JP2008545590A - Water-soluble liquid containing pouch - Google Patents

Abstract

  A water-soluble pouch containing a liquid composition, wherein the water-soluble pouch is made from a film containing a copolymer of vinyl alcohol and carboxylic acid, and the liquid composition contained in the pouch contains carboxylates At least one dissolved ionic component selected from the group consisting of phosphonates, and mixtures thereof, 5% to 15% water by weight of the liquid composition, and the pouch is formed by vacuum forming horizontal Processed using a mold-bag-fill-seal process.

Description

  The present invention relates to a water-soluble / liquid-containing pouch, and more particularly to a pouch that contains cleaning liquids such as detergents and hard surface cleaning agents. More specifically, the present invention provides improved compatibility when used in combination with a selected concentration of water and an ionic component selected from the group consisting of carboxylates, phosphonates, and mixtures thereof. The present invention relates to a water-soluble pouch.

  Liquid filled pouches are known as a convenient form of packaging consumer products in addition to industrial products. The liquid may be provided in a pre-metered amount for use as a “single dose”. The film wrapping the liquid product forms a pouch wall and is soluble in water. A water-soluble film that is particularly suitable for this purpose is made from polyvinyl alcohol, and in this context, the present invention is particularly advantageous for single dose packaging of liquid detergents. Known water-soluble pouches generally are either vertical bag-fill-seal (VFFS) processes or horizontal bag-fill-seal (HFFS) processes. Either directly or by thermoformed water soluble packaging material.

  The liquid product is packaged in a water-soluble film, which is made from a water-soluble copolymer containing vinyl alcohol and carboxylic acid groups. However, many of such water-soluble films are dissolved ions selected from the group consisting of carboxylates, phosphonates, and mixtures thereof when used in combination with the composition filled therein. When it contains a sex component, it shows poor compatibility. Such ionic components are desirable in liquid detergents because they generally function as builders or chelating agents. The incompatibility described above results in a significant loss of solubility in water-soluble pouches made from films containing vinyl alcohol and carboxylic acid copolymers. This solubility loss is particularly problematic when the water-soluble pouch is stored for a long period of time, and may cause a polymeric residue of a water-soluble film on the fabric after washing.

  The insolubilization phenomenon is believed to result from the undesirable formation of lactone rings within and / or on the surface of the water-soluble film. Lactone formation that has already occurred within the film itself comprising a copolymer of vinyl alcohol and carboxylic acid is particularly facilitated when the composition is filled inside a pouch containing dissolved ionic components. The presence of such dissolved ionic components facilitates exchange between counter ions associated with carboxylate groups in the film and hydrogen ions in the liquid composition, thereby promoting lactone formation.

  Even more surprisingly, the addition of the amount of water normally required in a detergent composition to stably dissolve these ionic components is a water solubility made from a film comprising a copolymer of vinyl alcohol and carboxylic acid. An adverse effect on the effect of ionic components on the solubility of the pouch was observed.

  PCT International Publication No. WO 01/79417 discloses a polymer containing a non-aqueous liquid composition comprising an ionic component and an excess of stabilizing compound, which is effective to reduce lactone formation in the film. A water-soluble packaging container formed from a film is disclosed.

  US Pat. No. 6,185,410 describes a pouch made of a water soluble film and containing a liquid composition comprising a solid builder / chelating agent and an anionic surfactant.

  PCT International Publication No. WO 2004/085586 includes a water-soluble pouch containing a liquid containing a dissolved ionic component selected from the group consisting of carboxylates, phosphonates and mixtures thereof, where the pouch is in particular Made from a modified water-soluble film).

  Although the systems disclosed in the prior art provide a solution for obtaining improved compatibility with the ionic components of water-soluble pouches, there remains a need for simpler and less expensive alternative systems.

  Accordingly, while providing a water-soluble liquid-containing pouch that exhibits excellent compatibility with a dissolved ionic component selected from the group consisting of carboxylates, phosphonates, and mixtures thereof, the dissolved ionic component is excellent. It is an object of the present invention to ensure stability and thereby provide improved water solubility of the liquid-containing pouch upon long-term storage.

  The purpose is a liquid-containing water-soluble pouch comprising a dissolved ionic component selected from the group consisting of carboxylates, phosphonates, and mixtures thereof, said pouch being a horizontal bag-fill-seal process (HFFS) It is found that can be satisfied by providing a liquid composition having a carefully selected amount of water.

  Advantageously, the water-soluble liquid-containing pouches of the present invention provide enhanced dissolution and dispersion properties even after long-term storage. Furthermore, when the water-soluble pouches of the present invention provide stable dissolution of ionic components, the latter performs a significantly improved function and requires fewer such components.

  A further advantage of the water-soluble pouches of the present invention is that they may be made using commercially available water-soluble films without requiring any further modification.

  The present invention includes a water-soluble pouch containing a liquid composition, wherein the water-soluble pouch is made from a film comprising a copolymer of vinyl alcohol and carboxylic acid, and the liquid composition contained in the pouch comprises a carboxylate And at least one dissolved ionic component selected from the group consisting of phosphonates and mixtures thereof, and 5-15% water by weight of the liquid composition, and the pouch is vacuum formed Processed using a horizontal, bag-fill-fill-seal process.

  In another embodiment, the present invention includes a method of making a water-soluble pouch having improved water solubility upon storage, said process comprising (a) carboxylates, phosphonates, and mixtures thereof. Blending a liquid composition comprising at least one dissolved ionic component selected from the group and 5-15% water by weight of the liquid composition; and (b) vacuum forming and horizontal mold Using a bag-fill-seal process to process a film comprising a copolymer of vinyl alcohol and carboxylic acid into a water-soluble pouch containing the liquid composition.

Water-soluble film According to the present invention, the water-soluble film comprises a copolymer of vinyl alcohol and carboxylic acid.

  Preferably, the concentration of the copolymer in the film material is at least 60% by weight of the film. The polymer may have any weight average molecular weight, preferably 1.66E-21 g (1,000 daltons) to 1.66E-18 g (1,000,000 daltons), more preferably 66E-20g (10,000 Daltons) to 4.98E-19g (300,000 Daltons), even more preferably, 2.49E-20g (15,000 Daltons) to 3.32E-19g (200,000 Daltons) Most preferably, it is from 3.32E-20 g (20,000 Daltons) to 2.49E-19 g (150,000 Daltons).

  Preferably, the copolymer present in the film is hydrolyzed from 60% to 98%, more preferably from 80% to 95% to improve the dissolution of the material.

  In a highly preferred embodiment, the copolymer comprises 0.1 mol% to 30 mol%, preferably 1 mol% to 6 mol% of the carboxylic acid.

  The water-soluble film of the present invention may further comprise an additional comonomer. Suitable additional comonomers include sulfonates and ethoxylates. An example of a preferred sulfonic acid is 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS).

  A suitable water-soluble film for use in the context of the present invention is commercially available from Mono-Sol Corporation (Indiana, USA) under the trade name M8630®.

  The water-soluble film herein may also contain components other than the polymer or polymer material. For example, plasticizers such as glycerol, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1,3-propanediol, sorbitol and mixtures thereof, additional water, disintegration aids, fillers, antifoaming agents, emulsifying / It may be beneficial to add a dispersant, and / or an antiblocking agent. It may be useful that the pouch or water-soluble film itself contains detergent additives to be supplied to the wash water, such as organic polymeric soil release agents, dispersants, dye transfer inhibitors and the like. If desired, a fine powder may be sprayed on the surface of the pouch to reduce the coefficient of friction. Sodium aluminosilicate, silica, talc and amylose are examples of suitable fine powders.

Liquid Composition The term “liquid” is used herein to broadly include, for example, mixtures, solutions, dispersions and emulsions, with homogeneous liquids being most preferred. The liquid may have a low to very high viscosity and includes gels and pastes. The preferred viscosity may be 10,000 mPa · s or less, measured at 20 sec-1 and 21 ° C., more preferably 100 to 3,000 mPa · s, most preferably 300 to 1,500 mPa · s. . The liquid may contain active ingredients suitable for various uses. Examples of such applications are household and consumer products such as laundry washing and treatment, tableware and hard surface cleaning, shampoos, bath additives; agricultural chemicals such as pesticides, herbicides, fungicides, Pesticides; industrial chemicals such as materials used in the construction industry, materials used in the photographic, printing and textile industries; water treatment chemicals such as swimming pools, water heating systems, sewage and drainage systems; health and beauty For products such as pharmaceutical and cosmetic applications. Particularly preferred liquids are suitable for use as liquid detergents in the cleaning of clothing, tableware and other household surfaces.

  The liquid composition preferably has a density of 0.8 kg / L to 1.3 kg / L, preferably about 1.0 to 1.1 kg / L. The liquid composition can be prepared by any method, and can usually have any viscosity according to its components. If necessary, the viscosity may be adjusted by using various viscosity modifiers such as hydrogenated castor oil and / or solvents. Hardened castor oil is commercially available as Thixcin®. Suitable solvents are described in more detail below.

  The liquid composition of the present invention is preferably a homogeneous solution, and in particular, the ionic component is preferably dissolved in the homogeneous liquid.

  The liquid of the present invention desirably has a pH of less than 9, preferably less than 8, as measured by dissolving the liquid in demineralized water at a concentration of 1%.

Ionic Component The liquid composition of the present invention comprises at least one dissolved ionic component selected from the group consisting of carboxylates, phosphonates, and mixtures thereof. Such ionic components may be suitable as builder / chelant actives used to bind metal ions in aqueous solution.

  In one embodiment of the invention, the ionic component is a carboxylate, preferably a carboxylate builder, and even more preferably a polycarboxylate builder. As used herein, the term “carboxylate” encompasses the acid form of a salt and also refers to a compound having a plurality of carboxylate groups, preferably at least three carboxylates, “polycarboxylate”. Is also included. Suitable polycarboxylate builders can preferably be added to the composition in acid form, but can also be added in the form of neutralized salts. When used in the salt form, alkali metal salts such as sodium, potassium, and lithium, or alkanol ammonium salts are preferred.

  Various classes of useful substances are included in the polycarboxylate builder. One important class of polycarboxylate builders are US Pat. No. 3,128,287 (Berg, issued April 7, 1964) and US Pat. No. 3,635,830 (Lamberti). ) Et al., Issued on Jan. 18, 1972) ether polycarboxylates comprising oxydisuccinate. See also the “TMS / TDS” builder in US Pat. No. 4,663,071 (Bush et al., Issued May 5, 1987). Suitable ether polycarboxylates include cyclic compounds, particularly U.S. Pat. Nos. 3,923,679, 3,835,163, 4,158,635, and 4,120,874. And alicyclic compounds such as those described in U.S. Pat. No. 4,102,903.

  Other useful detergent builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and Various alkali metal salts, ammonium salts and substituted ammonium salts of polyacetic acid such as carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as melittic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3 , 5-tricarboxylic acid, carboxymethyloxysuccinic acid, and polycarboxylates such as their soluble salts.

  Citrate builders such as citric acid and its soluble salts (especially sodium salts) are polycarboxylates that are of particular importance for heavy liquid detergent formulations because of their availability from renewable resources and their biodegradability. You are a rate builder. Oxydisuccinate is also particularly useful in such compositions and combinations.

Also, 3,3-dicarboxy-4-oxa-1,6-hexanedioates disclosed in US Pat. No. 4,566,984 (Bush, issued on Jan. 28, 1986) and Related compounds are also suitable for the liquid detergent composition of the present invention. Useful succinic acid builders include C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. It is done. Lauryl succinate is a preferred builder of this group and is described in European Patent A0200263 (published 5 November 1986).

  Specific examples of nitrogen-free phosphor-free aminocarboxylates include ethylenediamine disuccinic acid and its salts (ethylenediamine disuccinate, EDDS), ethylenediaminetetraacetic acid and its salts (ethylenediaminetetraacetate, EDTA). And diethylenetriaminepentaacetic acid and salts thereof (diethylenetriaminepentaacetate, DTPA).

  Other suitable polycarboxylates are described in U.S. Pat. No. 4,144,226 (Crutchfield et al., Issued March 13, 1979) and U.S. Pat. No. 3,308,067 (Diehl, Issued on March 7, 1967). See also U.S. Pat. No. 3,723,322 (Diehl). Such materials include water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, and methylenemalonic acid.

  In another embodiment of the invention, the ionic component is a phosphonate component. As used herein, the term phosphonate encompasses the acid forms of the salts. Suitable phosphonates for use in the present invention may be selected from the group consisting of inorganic and organic phosphonates.

  In a preferred embodiment, the phosphonate is selected from organic phosphonates. Examples of organic phosphonates suitable for use herein are aminoalkylene poly (alkylene phosphonates), alkali metal ethane-1-hydroxybisphosphonates and nitrilotrimethylene phosphonates. Preferred organic phosphonates for use herein are diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxy-ethylene-1,1-diphosphonate (HEDP). is there. In the context of the present invention, HEDP is very preferred.

  Preferably, the at least one ionic component is 0.2% to 4.0%, preferably 0.5% to 3.0%, more preferably 0.5% by weight of the liquid composition. It may be incorporated at a concentration of from% to 2.0% by weight.

Water Content Although the liquid compositions of the present invention are concentrated compositions, they still contain some water.

  The liquid composition contained in the water-soluble liquid-containing pouch of the present invention is, as a first essential requirement, 5%, 6%, 7%, 8%, 9% by weight (in this order) of the composition. To 15 wt.%, 14 wt.%, 13 wt.%, 12 wt.%, 11 wt.%, 10 wt. (More preferred sequentially in this order).

  More specifically, the liquid composition contained in the water-soluble liquid-containing pouch of the present invention is 5% to 15% by weight of the liquid composition, preferably 6% to 12% by weight, more preferably It should contain 7% to 10% by weight, most preferably 8% to 10% by weight of water.

  Surprisingly, the water content of the liquid composition is 5% to 15%, preferably 6% to 12%, more preferably 7% to 10%, most preferably the liquid composition. Is maintained within the range of 8% to 10% by weight, an optimized and stable dissolution of an ionic component selected from the group consisting of carboxylates, phosphonates, and mixtures thereof is obtained. I know that.

Horizontal Bag Making-Filling-Sealing Process As a second essential requirement, the water-soluble liquid containing pouch of the present invention must be processed using a vacuum forming, horizontal die, bag making-filling-sealing process (HFFS). .

  The pouch of the present invention may be processed according to any of the horizontal bag making-fill-seal methods generally known in the art. Suitable methods are described, for example, in PCT International Publication No. WO 02/60758.

  A preferred HFFS process for forming the water-soluble liquid containing pouch of the present invention comprises: (a) applying a first water-soluble film to a horizontal portion of an endless surface (consisting of a plurality of molds) that moves continuously and rotatably; Feed continuously, (b) from the bottom of the mold, on the horizontal part of the continuous moving surface, and from the film in the mold on the surface, the horizontally arranged web of the open pouch that moves continuously Forming by applying a vacuum on the film; (c) a horizontally moving open horizontally filled pouch filled with liquid in a horizontally arranged web of open pouches (D) continuously feeding the second water-soluble film onto an open, filled pouch on a horizontally disposed web; Bed a continuously closed, to obtain a closed pouch, and consists of (e) a closed each step of the thermally fusing the pouch is a continuous process.

  Alternatively, step (e) may be performed by solvent bonding (as described in PCT International Publication No. WO 03/008486) and solvent or wet sealing.

  When using a vacuum forming, horizontal mold, bag making-fill-seal process, the first water-soluble film typically has a thickness of 20-100 microns prior to thermoforming.

  Surprisingly, 5% to 15%, preferably 6% to 12%, more preferably 7% to 10%, most preferably 8% to 10% by weight of water of the liquid composition. A water-soluble pouch containing a liquid composition containing at least one dissolved ionic component selected from the group consisting of carboxylates, phosphonates and mixtures thereof, It has been found that when processed using a bag-fill-seal process, the water solubility of the liquid-containing pouch is greatly improved.

  The enhanced water-solubility of the pouches of the present invention is greater than that of similar pouches manufactured using alternative pouch making methods commonly known in the art such as vertical bag-fill-seal processes. Is also clearly observed. The improvement in water solubility after storage of the liquid-containing pouch for several weeks is particularly noticeable.

Preferred optional components of the liquid composition A highly preferred optional component of the liquid composition is a metal salt. Without being bound by any theory, such metal salts further contribute to obtaining a stable dissolution of the ionic component in the liquid composition contained in the water-soluble pouch of the present invention. It is considered to be. Preferably, the metal salt is selected from the group consisting of magnesium salts and calcium salts. Particularly preferred salts are magnesium chloride, magnesium sulfate, magnesium sulfite and magnesium bisulfite. In the context of the present invention, magnesium chloride is a highly preferred salt. However, the Applicant has found that chloride ions can have a long lasting detrimental effect on production equipment, especially at high temperatures. In this case, the most preferred metal salt is magnesium hydrogen sulfite. The use of magnesium bisulfite also provides further advantages. Potassium sulfite provides the known benefit of improving the aesthetics of the composition over time. The use of magnesium bisulfite allows the detergent manufacturer to benefit from one component in two ways. Magnesium stabilizes the dissolved ionic component, and bisulfite provides the aforementioned aesthetic benefits.

  Preferably, the liquid composition comprises less than about 1%, more preferably less than 0.5%, and most preferably less than 0.3% by weight of the metal salt of the composition.

  When the liquid composition is a detergent composition, at least a surfactant and / or builder, preferably at least an anionic surfactant and preferably further a nonionic surfactant, and preferably at least a builder, more preferably a phosphate builder and It is preferable that at least a water-soluble builder such as a fatty acid builder is present. Other preferred ingredients are enzymes and / or bleaching agents such as preformed peroxyacids.

  Other preferred optional ingredients are also perfumes, brighteners, buffers, fabric softeners including clays and silicones, benefit agents, and suds suppressors.

  In hard surface cleaning and dishwashing compositions, it is preferred that at least a water-soluble builder such as phosphate is present, and preferably further surfactants, perfumes, enzymes, bleaching agents are present.

  In the fabric enhancing composition, it is preferred that at least a fragrance and a fabric benefit agent, such as a cationic softener or clay softener, a wrinkle resistant agent, a textile direct dye, are present.

  Other highly preferred optional ingredients in all the above compositions are also alcohols, diols, monoamine derivatives, glycerol, glycols, polyalkylane glycols (polyethylene glycol, propanediol, monoethanolamine, etc.) And so on. Highly preferred are mixtures of solvents such as mixtures of alcohols or mixtures of diols and alcohols. Highly preferred is (at least) an alcohol, diol or monoethanolamine, preferably glycerol is also present in the composition. The composition of the present invention is preferably a concentrated liquid having less than 50% or even less than 40% by weight of solvent (other than water), preferably less than 30% or even less than 20% by weight of solvent (other than water). . Preferably, the solvent is present at a concentration of at least 5% or even at least 10% or even at least 15% by weight of the composition.

  It is highly preferred that the composition comprises a plasticizer for the water-soluble pouch material, for example one of the above plasticizers, for example glycerol. Such plasticizers can have the dual purpose of being a solvent for the other components of the composition and a plasticizer for the pouch material.

  Further highly preferred components are polycarboxylated polymers (eg polyacrylic acid, polyacrylic acid-maleic acid copolymers), cationic ethoxylated amines, zwiterrionic polymers (European Patent Application No. Other ionic components selected from the group consisting of anionic soil free polymers, such as those described in No. 0447256.

  In another embodiment of the present invention, (a) at least one dissolved ionic component selected from the group consisting of carboxylates, phosphonates, and mixtures thereof, and from 5% to 5% by weight of the liquid composition Formulating a film containing vinyl alcohol and a carboxylic acid copolymer using a liquid composition containing 15% water by weight and (b) a vacuum forming, horizontal, bag making-fill-seal process. Thus, there is provided a method for producing a water-soluble pouch having improved water solubility during storage, comprising the step of processing into a water-soluble pouch containing the liquid composition.

Test Method Polymer Residue Grade Test A so-called “Black Pouch Solubility Method” has been developed to evaluate the solubility of liquid detergent pouches during cleaning. The method provides a corresponding assessment for the solubility of the liquid detergent pouch under the consumer's corresponding specific conditions. Data is obtained by visual grading of PVA residue against a defined grading scale.

  Equipment required: 4 Miele washing machines, model W467 (connected to the water temperature control system) and 16 black velvet pouches (a piece of black velvet (23.5X47cm) inside the velvet) Folded and sewed to produce). Fabric used in Black Cotton Pie Velvet (Quality 8897) (commercially available from Denholme Velvets (Denholm, UK)).

  Test preparation: Liquid detergent-containing PVA pouch (at recommended dose under normal conditions) was added into the black velvet pouch in a standardized manner. The resulting black pouch is then sewn and closed. Four black pouches are attached to each of the four washing machines by a standardized method. Different liquid detergent pouches may be added to one washing machine, but four external copies are required for each product.

Test conditions: Wool washing program at 40 ° C (14 ° C +/- 1 ° C tap water is used through a water temperature control system)
Visual grading: At the end of the wash cycle, the black pouch is opened and a visual grading of the polymer residue on the fabric is immediately performed by at least two people according to a predefined grading scale. The overall grade is a statistical average of different replicates. The grade scale varies from 0 (meaning that there is no significant PVA residue on the fabric after washing) to 7 (meaning that there is virtually no dissolved PVA pouch). To do. In the context of this test, good pouch dissolution is obtained with a score of less than 3. A score of 3 means that an opaque PVA residue with a maximum average diameter of more than 2 cm cannot be seen on the fabric after washing. Ideally, the score should be minimal.

The following examples further illustrate the invention. A composition is prepared by mixing the listed components in the listed proportions (wt% unless otherwise specified). The example compositions 1-4 are intended to illustrate the compositions of the present invention and are not necessarily used to limit or define the scope of the present invention.

  Dodecylbenzene sulfonic acid is commercially available from Ifrachem.

  C12-C14 alcohol, 7x ethoxylated, is commercially available from Sasol.

  C8-C10 amidopropyldimethylamine is commercially available from Akzo Nobel Chemicals LTD.

  Citric acid is commercially available from Citrigue Belgium NV.

  C12-C18 alkyl fatty acids are commercially available from Akzo Nobel Chem. GMBH.

  Hydroxyethanediphosphonic acid is commercially available from Solutia Europe NV.

  Diethylenetriamine pentamethylene phosphonic acid is commercially available from Albright & Wilson LTD.

  Enzymes are proteolitic and amylolytic enzyme solutions commercially available from Genencor and Novozymes, respectively.

  Magnesium chloride is commercially available from Nedmag.

  Potassium sulfite is commercially available from BASF.

  Polyethyleneimine ethoxylate PEI600 E20 is commercially available from BASF.

  The zwitterionic polyamine is Lutensit Z96® available from BASF.

  The optical brightener is disodium-4,4'-bis- (2-sulfostyryl) biphenyl, commercially available from Ciba AG.

  Hardened castor oil is commercially available from Brazil Oleo De Mamona.

  Propylene glycol is commercially available from BASF.

  Glycerin is commercially available from NAT OLEO.

  Polydimethylsiloxane is commercially available from Dow Corning.

  Monoethanolamine is commercially available from Sasol.

  The liquid compositions 1, 2, 3, and 4 were filled into film pouches (each pouch contains about 50 mL of liquid) using a vacuum forming, horizontal mold, bag making-fill-seal process. The film was made from a polyvinyl alcohol / carboxylate copolymer resin (M8630®, manufactured by Mono-Sol, Inc., Indiana, USA). The resulting pouch contains completely homogeneous liquids. The dissolution and degradation profile of each pouched composition is good. The pouch dissolves / decomposes quickly in water without leaving any residue even after long-term (8 weeks) storage at 35 ° C.

Comparative data The following examples further illustrate the invention. A composition is prepared by mixing the listed components in the listed proportions (wt% unless otherwise specified). The example compositions 5-6 are intended to illustrate the compositions of the present invention and are not necessarily used to limit or define the scope of the present invention. Example compositions A, B, and C are comparative examples.

  Formic acid is commercially available from BASF.

  Ethoxylated tetraethylenepentamine is commercially available from BASF.

  The optical brightener is disodium-4,4′-bis- (2-sulfostyryl) biphenyl commercially available from Ciba AG in Compositions 5 and B. Compositions 6, A and C Among them, disulfated di-aminostilbene-based fluorescent whitening agents commercially available from Hickson & Welch LTD.

  Experiment 1: Effect of water content of the liquid composition on the physical stability and solubility of various PVA pouches after storage.

  The liquid compositions 5, A, and B were filled into film pouches (each pouch contains about 50 mL of liquid) using a vacuum forming, horizontal mold, bag making-fill-seal process. The film was made from a polyvinyl alcohol / carboxylate copolymer resin (sold by Mono-Sol Corporation (Indiana, USA) under the trade name M8630®). The corresponding pouch was stored at 35 ° C. for 8 weeks.

  The physical stability after storage was evaluated by visual observation of the corresponding pouch. The solubility of the liquid-containing pouch at the time of washing was evaluated using the “black pouch solubility method” described above in the present specification.

The results are shown in the table below.

  The above results clearly show the improved physical stability and solubility after storage of the water-soluble pouch of the present invention (pouched composition 5) versus the comparative water-soluble pouch (pouched compositions A and B).

  Experiment 2: Effect of the water-soluble pouch manufacturing process on the solubility during washing after storage of the liquid-containing pouch.

  Liquid compositions 6 and C had the same chemical composition but were filled into two different types of film pouches. Both contain about 50 mL of liquid composition, but were processed using two different manufacturing processes. The first set of pouches is manufactured using vacuum forming, horizontal type, bag making-fill-seal process (HFFS) (Composition 6 with pouch), and the second set of pouches is vertical type bag making-filling. -Manufactured using the sealing process (VFFS) (Pouched Composition C). The film was made from a polyvinyl alcohol / carboxylate copolymer resin (sold by Mono-Sol Corporation (Indiana, USA) under the trade name M8630®). The corresponding pouch was stored at room temperature for 10 months.

  The solubility of the liquid-containing pouch at the time of washing was evaluated using the “black pouch solubility method” described above in the present specification.

The results are shown in the table below.

  The above results use the water-soluble pouch of the present invention (ie, vacuum forming / horizontal / bag making-fill-sealing process) when compared to a water-soluble pouch that is not of the present invention (composition C with pouch). The improved solubility after storage of the processed pouched composition 6) is clearly shown.

Claims (11)

  A water-soluble pouch containing a liquid composition, wherein the water-soluble pouch is made from a film comprising a copolymer of vinyl alcohol and carboxylic acid, and the liquid composition contained in the pouch comprises a carboxylate And at least one dissolved ionic component selected from the group consisting of phosphonates and mixtures thereof, wherein the liquid composition comprises 5% to 15% water by weight of the liquid composition, and A water-soluble pouch wherein the pouch is processed using a vacuum forming, horizontal mold, bag making-fill-seal process.   The water-soluble pouch of claim 1, wherein the at least one ionic component is a phosphonate.   The water-soluble pouch according to claim 2, wherein the at least one ionic component is hydroxy-ethylene-1,1-diphosphonate.   4. The liquid composition of claim 1-3, wherein the liquid composition comprises 6% to 12%, preferably 7% to 10%, more preferably 8% to 10%, by weight of the liquid composition. The water-soluble pouch according to any one of the above.   The liquid composition is 0.2 wt% to 4.0 wt%, preferably 0.5 wt% to 3.0 wt%, more preferably 0.5 wt% to 2.0 wt% of the liquid composition. The water-soluble pouch according to claim 1, comprising% of the at least one ionic component.   The water-soluble pouch according to any one of claims 1 to 5, wherein the liquid composition further comprises a metal salt selected from magnesium salts and calcium salts, preferably magnesium salts.   The water-soluble pouch according to claim 6, wherein the metal salt is selected from magnesium chloride, magnesium bisulfite, or a mixture thereof.   The water-soluble pouch of claim 6, wherein the liquid composition comprises less than 1%, preferably less than 0.5%, more preferably less than 0.3% by weight of the metal salt of the liquid composition. .   One or more selected from the group consisting of polycarboxylic acid, polycarboxylate salt, polyphosphoric acid, polyphosphonate salt, cationic ethoxylated amine, zwitterionic polymer, enzyme, and mixtures thereof The water-soluble pouch according to any one of claims 1 to 8, further comprising:   After storage at 35 ° C. for 8 weeks, the pouch exhibits water solubility according to the “black pouch solubility method” so that film residues with an average diameter of more than 2 cm at the maximum cannot be visually observed on the washed fabric. The water-soluble pouch according to any one of claims 1 to 9. A method for producing a water-soluble pouch having improved water solubility during storage,
(A) a liquid composition comprising at least one dissolved ionic component selected from the group consisting of carboxylates, phosphonates, and mixtures thereof, and 5% to 15% water by weight of the liquid composition. Blending the product,
(B) Process of processing a film containing a copolymer of vinyl alcohol and carboxylic acid into a water-soluble pouch containing the liquid composition using a vacuum forming / horizontal / bag making-filling-sealing process. When,
Including a method.