon atoms, more preferably a lauryl sulphate.
The salts of alkyl sulfates including lauryl sulfate are alkyl metal salts, preferably sodium or potassium salts, most preferably sodium salts.
The present disclosure is based on the following unexpected and surprising findings: when polyvinyl alcohol or a copolymer based on polyvinyl alcohol is used as a substrate for a sheet for washing, surprisingly, among a large number of surfactants (nonionic surfactant, ionic surfactant, amphoteric surfactant, etc.), surfactants of specific structures are preferable in terms of the object of the present disclosure, film-forming property, cleaning property, stability, etc., and among them, in particular, alkali metal alkylsulfates having 8 to 18 carbon atoms are highly preferable, more preferably alkali metal lauryl sulfate (most preferably sodium lauryl sulfate).
The sheet for washing according to the present disclosure has the following features: (1) it is easily dissolved in low-temperature water to provide excellent cleaning performance, (2) prevents the liquid type active ingredient from oozing out of the sheet until put into a washing machine, (3) has tensile strength sufficient to prevent it from breaking upon use and exhibits flexibility, (4) has distribution stability due to resistance to absorption of ambient moisture, and (5) shows excellent cleaning performance.
In the sheet for washing according to the present disclosure, polyvinyl alcohol or a copolymer based on polyvinyl alcohol is highly preferably used as a base material for forming the sheet for washing among various polymers such as gelatin, pectin, dextran, hyaluronic acid, collagen, agar, gum arabic, acacia rubber, alginic acid, sodium alginate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, sodium carboxymethyl cellulose, starch, dextrin, carboxymethyl starch, polyvinyl pyrrolidone, polyvinyl methacrylate, polyacrylic acid, polyethylene oxide, and the like.
That is, unlike other film-forming components, polyvinyl alcohol or a polyvinyl alcohol-based copolymer can maintain material properties such as tensile strength of a film and the like even if a large amount of active components (e.g., surfactants) are embedded in a matrix formed of polyvinyl alcohol or a polyvinyl alcohol-based copolymer. The present inventors have also found that polyvinyl alcohol or a polyvinyl alcohol-based copolymer exhibits excellent cleaning performance even with a water storage texture of a standard size, because the polyvinyl alcohol or polyvinyl alcohol-based copolymer per unit area can accommodate a large amount of surfactant within the material performance limit required for a sheet-type detergent.
In the sheet for washing of the present disclosure, particularly, polyvinyl alcohol or a copolymer based on polyvinyl alcohol has various molecular weights and saponification degrees, and when film forming property, solubility, ease of manufacture, storage stability, cleaning property, process efficiency (viscosity of a mixed solution), and the like are comprehensively considered, it is preferable to use a copolymer having a number average molecular weight of 10,000 to 100,000, more preferably to use a copolymer having a number average molecular weight of 20,000 to 50,000, and even more preferably to use a copolymer having a number average molecular weight of 20,000 to 30,000.
Further, the preferred degree of saponification of the polyvinyl alcohol or polyvinyl alcohol-based copolymer varies depending on the purpose of the present disclosure, on whether the polymer is a copolymer, whether an alkaline builder is used, and the like. More specifically, when the polymer is polyvinyl alcohol and an alkali builder is not used, the preferred degree of saponification is 80% to 90%. Further, when the polymer is preferably a specific copolymer including a comonomer of the following chemical formula 1 or 2 according to the present disclosure and an alkali builder is used, the saponification degree is preferably 60% to 90%, more preferably 70% to 85%, even more preferably 70% to 82%.
The present disclosure also provides a tablet for washing comprising a polymer, a surfactant and an alkali builder,
wherein i) the polymer is a polyvinyl alcohol-based copolymer comprising an anionic monomer unit having a carboxyl group, and
ii) the surfactant is a non-aromatic surfactant which does not contain an ethylene oxide group in the structure, preferably an alkyl sulphate having 8 to 18 carbon atoms, more preferably a lauryl sulphate.
As the copolymer, a copolymer comprising a vinyl alcohol monomer unit of the following chemical formula 1 or 2 and an anionic monomer unit is preferable, and a copolymer composed of a vinyl alcohol monomer unit of the following chemical formula 1 or 2 and an anionic monomer unit is more preferable. In this case, copolymers containing 0.5 to 5 mol% of anionic monomer units are particularly preferred.
< chemical formula 1>
< chemical formula 2>
In chemical formulas 1 and 2, R1、R2And R3Each of which is independently H or methyl, and n is independently an integer of 0 to 3.
When polyvinyl alcohol (PVA) is used as a main formulation, there is a problem in that it may be solidified by an alkaline builder, which is one of the cleaning active components. When a polyvinyl alcohol-based copolymer is used as a film-forming substrate instead of PVA, film-forming properties, solubility of a film, and cleaning efficiency of a sheet for washing can be improved at the same time, even in the presence of an alkaline builder. However, surprisingly, all anionic monomers are not suitable as monomers for the copolymer, and only copolymers comprising anionic monomers having a carboxyl group are suitable for the purposes of the present disclosure. For example, containing a compound having-SO3Anionic mono-of HThe PVA copolymer in bulk is easily gelled by alkaline builder, and as a result, the sheet is difficult to dissolve after being manufactured.
Further, quite particularly, in the sheet for washing containing the metal salt of alkyl sulfate, the alkali builder, and the PVA copolymer, the saponification degree of the PVA copolymer is preferably 60% to 90%, more preferably 70% to 85%, even more preferably 70% to 82%. Specifically, when the saponification degree is too high (e.g., more than 90%), a phenomenon in which the solubility of the sheet after manufacture is greatly reduced occurs, and when the saponification degree is too low (e.g., less than 60%), the water solubility of the copolymer is reduced. Notably, this result is different from the results discussed above for the preferred degree of saponification of PVA.
The present disclosure is based on the following unexpected and surprising findings: in the case of using polyvinyl alcohol or a polyvinyl alcohol-based copolymer as a substrate of a sheet for washing, quite particularly, among various surfactants (nonionic surfactant, ionic surfactant, amphoteric surfactant, etc.), a non-aromatic surfactant not containing an ethylene oxide group in the structure is highly preferably used as a main surfactant in terms of film formability, cleaning performance, stability, etc., in accordance with the object of the present disclosure. Among the non-aromatic surfactants having no ethylene oxide group in the structure, in particular, alkali metal alkylsulfates having 8 to 18 carbon atoms are more preferable, and even more preferable are alkali metal lauryl sulfates, and most preferable are sodium lauryl sulfates.
Preferably, the primary surfactant is present in an amount of 50 wt% or more, more preferably 60 wt% or more, and even more preferably 70 wt% or more, based on the total weight of the surfactant.
When a surfactant containing a large amount of ethylene oxide groups in the structure, for example, Sodium Lauryl Ether Sulfate (SLES) or a nonionic surfactant to which EO is added, is used as a main surfactant, the film-forming properties are greatly reduced. The structural property of ethylene oxide to attract water molecules is considered to be a cause of the decrease in solubility of polyvinyl alcohol in water and the deterioration of material properties of the sheet for washing; however, the present disclosure is not limited to this theoretical assumption.
Further, in the case of using a surfactant having an aromatic group, for example, Linear Alkylbenzenesulfonate (LAS), when the sheet is manufactured with the surfactant together with polyvinyl alcohol, film-forming properties, storage stability, and the like are greatly reduced. When a surfactant having an aromatic group is used as the main surfactant, compatibility with polyvinyl alcohol or a polyvinyl alcohol copolymer used as a film-forming substrate is poor, and good film properties cannot be ensured.
Thus, more preferably, in a sheet for washing comprising a polyvinyl alcohol polymer/copolymer and a surfactant, the present disclosure includes a non-aromatic surfactant having no ethylene oxide group in the structure as the surfactant. Further, more preferably, the non-aromatic surfactant containing no ethylene oxide group is a main surfactant regarded as preferably accounting for 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more, based on the total content of the surfactants.
The non-aromatic surfactant without ethylene oxide groups used as the primary surfactant may be an alkyl sulfate RSO4 -M+(M is an alkali metal, preferably sodium or potassium, more preferably sodium), an alpha olefin sulfonate, an alkali metal alkane sulfonate (preferably potassium salt), an alkali metal aliphatic sulfonate (preferably potassium salt), a fatty acid, an alkyl glycoside, and the like, in which case alkyl sulfates are particularly preferred for various purposes of the present disclosure, and particularly surprisingly, sodium lauryl sulfate is more preferred for various purposes of the present disclosure (including film forming and the like). The number of carbon atoms of the alkyl group or alkane in the structure contained in the non-aromatic surfactant containing no ethylene oxide group is preferably C8 to C18, and the number of carbon atoms of the fatty acid is preferably C8 to C18.
While not being bound by theory, it is suggested that alkyl sulfate surfactants comprising saturated hydrocarbons of C8 to C22 (preferably C8 to C18, more preferably C12 to C16) are particularly preferred because they can improve cleaning performance while giving good strength to the tablet formulation due to their excellent compatibility with polyvinyl alcohol polymers/copolymers as film forming substrates, even at high surfactant levels; however, the present disclosure is not limited to this theoretical assumption.
If a sheet for washing is manufactured using the polyvinyl alcohol polymer/copolymer according to the present disclosure and a specific surfactant, the total content of all surfactants is preferably 30 to 80 wt% (more preferably 40 to 70 wt%) based on the total weight of the sheet after drying, and the content of the polyvinyl alcohol polymer/copolymer is preferably 20 to 50 wt% (more preferably 30 to 50 wt%, even more preferably 35 to 50 wt%) based on the total weight of the sheet after drying.
As shown in the following experimental results, when the content of the polyvinyl alcohol polymer/copolymer is less than 35 wt%, the material property (i.e., strength) of the sheet is good, but there is a possibility that a surfactant component oozes out (smear) based on storage conditions, and when the content of the polyvinyl alcohol polymer/copolymer is less than 30 wt%, the strength of the sheet is significantly reduced while having the above-mentioned problems, so that use defects may occur.
When the content of the surfactant is less than the above range, the cleaning performance is reduced, and when the content exceeds the above range, the content of the polyvinyl alcohol polymer/copolymer is relatively reduced, and thus, the sheet formulation is difficult to manufacture.
In addition to the polyvinyl alcohol polymer/copolymer and surfactant, the sheet for washing may also contain additives described below, for example, fluorescent dyes, enzymes, and the like.
Preferably, the present disclosure provides a sheet for washing comprising a polyvinyl alcohol polymer/copolymer and a surfactant, wherein the surfactant comprises:
(a) a primary surfactant which is a non-aromatic surfactant (more preferably of the formula RSO) which does not contain ethylene oxide groups in the structure4 -M+(M is an alkali metal, preferably sodium or potassium, most preferably sodium) having from 8 to 18 carbon atoms,even more preferably sodium alkyl sulfate, most preferably sodium lauryl sulfate), and
(b) the co-surfactant is heptyloxyethylated lauryl alcohol (LA7), nonyloxyethylated alcohol (LA9) or a mixture thereof.
The present disclosure is also based on the following surprising findings: in the sheet for washing manufactured using polyvinyl alcohol or a copolymer based on polyvinyl alcohol and a surfactant as a cleaning active component, when a non-aromatic surfactant (more preferably an alkyl sulfate having 8 to 18 carbon atoms, even more preferably an alkyl sodium sulfate, most preferably sodium lauryl sulfate) having no ethylene oxide group in the structure is used as a primary surfactant and a nonionic surfactant LA7 or LA9 (preferably LA7) is used as a secondary surfactant, cleaning performance can be greatly improved while film forming properties are maintained. When other surfactants with excellent cleaning performance are combined with the polyvinyl alcohol polymer/copolymer and lauryl sulfate system, surprisingly, LA7 or LA9 only reduces film formation to a low degree or performs well in improving cleaning performance.
Therefore, more preferably, the present disclosure provides tablets for washing manufactured using a surfactant containing only (a) lauryl sulfate (most preferably sodium salt) as a main surfactant and (b) LA7 and/or LA9 (preferably LA 7).
Further, preferably, the present disclosure provides a tablet for washing, characterized in that the mixing ratio (a: b) between (a) and (b) is 90: 10 to 60: 40, more preferably 80: 20 to 70: 30.
When too much LA7 or LA9 was mixed as a co-surfactant, it penetrated through the sheet and deteriorated the properties of the sheet, which may make it difficult to handle, while when too little LA7 or LA9 was mixed as a co-surfactant, the improvement in cleaning performance was not significant.
Accordingly, the present disclosure provides a sheet for washing manufactured using polyvinyl alcohol or a copolymer based on polyvinyl alcohol, alkyl sulfate, which is a polymer made of RSO, as a primary surfactant, LA7, LA9, or a mixture thereof, as a secondary surfactant4 -M+(M is an alkali metal, preferably sodium or potassium, most preferably sodium) (preferably sodium alkyl sulfate, more preferably sodium lauryl sulfate), wherein the content of the polyvinyl alcohol or the copolymer based on polyvinyl alcohol is 30 to 50% by weight, the content of the sodium alkyl sulfate used as the primary surfactant is 30 to 60% by weight, and the content of the secondary surfactant is 10 to 20% by weight, based on the total weight of the dried sheet.
In the formulations according to the present disclosure, the present disclosure is also based on the following surprising findings: preferably, substantially no starch is used as a formulation (film-forming substrate). When starch is mixed and used as a formulation (i.e., starch is contained as one of the components constituting the tablet), a desorption phenomenon of the surfactant (poor compatibility) occurs after drying, and the strength of the tablet decreases as the starch content increases. Furthermore, as the starch content increases, the solubility decreases.
In the present disclosure, "substantially not used" means "comprising 5 wt.% or less, preferably 3 wt.% or less, more preferably 1 wt.% or less, even more preferably zero", based on the dry weight of the sheet.
The sheet for washing according to the present disclosure may further include the following to improve cleaning performance or film-forming performance within a range that does not deteriorate film-forming property, storage stability, ease of manufacturing, and the like: fluorescent whitening enzymes (e.g., cellulases, proteases, etc.), alkaline builders (e.g., sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium metasilicate, alkaline sodium silicate, neutral sodium silicate, sodium tripolyphosphate, sodium pyrophosphate, sodium borate, zeolites (sodium aluminosilicates), sesquicarbonates, MEA, TEA), disintegrants/disintegration aids (e.g., starches, cellulose derivatives, sodium chloride, citric acid, glycerol, propylene glycol), fabric softeners (e.g., cationic surfactants of quaternary ammonium chloride groups, silicone fabric softening components), bleaching agents (e.g., perborates, percarbonates, acidic phosphates (superphosphates), diacyl, tetraacyl peroxides); dispersing/emulsifying agents (e.g., polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene polyoxypropylene block polymers), bactericides/disinfectants (e.g., sodium hypochlorite, hydrogen peroxide, urea peroxide); perfumes, preservatives, dyes, antimicrobial agents, and the like.
The thickness of the sheet for washing according to the present disclosure is preferably 1 μm to 1cm, more preferably 5 μm to 0.5cm, and most preferably 50 μm to 1 mm. When the thickness of the dried sheet for washing is less than 1 μm, the support of the active component is insufficient, the strength of the film is low, it is difficult to obtain desired properties, and when the thickness of the dried sheet for washing is more than 1cm, dissolution becomes slow, and deterioration of cleaning properties becomes noticeable.
More preferably, the present disclosure provides a tablet-type water-soluble laundry detergent comprising 20 to 50 wt% (preferably 30 to 50 wt%) PVA, 30 to 50 wt% SLS, 10 to 20 wt% LA7/9, optionally 1 to 5 wt% fluorescent whitening agent, and optionally 1 to 5 wt% enzyme, based on the total weight of the dried tablet. When the sheet type laundry detergent of the present disclosure is put into a washing machine together with laundry and used therein, it is completely dissolved, thereby eliminating the need for a removal process.
In addition to the polyvinyl alcohol or the polyvinyl alcohol-based copolymer, the primary surfactant, and the co-surfactant, the sheet for washing according to the present disclosure may further contain another co-surfactant in a narrow range amount so as not to hinder the object of the present disclosure. A surfactant containing an ethylene oxide group in the structure may be further included as another co-surfactant, and sodium laureth sulfate may be used as a surfactant containing an ethylene oxide group in the structure.
The sheet for washing according to the present disclosure may further include, as a co-surfactant, an aromatic surfactant in a range such that the object of the present disclosure is not hindered, in addition to the polyvinyl alcohol or the copolymer based on polyvinyl alcohol and the primary surfactant, and may use an alkyl benzene sulfonate as the aromatic surfactant, and preferably, the alkyl group of the alkyl benzene sulfonate is a linear alkyl group having 8 to 18 carbon atoms.
The sheet for washing of the present disclosure may be used in a state of being divided into at least two layers, one layer of which is stacked and integrated thereon according to the present disclosure.
The sheet for washing according to the present disclosure may be manufactured by the following steps: dissolving polyvinyl alcohol or a polyvinyl alcohol-based copolymer in an appropriate amount of water to prepare a polyvinyl alcohol polymer/copolymer solution, mixing the solution with other components including a surfactant and the like, molding the resultant into a sheet of uniform thickness, and drying. Further, the sheet for washing according to the present disclosure is not limited to the aforementioned manufacturing method, and for example, the manufacturing method may include dissolving other components (e.g., surfactant) before dissolving the polyvinyl alcohol or the polyvinyl alcohol-based copolymer in water.
The present disclosure is also based on the fact that: it is preferable to further include a foaming process in the manufacturing method to improve the solubility of the tablet of the present disclosure in water, and many advantages of the tablet for washing in terms of water solubility, water dissolution rate, etc. can be better provided when the specific gravity is adjusted to 0.6 to 0.9 by the foaming process. Accordingly, the present disclosure provides a method of manufacturing a tablet for washing comprising the steps of: preparing a solution comprising polyvinyl alcohol or a polyvinyl alcohol-based copolymer and a surfactant, foaming, and drying. That is, the present disclosure provides a sheet for washing comprising a plurality of holes formed by a foaming process.
Accordingly, the present disclosure also provides a sheet for washing having the above technical features and additional features of a specific gravity of 0.6 to 0.9.
Advantageous effects
The present disclosure provides a tablet for washing, which is completely dissolved and thus does not need to be removed after washing, has excellent cleaning performance, is simple and easy to use, ensures storage stability, and does not involve or cause inconvenience in use.
Drawings
FIG. 1 is a graph showing the molecular weight, PVA content and solid phase base of polyvinyl alcohol (PVA)Graph of experimental results of sheet tensile strength change in water content of body. For example, in the value "03-40-170" on the X-axis, the first value indicates the degree of polymerization/100 (i.e., 03 indicates the degree of polymerization is 300), the second value indicates the PVA content (wt%), and the third value indicates the water content (wt%) on a solid basis. PVA has a molecular weight of about 50 times the degree of polymerization. The value on the Y-axis represents the tensile strength in kilograms of force per centimeter2(kgf/cm2)。
Fig. 2 is a graph illustrating the results of changes in tensile strength caused by substituting starch for a portion of PVA used as a formulation. In the figure, the value on the Y-axis represents the tensile strength in kgf/cm2. In FIG. 2, the red boundary line shows that the minimum tensile strength required when the sheet is used is 5kgf/cm2(if less than this minimum tensile strength, the sheet is susceptible to tearing or rupture).
FIG. 3 is a graph illustrating the change in viscosity with increasing molecular weight of PVA at specific levels. In this case, the water content was 240% on a solid basis for each mixed solution.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in detail to help understanding the present disclosure. However, various changes and modifications may be made to the embodiments of the present disclosure, and it is to be understood that the scope of the present disclosure is not limited to the following embodiments. Embodiments of the present disclosure are intended to provide those skilled in the art with a more complete description of the disclosure.
< example 1> selection of suitable polymers for washed tablets
Sheets for washing were manufactured using different polymers according to table 1, evaluated in terms of film forming properties, solubility and storage stability of the polymers. The results are shown in table 1 below.
A polymer solution or suspension was prepared by dissolving or suspending 100g of the corresponding polymer in an appropriate amount of distilled water or ethanol (about 400 g). The sheet for washing (thickness: 0.01cm) was manufactured by applying the polymer solution or suspension to a release film (release film) at a predetermined thickness using an Elcometer film applicator, and dried in a drying oven at 115 ℃ for 10 minutes. The film forming properties were evaluated at three levels (excellent, good and poor) using the sheet during and after manufacture.
The solubility was evaluated as follows. The prepared film was cut into 5cm × 5cm, and then about 300ml of pure water of 15 ℃ was put into a 500ml beaker and stirred at a constant speed. The length of time it takes for the film to completely decompose and dissolve is measured and solubility is evaluated on three levels: excellent (equal to or less than 3 minutes), good (3 to 5 minutes) and poor (greater than 10 minutes).
TABLE 1
In Table 1, ATC denotes [2- (acryloyloxy) ethyl ] trimethylammonium chloride; DMAEMA represents dimethylaminoethyl methacrylate; HEA represents hydroxyethyl acrylate, HEC represents hydroxyethyl cellulose; and HPMC denotes hydroxypropylmethylcellulose.
As shown in table 1, polyvinyl alcohol is most preferable as the polymer for producing a sheet for washing in terms of film forming property for producing a sheet for washing and solubility of the resulting sheet, ease of production, and storage stability.
< example 2> evaluation of the Effect on the content and molecular weight of PVA
Further, as a result of evaluating film formability, solubility, ease of manufacture, storage stability, cleaning performance, and process efficiency (viscosity of a mixed solution) using polyvinyl alcohols having various molecular weights and saponification degrees, according to the purpose of the present disclosure, when considering the relationship with the content used, polyvinyl alcohol or a polyvinyl alcohol copolymer having a number average molecular weight of 10,000 to 100,000 is preferable, a polymer having a molecular weight of 20,000 to 50,000 is more preferable, and PVA having a molecular weight of 20,000 to 30,000 or a copolymer thereof is even more preferable. Further, as for the degree of saponification, when an alkali builder is not mixed, a polymer having a degree of saponification of 80% to 90% is preferable, and when a PVA copolymer is used and an alkali builder is mixed, a polymer having a degree of saponification of 60% to 90% (more preferably 70% to 85%, even more preferably 70% to 82%) is particularly preferable. When a polymer having a saponification degree in a lower range than the above saponification degree is used, the water solubility is lowered, whereas when a polymer having a saponification degree in a higher range than the above saponification degree is used, a gelation phenomenon occurs.
The results of experiments confirming the above disclosure are shown in tables 3 and 4 below. The production and evaluation of the sheet were carried out in a similar manner to example 1. In this case, the casting condition was 1100 μm (coating thickness of the mixed solution), and the drying condition was 115 ℃ and 15 minutes. The film material properties including transfer index, etc. (the "dried surface") were scored and evaluated. For example, 1 point indicates that no abnormality is found in the film except for a residue on the surface, and 3 points indicates that a phase separation phenomenon has occurred on the film surface and a residue remains on the surface. The evaluation criteria for solubility and tensile strength are shown in table 2 below.
TABLE 2
In the case where the content of the polymer was changed, the total solid (PVA, SLS, LA7 and others) content was adjusted to 100% by supplementing or reducing the surfactant (SLS, LA7) and the content of other components (fluorescent whitening agent, enzyme, perfume, etc.) was fixed to 5% by weight. 40% by weight of PVA, 45% by weight of SLS, 10% by weight of LA7 and 5% by weight of the other components were used as a base formulation (formulation No. 1). In Table 3, the content of PVA indicates that PVA accounts for the weight% of the total solids other than water, and the water content indicates that water accounts for the weight% of the total solids when preparing the mixed solution. That is, in the formulation No.1, a PVA content of 40% means that 40% by weight of PVA is contained in the total solids, and since a water content of 63% means that 37% of solids and 63% of water are contained in the mixed solution for producing a sheet, the water content is about 170 assuming that the solids content is 100.
TABLE 3
TABLE 4
In formulation No.13, the drying time was increased by two minutes.
As shown in tables 3 and 4, in the case where the number average molecular weight of PVA is less than or equal to about 15,000, the strength of the sheet is low, and a desorption phenomenon of the surfactant (poor compatibility) occurs after drying. To solve this problem, the content of PVA in the sheet is increased to improve the formability and strength of the sheet, but the cleaning performance is also decreased due to the decreased content of active components.
Meanwhile, as the molecular weight increases, the surface of the sheet is stabilized (compatibility improves) and the strength of the sheet increases. Therefore, the higher the molecular weight, the more advantageous it is to ensure the formability of the sheet at a low PVA content; however, since the viscosity of the mixed solution is too high, it is basically difficult to ensure process efficiency suitable for mass production. At the same time, the water content can be increased to improve this problem (i.e. lower viscosity), but this involves a significant reduction in yield.
Therefore, as a result, the number average molecular weight of PVA or a copolymer thereof used is preferably 20,000 or more in view of sheet strength and compatibility with the cleaning active component. Further, in the case of having a predetermined PVA content (about 30%) and a predetermined water content (240% by weight on a solid basis), 5,000cps or less is appropriate in view of the manufacturing process, and therefore, the number average molecular weight of the PVA or its copolymer is preferably 5,000 or less, more preferably 30,000 or less.
In connection with this, when 30 wt% PVA, 52 wt% SLS, 13 wt% LA7, and 5 wt% of other components were used, and 240 parts by weight of water was used to manufacture a sheet based on 100 parts by weight of the solid sheet, the viscosity of the polymer solution, which varied as the molecular weight of PVA increased, was measured, and the results thereof are shown in table 3. Neither too high or too low a viscosity of the polymer solution used in the manufacturing process is preferred, and it has been found that the viscosity of polymer solutions containing the components of the present disclosure increases rapidly starting from a molecular weight of about 50,000.
For reference, the results of measuring the change in tensile strength of the sheet based on molecular weight, PVA content, and water content based on solids are shown in fig. 1. Depending on the use of the sheet, 5kgf/cm is required2Or more (when the tensile strength is 5 kgf/cm)2Or less, it is easily torn or broken), 10kgf/cm2Or more, are determined as good levels, depending on the tensile strength, for example, the 05-40-170 formulation, 10-40-170 formulation, 15-30-200 formulation, 10-40-200 formulation, 15-40-240 formulation, 10-30-200 formulation, and 10-35-200 formulation are preferable.
< example 3> evaluation of selection of main surfactant
Tablets for washing were produced according to the components and contents listed in Table 5, and comparative evaluations were made of film forming property and cleaning property of the produced tablets
TABLE 5
Numbering | Components | Content (unit:%) |
1 | Polyvinyl alcohol (PVA) | 40% |
2 | Surfactants of Table 3 | 55% |
3 | |
2% |
4 | Enzyme | 1.5% |
5 | Fragrances and others | 1.5% |
Specifically, a PVA solution was prepared by: 145g of PVA (degree of saponification: 86.5%, average degree of polymerization: 500) was put into 630g of distilled water, and dissolved at 80 ℃ for 2 hours. The other components of table 5 were added to the prepared PVA solution and mixed with a mechanical stirrer. The mixed solution was applied to a release film at a predetermined thickness by using an Elcometer film applicator, and dried in a drying oven at 115 ℃ for 10 minutes to manufacture a PVA film containing a surfactant as a cleaning component.
The evaluation results of the film forming property and the cleaning property based on the surfactant type are shown in table 6. The film forming property was evaluated on three levels (excellent, good and poor) in the same manner as in example 1. The cleaning performance was evaluated by the method specified below, and the cleaning ability of 60% or more based on the soiled fabric (japan) was determined to be excellent, 50% to 59% being good, and 50% or less being poor.
Specifically, the cleaning ability was evaluated using a washing machine of the same condition, in which case rinsing was performed using tap water. Further, the washing temperature was the same cold water as the conditions used at home, wet artificially soiled fabrics (manufactured by the japanese laundry scientific association) and protein-stained fabrics (EMPA 116) were used as the soiled fabrics for detergency evaluation. Furthermore, the evaluation can be carried out under the condition that the soiled fabric belongs to an all-cotton T-shirt. In addition, a comparative evaluation was performed by a statistical method using 16 soiled fabrics having a size of 5cm × 5 cm. In this case, WB values representing the whiteness index of the stained fabric were measured before and after washing using a color difference meter. The sheet for washing manufactured in the above example was cut into a size of 20cm × 15cm, and two pieces of the cut detergent were used. At the beginning of washing the laundry, the pieces for washing manufactured in the examples were put into a washing machine together with the soiled fabrics, respectively, washed under the conditions of the standard procedure of the washing machine (20 minutes of washing, twice rinsing) and a medium water level, and after dehydration the soiled fabrics were dried in a room (25 ℃, 20% RH) having stable temperature and humidity for one week, ironed, and WB values were measured using the same colorimeter. The obtained results were substituted into the Kubelka-Munk equation expressed as the following equation 2 to calculate the cleaning ability, and the results are shown in table 6.
In equation 1, Rs represents the surface reflectance of the soiled fabric, Rc represents the surface reflectance of the soiled fabric after the washing process, and Ro represents the surface reflectance of the white cotton fabric.
TABLE 6
As shown in table 6, very surprisingly, when polyvinyl alcohol was used as the polymer base material, only Sodium Lauryl Sulfate (SLS) was excellent in film forming property, while other surfactants used for washing were good or poor in film forming property. For example, surfactants LAS, SLES and MEA undergo phase separation during manufacture, have low compatibility with PVA, and the manufactured sheets are sticky or brittle, and thus are not suitable in terms of storage stability and ease of handling of the manufactured sheets.
< example 4> evaluation of selection of cosurfactant
Various tablets for washing were manufactured according to the formulation of table 7 using sodium lauryl sulfate as a primary surfactant and various nonionic surfactants as co-surfactants, and evaluated. A sheet for washing was produced by a method similar to example 3.
TABLE 7
In Table 7, PVA(1)Polyvinyl alcohol, SLS, showing a degree of saponification of 86.5% and an average degree of polymerization of 500(2)Tinopal CBS-X (Ciba Specialty chemical) was used as fluorescent dye corresponding to sodium lauryl sulfate(3)。
The tablets for washing manufactured above were tested by the same method as in example 1 or example 3, and the tablets were evaluated based on the criteria of table 8, with the results shown in table 9.
The tensile strength of the film was evaluated as follows. Test methods were in accordance with the test method of ISO 527-3 standard, using the universal test apparatus Zwick 1120. Each sample was made with a uniform thickness of 0.2mm and cut into 2X 10 (cm)2) The specimen was clamped with screw clamps, the distance between the clamps was maintained at 50mm, and the tensile test was performed at a speed of 20 mm/min. The point of time when the film could not withstand the tensile force and was broken was set as the tensile strength, and the values of table 8 were set as standards in view of the convenience of use.
TABLE 8
TABLE 9
As shown in table 9, LA7 and LA9 were overall better than other nonionic surfactants in terms of cleaning ability and material properties, and LA7 was better than LA9 in terms of cleaning ability.
< example 5> evaluation of effects of SLS as a primary surfactant and LA7 content as a secondary surfactant.
Tablets for washing were made while varying the content of SLS as the primary surfactant and LA7 as the secondary surfactant, along with the components and content of table 10. The manufacturing method was the same as in example 4.
The film forming property and cleaning property of the sheet for washing thus manufactured were evaluated by the same evaluation method as example 4, and the results are shown in table 11.
TABLE 11
As shown in table 11, when film-forming property and cleaning property are considered, the preferred SLS content is preferably 40 to 50 wt%, and the preferred LA7 content as the nonionic surfactant is 5 to 15 wt%, based on the total weight of the sheet.
< example 6> comprehensive evaluation
Water-soluble tablets were manufactured according to the formulation and content of table 12 and evaluated in various aspects. The manufacturing method was the same as in example 4.
TABLE 12
In Table 12, PVA having a saponification degree of 86.5% and an average polymerization degree of 500 was used as PVA, polyoxyethylene alkyl ether LA7 was used as a nonionic surfactant, AOS was an α -olefin sulfonate, and Tinopal CBS-X (Ciba Specialty chemical) was used as a fluorescent dye.
Evaluation of tabletability
The formability of the water-soluble sheet detergents produced in the above examples and comparative examples was evaluated by macroscopic observation based on the following criteria, and the results are shown in table 13.
Very good: the tablet preparation is flexible and excellent and has no phenomenon of exudation of yin.
O: the tablet formulation is flexible, but has a slight exudation of the liquid component.
Δ: the sheet was not flexible enough and slight vaginal bleeding occurred.
X: no tablet formulation was formed and a large amount of the liquid component was oozed out.
Watch 13
As shown in table 13, it was found that examples a, b, c, d, k and l were excellent in the sheeting property, and the film forming property was significantly reduced as the content of the nonionic surfactant and SLES was increased.
Evaluation of solubility and tensile Strength
The tablets for washing manufactured in the above examples and comparative examples were tested by the same method as example 4, and the solubility and tensile strength thereof were evaluated. The results are shown in table 14.
TABLE 14
In the case of comparative examples a and c, no sheet formulation was formed, and thus the solubility and tensile strength could not be measured.
As shown in table 14, examples a, b, c, d, k and l were particularly excellent in both solubility and tensile strength.
Evaluation of cleaning ability
The tablets for washing produced in the above examples and comparative examples were evaluated for their cleaning ability, which could be produced by the following method (comparative examples a and c were evaluated using the same amount of active ingredient mixed solution instead of water-soluble detergent tablets).
Specifically, the cleaning ability was evaluated using a washing machine of the same condition, in which case rinsing was performed using tap water. Further, the washing temperature was the same cold water as the conditions used at home, and wet artificially soiled fabrics (manufactured by the japan laundry science association) and protein-stained fabrics (EMPA 116) were used as the soiled fabrics for evaluation of detergency. Furthermore, the evaluation was performed under the condition that the soiled fabric was an all-cotton T-shirt. In addition, a comparative evaluation was performed by a statistical method using 16 soiled fabrics having a size of 5cm × 5 cm. In this case, WB values representing the whiteness index of the stained fabric were measured before and after washing using a color difference meter. The pieces for washing produced in the above examples were cut into a size of 20cm × 15cm, and two pieces of the cut detergent were used. At the beginning of washing the laundry, the tablets for washing and the detergent were put into the washing machine together with the soiled fabric, the washing was carried out under the conditions of the standard procedure of the washing machine (20 minutes of washing, twice rinsing) and the medium water level, and after dehydration, dried for one week in a room (25 ℃, 20% RH) with stable temperature and humidity, ironed, and then the W was measured using the same colorimeterBThe value is obtained. The obtained results were substituted into the same Kubelka-Munk equation as example 3 to calculate the cleaning ability, and the results are shown in Table 15.
Watch 15
As shown in table 15, of examples a, b, c, d, k and l having appropriate sheeting property, solubility and tensile strength, example d, which contained 15 wt% of polyoxyethylene alkyl ether as a nonionic surfactant, exhibited the best cleaning performance.
< example 7> evaluation of stability (moisture absorption)
The stability of the tablets for washing manufactured in example d of example 6 was evaluated, and the results are shown in table 16.
TABLE 16
The initial dried residue of the sheet was 95 wt% and the water content was 5 wt%, and the dried residue was measured using a Halogen moisture analyzer after drying at 105 ℃ for 10 minutes.
As shown in table 16, although the product was a water-soluble tablet detergent, stability as a product was ensured under various conditions (including under rainy season conditions of high temperature and high humidity).
< example 8> evaluation of use of PVA copolymer
Tablets for washing were manufactured according to the formulation of table 17 in the same manner as in example 4.
TABLE 17
In Table 17, PVA(1)Representing a polyvinyl alcohol having a degree of saponification of 86.5% and an average degree of polymerization of 500, a copolymer of vinyl alcohol (98 mol%, degree of saponification: about 77 mol%) -methacrylic acid (2 mol%) was used as the PVA copolymer(2),SLS(3)Sodium carbonate (soda) was used as builder, corresponding to sodium lauryl sulfate(4)Tinopal CBS-X (Ciba Specialty chemical) was used as fluorescent dye(5)。
The produced tablets for washing were evaluated by the same method as in example 4, and the results are shown in table 18.
As shown in table 18, when a builder was added to PVA, PVA solidified, so that solubility and material properties were significantly deteriorated, and cleaning properties did not produce the effect of the builder due to such insoluble components. However, when the PVA copolymer is used, solidification does not occur even if a builder is added, and cleaning performance is improved due to the builder, and when the viscosity is greater than or equal to a predetermined level, the effect is offset due to a decrease in cleaning performance due to a relative decrease in the amount of the surfactant. Further, when the amount of the builder is 7.5% or more, the strength of the sheet is reduced due to a large amount of the builder in the film.
< example 9> evaluation of Effect of starch addition
Tablets were made according to the formulation of table 19, using PVA, starch or mixtures thereof as a formulation to evaluate the effect of adding starch. Evaluation was performed in the same manner as in the experiment of example 2, and the results are shown in table 20, and the tensile strength in the results of table 20 is shown in fig. 2.
Watch 19
Raw materials | Content (wt.) | |
1 | Formulation | 40% |
2 | SLS | 45% |
3 | |
10% |
4 | Others | 5% |
Water (W) | 170 (tablet solid relative to 100) |
As shown in table 20 and fig. 2, when starch was mixed and used together as a formulation (i.e., including starch as a component of a tablet), a desorption phenomenon (poor compatibility) of the surfactant occurred after drying, and as the starch content increased, the strength of the tablet decreased. Furthermore, as the starch content increases, the solubility also decreases. Thus, it was found that starch is preferably not used in the manufacture of tablets for washing according to the present disclosure. In order to overcome the problems of compatibility and tensile strength, there is a drawback that the content of the formulation in the tablet has to be increased (50% or more), and in order to improve the solubility, there is a drawback that the starch has to be gelatinized first.
The following corresponds to the original claims in the parent application, which are now incorporated as part of the specification:
1. a sheet for washing, which is manufactured using polyvinyl alcohol or a polyvinyl alcohol-based copolymer as a polymer and which comprises a surfactant, wherein the surfactant does not contain an ethylene oxide group in the structure and is non-aromatic.
2. A sheet for washing according to item 1, wherein the surfactant which does not contain an ethylene oxide group in the structure and is non-aromatic is composed of RSO4 -M+Alkyl sulfates represented by (M is an alkali metal), alpha-olefin sulfonates, alkali metal alkanesulfonates, alkali metal aliphatic methylsulphonates, fatty acids, alkyl glycosides or mixtures thereof.
3. The tablet for washing according to item 1, wherein the surfactant comprises an alkali metal alkylsulfate having 8 to 18 carbon atoms.
4. A tablet for washing according to item 3, wherein the alkali metal alkylsulfate is sodium lauryl sulfate.
5. The tablet for washing according to item 1, wherein the surfactant which does not contain an ethylene oxide group in the structure and is non-aromatic is a main surfactant in an amount of 50% by weight or more based on the total content of the surfactant.
6. The tablet for washing according to item 3, wherein the alkali metal alkylsulfate is a main surfactant in an amount of 50% by weight or more based on the total content of the surfactant.
7. The tablet for washing according to item 5 or 6, wherein the content of the main surfactant is 60% by weight or more based on the total content of the surfactant.
8. The sheet for washing according to item 1, wherein the total content of the surfactant is 40 to 70% by weight based on the total weight of the sheet, and the total content of the polyvinyl alcohol or the polyvinyl alcohol-based copolymer is 30 to 50% by weight based on the total weight of the sheet.
9. The sheet for washing according to item 1, wherein the polyvinyl alcohol or the polyvinyl alcohol-based copolymer has a number average molecular weight of 20,000 to 50,000.
10. The sheet for washing as set forth in item 1, wherein the polymer is polyvinyl alcohol having a saponification degree of 80% to 90%.
11. The tablet for washing according to item 1, wherein the tablet further comprises heptyloxyethylated lauryl alcohol (LA7), nonyloxyethylated lauryl alcohol (LA9), or a mixture thereof as a co-surfactant, in addition to the primary surfactant.
12. The tablet for washing according to item 11, wherein the mixing weight ratio of the primary surfactant to the secondary surfactant (the primary surfactant: the secondary surfactant) is from 90: 10 to 60: 40.
13. The sheet for washing according to item 11, wherein the total content of the polyvinyl alcohol or the polyvinyl alcohol-based copolymer in the sheet is 30 to 50% by weight based on the total weight of the sheet after drying, the content thereof is 30 to 60% by weight, and the total content of the secondary surfactant is 10 to 20% by weight, comprising an alkali metal lauryl sulfate as the primary surfactant.
14. The tablet for washing according to item 1, wherein the tablet for washing has improved water solubility by containing pores formed through a foaming process.
15. The sheet for washing according to item 14, wherein the specific gravity of the sheet for washing is from 0.6 to 0.9.
16. A tablet for washing, comprising a polymer, a surfactant and an alkali builder, wherein the polymer is a polyvinyl alcohol-based copolymer comprising a monomer unit having a carboxyl group, the surfactant does not contain an ethylene oxide group in the structure and is non-aromatic.
17. The sheet for washing according to item 16, wherein the copolymer comprises a vinyl alcohol unit of the following chemical formula 1 or 2 and an anionic monomer unit, the content of the anionic monomer unit being 0.5 to 5 mol%:
< chemical formula 1>
< chemical formula 2>
Wherein R is1、R2And R3Each of which is independently H or methyl, and n is independently an integer of 0 to 3.
18. A tablet for washing according to item 16, wherein the surfactant which does not contain an ethylene oxide group in the structure and is non-aromatic is composed of RSO4 -M+Alkyl sulfates represented by (M is an alkali metal), alpha-olefin sulfonates, alkali metal alkanesulfonates, alkali metal aliphatic methylsulphonates, fatty acids, alkyl glycosides or mixtures thereof.
19. A tablet for washing according to item 16, wherein the surfactant comprises an alkali metal alkyl sulfate having 8 to 18 carbon atoms.
20. The tablet for washing according to item 19, wherein the alkali metal alkylsulfate is sodium lauryl sulfate.
21. The tablet for washing according to item 19, wherein the alkali metal alkylsulfate is a main surfactant in an amount of 60% by weight or more based on the total content of the surfactant.
22. The sheet for washing of item 16, wherein the total content of the surfactant is 40 to 70% by weight based on the total weight of the sheet, and the total content of the polyvinyl alcohol-based copolymer is 30 to 50% by weight based on the total weight of the sheet.
23. The sheet for washing according to item 16, wherein the polyvinyl alcohol-based copolymer has a number average molecular weight of 20,000 to 50,000.
24. The sheet for washing according to item 16, wherein the polyvinyl alcohol-based copolymer has a saponification degree of 60% to 85%.
25. The tablet for washing of item 16, wherein the tablet further comprises heptyloxyethylated lauryl alcohol (LA7), nonyloxyethylated lauryl alcohol (LA9), or a mixture thereof as a co-surfactant, in addition to the primary surfactant.
26. The tablet for washing according to item 16, wherein the tablet for washing has improved water solubility by containing pores formed through a foaming process.
27. The tablet for washing of item 26, wherein the tablet for washing has a specific gravity of 0.6 to 0.9.
28. A tablet for washing according to item 1 or 16, wherein the tablet is substantially free of starch.
29. A method of making a tablet for washing, comprising:
preparing a solution comprising polyvinyl alcohol or a polyvinyl alcohol-based copolymer and a surfactant;
foaming the solution; and
the solution is dried.
30. The method of item 29, wherein the surfactant comprises an alkali metal alkyl sulfate having 8 to 18 carbon atoms.
Claims (17)
1. A sheet for washing, which is manufactured using polyvinyl alcohol or a polyvinyl alcohol-based copolymer as a polymer and which contains a surfactant,
the sheet for washing comprises the surfactant embedded in a polymer matrix, formed by mixing the polymer and the surfactant together,
wherein the surfactant comprises sodium lauryl sulfate,
wherein the thickness of the sheet is 50 μm to 1cm, and
wherein the sheet comprises bubbles.
2. A sheet for washing according to claim 1, wherein the polyvinyl alcohol or the polyvinyl alcohol-based copolymer is contained in a total amount of 30 to 50% by weight based on the total weight of the sheet after drying.
3. A sheet for washing according to claim 1, wherein the polyvinyl alcohol or the polyvinyl alcohol-based copolymer has a number average molecular weight of 20,000 to 50,000.
4. A tablet for washing according to claim 1, wherein the content of the sodium lauryl sulfate as a main surfactant is 50% by weight or more based on the total content of the surfactant.
5. A tablet for washing according to claim 1, further comprising a co-surfactant.
6. A tablet for washing according to claim 5, said co-surfactant comprising sodium laureth sulfate (SLES), heptyloxyethylated lauryl alcohol (LA7), nonyloxyethylated lauryl alcohol (LA9), or a mixture thereof.
7. A tablet for washing according to claim 1, wherein the total content of starch in the tablet is 5 wt% or less based on the total weight of the tablet after drying.
8. A tablet for washing according to claim 1 or 5, wherein the tablet for washing further comprises at least one selected from the group consisting of: alkaline builders, perfumes, enzymes and dyes.
9. A laundry sheet which is produced using a polyvinyl alcohol-based copolymer as a polymer and which contains an alkali builder,
said laundry tablet comprising said alkaline builder embedded in a polymer matrix, formed by mixing together said polymer and said alkaline builder, and
wherein the laundry tablets dissolve during the washing process and do not need to be removed after washing,
the copolymer includes a vinyl alcohol unit of the following chemical formula 1 or 2 and an anionic monomer unit, and the content of the anionic monomer unit is 0.5 to 5 mol%:
< chemical formula 1>
< chemical formula 2>
Wherein R is1、R2And R3Each of which is independently H or methyl, and n is independently an integer of 0 to 3.
11. Use of a copolymer according to claim 10 for the manufacture of a laundry tablet.
12. A surfactant comprising an alkali metal salt of an alkyl sulfate having 8 to 18 carbon atoms.
13. Use of a surfactant according to claim 12 for the manufacture of a laundry tablet.
14. Surfactants including Sodium Lauryl Ether Sulfate (SLES), heptyloxyethylated lauryl alcohol (LA7), nonyloxyethylated lauryl alcohol (LA9), or mixtures thereof.
15. Use of a surfactant according to claim 14 for the manufacture of a laundry tablet.
16. Use of a fluorescent whitening enzyme, an alkaline builder, a disintegrant/disintegration aid, a fabric softener, a bleach, a dispersant/emulsifier, a bactericide/disinfectant, a perfume, a preservative, a dye or an antibacterial agent for the manufacture of laundry tablets.
17. From RSO4 -M+(M is an alkali metal), an alpha-olefin sulfonate, an alkali metal alkane sulfonate, an alkali metal aliphatic methyl ester sulfonate, a fatty acid, an alkyl glycoside, or a mixture thereof for producing a laundry tablet.
Applications Claiming Priority (11)
Application Number | Priority Date | Filing Date | Title |
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KR20110045256 | 2011-05-13 | ||
KR10-2011-0045257 | 2011-05-13 | ||
KR10-2011-0045256 | 2011-05-13 | ||
KR1020110045257A KR101146292B1 (en) | 2011-05-13 | 2011-05-13 | Laundry sheet comprising lauryl sulfate salt |
KR20110045255 | 2011-05-13 | ||
KR10-2011-0045255 | 2011-05-13 | ||
KR1020110132080A KR101358923B1 (en) | 2011-05-13 | 2011-12-09 | Sheet for laundry |
KR10-2011-0132083 | 2011-12-09 | ||
KR1020110132083A KR101787652B1 (en) | 2011-05-13 | 2011-12-09 | Sheet for laundry |
KR10-2011-0132080 | 2011-12-09 | ||
CN201280029267.2A CN103608448B (en) | 2011-05-13 | 2012-04-17 | For the piece of washing |
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CN201280029267.2A Division CN103608448B (en) | 2011-05-13 | 2012-04-17 | For the piece of washing |
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CN201280029267.2A Active CN103608448B (en) | 2011-05-13 | 2012-04-17 | For the piece of washing |
CN202110242566.5A Pending CN113004991A (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
CN201810511711.3A Active CN108559679B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
CN201610879699.2A Active CN106978264B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
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CN201810511711.3A Active CN108559679B (en) | 2011-05-13 | 2012-04-17 | Washing sheet |
CN201610879699.2A Active CN106978264B (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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KR101772195B1 (en) * | 2015-12-22 | 2017-08-28 | 주식회사 엘지생활건강 | Sheet for laundry |
WO2017111498A1 (en) * | 2015-12-22 | 2017-06-29 | 주식회사 엘지생활건강 | Sheet for washing |
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 |
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CN111051489B (en) * | 2017-09-08 | 2022-06-24 | 株式会社Lg生活健康 | Washing sheet |
WO2019056336A1 (en) | 2017-09-25 | 2019-03-28 | The Procter & Gamble Company | Unitary laundry detergent article |
KR20200055734A (en) * | 2017-10-05 | 2020-05-21 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | Structured unit dose cleaning products |
KR102096260B1 (en) * | 2018-05-02 | 2020-05-28 | (주)넥스트업 | Laundry Detergent Sheet |
WO2020147008A1 (en) * | 2019-01-15 | 2020-07-23 | The Procter & Gamble Company | Flexible and dissolvable solid sheet article |
MX2022004169A (en) | 2019-11-29 | 2022-05-02 | Procter & Gamble | Flexible, porous, dissolvable solid sheet articles having large pores and method of making same. |
WO2021163965A1 (en) | 2020-02-20 | 2021-08-26 | The Procter & Gamble Company | Flexible, porous, dissolvable solid sheet articles containing cationic surfactant |
BR112023005054A2 (en) | 2020-10-09 | 2023-04-18 | Procter & Gamble | MULTILAYER DISOLUBLE SOLID ARTICLE CONTAINING SOLID PARTICLES FOR ITS PRODUCTION |
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Also Published As
Publication number | Publication date |
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CN108559679B (en) | 2021-03-26 |
WO2012157851A9 (en) | 2013-04-04 |
CN107881043B9 (en) | 2020-11-24 |
WO2012157851A3 (en) | 2013-01-24 |
CN108085146A (en) | 2018-05-29 |
CN107828567B (en) | 2019-06-14 |
CN106978264A (en) | 2017-07-25 |
CN107881043A (en) | 2018-04-06 |
WO2012157851A2 (en) | 2012-11-22 |
CN108559679A (en) | 2018-09-21 |
CN103608448B (en) | 2018-06-26 |
CN108085146B (en) | 2020-10-16 |
CN103608448A (en) | 2014-02-26 |
CN107881043B (en) | 2020-08-18 |
CN107828567A (en) | 2018-03-23 |
CN106978264B (en) | 2020-11-03 |
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