WO2001023460A1

WO2001023460A1 - Film and process for producing film

Info

Publication number: WO2001023460A1
Application number: PCT/JP2000/006662
Authority: WO
Inventors: Zenpei Meiwa; Hirohiko Hanada; Masafumi Miyamoto; Kenji Ishikawa
Original assignee: Kao Corporation
Priority date: 1999-09-30
Filing date: 2000-09-27
Publication date: 2001-04-05

Abstract

A film which has high storage stability even in a high-humidity atmosphere and feels good to the touch; a process for producing a film; and a packaging film which contains a perfume and hence emits a pleasant odor upon opening and/or dissolution. The film comprises a water-soluble film and a water-insoluble material present on a surface thereof, wherein the water-insoluble material is used in an amount of 0.1 to 80 parts by weight per 100 parts by weight of the water-soluble film and is in the form of particles having an average particle diameter of 500 νm or smaller or of fibers having a fiber length of 10 νm to 6 mm. A washing article is also provided which is a subdivision package employing the film as a packaging material. Specifically, the film production process comprises fixing the water-insoluble material to a surface of the water-soluble film by coating or printing.

Description

Specification

Technical field

TECHNICAL FIELD The present invention relates to a film having a function of dissolving or hydrolyzing a film when the film comes into contact with water or the like and releasing contents packaged in the film, and to a method for producing the film. Background art

Conventionally, water-soluble films have been functioning in applications such as foods, pharmaceuticals, agricultural chemicals, household goods and the like by dissolving the film when the contents are individually packaged and used, so that the contents can be taken out.

As a water-soluble film, Japanese Patent Application Laid-Open No. 61-25771 / 57 describes that by mixing sodium chloride in advance with a water-soluble polymer, sodium chloride can be evenly arranged on the film to make the seasoning uniform. Japanese Patent Application Laid-Open No. HEI 3-1974241 discloses a method in which a water-insoluble polymer is previously blended with a water-soluble polymer to control the release of a drug. However, it was unbearable for long-term storage or storage in a humid environment, and required separate packaging:> Also, there was a sticky feeling when touched by hand, and it was not satisfactory in terms of feel.

Japanese Patent Application Laid-open No. Hei 10-725259, Japanese Patent Laid-open No. Hei 9-104 617, Japanese Patent Laid-open No. Hei 5-11998, Japanese Utility Model Laid-open No. Hei 2-444029, Japanese Patent Laid-open Hei 1-2 The same applies to Japanese Patent No. 3713136 and Japanese Patent Application Laid-Open No. 50-73.

An object of the present invention is to provide a film having a high storage stability even in a humid environment and a film having a good feeling when touched by hand, and to provide a film manufacturing method. An object of the present invention is to provide a packaging film that can enjoy the smell when Z or is dissolved. Disclosure of the invention The present invention relates to a film comprising a water-insoluble material present on the surface of a water-soluble film, wherein the water-insoluble material is used in an amount of 0.1 to 80 parts by weight based on 10 parts by weight of the water-soluble film. A film in which the water-insoluble material is a powder having an average particle diameter of 500 μm or less, and a film in which the water-insoluble material is present on the surface of the water-soluble film, and The amount used is 0.1 to 80 parts by weight with respect to 100 parts by weight of the water-soluble film, and the water-insoluble material has a fiber length of 10 μm to 6 mm in a fibrous form. . That is, a water-soluble film surface, a film in which a water-insoluble material is present, wherein the amount of the water-insoluble material used is 0.1 to 80 parts by weight with respect to 100 parts by weight of the water-soluble film, A film in which the water-insoluble material is a powder having an average particle size of 500 μm or less or a fibrous form having a fiber length of 10 μm to 6 mm.

The present invention is a method for producing a film in which a water-insoluble material is present on the surface of a water-soluble film, and a method for fixing the water-insoluble material on the surface of the water-soluble film by coating or printing. The water-insoluble material may be a powder having an average particle size of 500 μm or less, or the water-insoluble material may have a fibrous form having a fiber length of 10 μm to 6 mm. A film containing 100 parts by weight of a water-soluble film surface and 0.1 to 80 parts by weight of a water-insoluble material, wherein the water-insoluble material has a powder or fiber length of less than 500 μππι. It has a fibrous morphology of 0 μm to 6 mm, and is a method for producing a film in which a water-insoluble material is present on the surface of a water-soluble film by coating or printing and is fixed.

Further, a water-insoluble material is present on the surface of the thin film of the water-soluble polymer having a water content of 50% by weight or more, and then dried. A mixture of the water-insoluble material and the binder solution is applied to the film manufacturing method or the water-soluble film surface. It is a process of making a film that is present and then dried.

The production method of the present invention has a water content of 50% by weight. /. A water-insoluble material is present on the surface of the thin film of the water-soluble polymer, and then dried to obtain a film. The amount of the water-insoluble material used is 0.1 to 80 parts by weight based on 100 parts by weight of the thin film of the water-soluble polymer. Parts by weight, and the water-insoluble material is powder or fiber with an average particle size of 5 μm or less 10 μπι! A film production method characterized by having a fibrous morphology of up to 6 mm, A mixture of the soluble material and the binder solution is allowed to exist, and then dried to obtain a film. The amount of the water-insoluble material used is 0.1 to 80 parts by weight with respect to 100 parts by weight of the water-soluble film. The present invention also includes a method for producing a film, wherein the material has a powdery form having an average particle diameter of 500 μm or less or a fibrous form having a fiber length of 10 m to 6 mm.

The film of the present invention and the film obtained by the manufacturing method of the present invention are useful for packaging laundry materials in use forms, and the present invention provides laundry articles packaged with these films. BEST MODE FOR CARRYING OUT THE INVENTION

Water-soluble film>

The water-soluble film is mainly composed of a water-soluble polymer, but its basis weight is 10 g from the viewpoint of film strength and solubility in water or water-dissolvability (hereinafter referred to as water-disintegrable).

Zm ² or more is preferable, and the range of 15 to 100 g / m ² is more preferable. The thickness is preferably 9 μπι or more, more preferably 13 to 90 zm.

The water-soluble polymer has a solubility of 80 parts by weight when one part by weight of a sample is dissolved in 99 parts by weight of water at 25 ° C. /. Refers to the above, with a solubility of 90 weight. /. The above are more preferred. The solubility is calculated by filtering the aqueous solution through filter paper (No. 2) and calculating the solid content in the filter paper.

Examples of such water-soluble polymers include polyvinyl alcohol and Z or derivatives thereof (itaconic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, maleic acid-modified polyvinyl alcohol, etc.), poly (meth) acrylic acid salts , (Meth) acrylic acid Z Alkali salt of (meth) acrylic acid ester copolymer, (meth) acrylic acid Z Alkaline salt of maleic acid copolymer, synthetic product such as polyvinylpyrrolidone; Semi-synthetic products such as tilcellulose, carboxymethylcellulosic sodium, hydroxyalkylcellulose, and starch derivatives; and natural polymers such as starch, gelatin, agar, seaweed, plant mucilage, and proteins. These may be used alone or in combination of two or more.

<Water-insoluble material>

As the water-insoluble material, a water-insoluble inorganic substance or a water-insoluble organic substance is used. here " "Water-insoluble" means that when 1 part by weight of a sample is dissolved in 99 parts by weight of water at 25 ° C, the solubility is 50 parts by weight. /. Refers to the following, 40 weight. /. The following are more preferable as the water-insoluble inorganic substances, such as zeolite, bentonite, talc, mai power, force ol, sepiolite, silica, calcium carbonate, titanium oxide, silicic anhydride, hydroxy 'calcium' apatite, phthalocyanine In addition to blue, herringdon pink, hansa orange and the like, pearls are mentioned, and zeolite, bentonite, talc, mica, kaolin, silica, titanium oxide, silicone and the like are preferably used. Examples of water-insoluble organic substances include polyethylene, polypropylene, polyamide, polyethylene terephthalate, polystyrene, polyurethane, and Z or a cross-linked product thereof, sodium poly (meth) acrylate or poly (meth) acrylic acid ester, and / or a cross-linked product thereof. Rubbers such as ethylene rubber, propylene rubber, styrene-butadiene rubber, butadiene rubber, silicone rubber, and synthetic polymers such as Z or cross-linked products thereof; cellulose and Z or derivatives thereof, chitosan and Z or derivatives thereof , Starch, natural shells such as fruit shells and Z or its derivatives, such as polyethylene, polyamide, polystyrene, sodium poly (meth) acrylate, poly (meth) acrylate, cellulose and / or cellulose. Derivatives, starch, etc. It used Mashiku. Where "poly (meth) acrylic acid" is replaced with "polyacrylic acid"

"Polymethacrylic acid" means both.

When the water-insoluble material is in powder form, the average particle size is 500 μm or less, preferably 300 m or less, and 0.01 from the viewpoint of the feel of the film and the prevention of powder particles falling off the film. ~ 300 μm is more preferable.

When the water-insoluble material has a fibrous form, the fiber length is 10 μπ, due to the feel of the film and the nodling property during film production. ~ 6 mm and 20 π! ~ 5 mm is preferred.

When the water-insoluble material is paper or non-woven fabric, those having a basis weight of 3 to 80 g Zm ² are preferable, and S SO g / m ² is more preferable, from the viewpoint of feeling when touching the film by hand and hydrolyzability. .

The water-insoluble material may be a true sphere, a substantially sphere, a plate, a bar, a fiber, a paper or a non-woven fabric. Such a sheet-like material is preferably used, and may also be of an irregular shape by pulverization or the like, and hollow or porous particles may also be used.

Further, as the water-insoluble material, two or more kinds of water-insoluble materials may be used. By using a mixture of two or more water-insoluble materials, the water-soluble film retains the water-solubility and water-decomposability, and has no stickiness, has a good feel, and has excellent usability.

The water-insoluble material is preferably used in an amount of 0.1 to 80 parts by weight, more preferably 0.3 to 70 parts by weight, based on 100 parts by weight of the water-soluble film.

The amount of the water-insoluble material present inside the water-soluble film is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 0% by weight of the total insoluble material used.

The film of the present invention has, for example, a water content of 50% by weight. /. A water-insoluble material is present on the surface of the thin film of the water-soluble polymer described above, and then dried.

If the water-insoluble material is present when the water content of the water-soluble polymer is less than 50% by weight, the adhesion between the surface of the water-soluble polymer and the water-insoluble material is insufficient, and the water-soluble polymer is easily detached. .

Here, the “water content of the water-soluble polymer” is defined by the following equation.

Water content of water-soluble polymer 军 (Heavy S%) =

[(Weight of aqueous solution of water-soluble polymer)-(Weight of aqueous polymer)]

X 100

(Weight of water-soluble polymer aqueous solution)

As a method of causing the water-insoluble material to be present on the surface of the water-soluble polymer thin film, a method of spraying or spraying the water-insoluble material on the surface of the water-soluble polymer thin film is preferably used.

In addition, when a water-insoluble material is present on the surface of a thin film of a water-soluble polymer, the water-soluble polymer contains a plasticizer, particularly in order to more reliably fix the water-insoluble material to the water-soluble film. It may be.

The plasticizer is water; phenolic compounds such as methanolic, ethanolic, isopropynoleanolic, etc .; glycols such as ethyleneglycol, diethyleneglycolone, triethyleneglycolone, polyethyleneglycol; glycerin, polyglycerin, G

0 And glycols such as polyethylene glycol; at least one selected from polyhydric alcohols such as glycerin, polyglycerin, trimethylolpropane, and pentaerythritol is preferably used for improving the plasticizing effect, drying speed, and production speed. obtain.

As a method of adding a plasticizer, there are a method of plasticizing only the thin film surface of a water-soluble polymer before spraying a water-insoluble material, and a method of mixing a water-containing water-soluble polymer and a plasticizer. By heating the film as necessary, the water-insoluble material becomes easier to adhere. In this case, the amount of the plasticizer is 1 part by weight or more based on 100 parts by weight of the water-soluble polymer from the viewpoint of the plasticizing effect, and 100 parts by weight from the viewpoint of the film forming property of the polymer sheet シート the strength of the polymer sheet. Parts by weight or less, more preferably 3 to 60 parts by weight.

After forming the desired film, the plasticizer is removed by a method such as drying if necessary.

In the film of the present invention, the water-insoluble plastic material may be fixed on the film surface by a binder. Such films are obtained by making a film from a water-soluble polymer, then presenting a mixture of a water-insoluble material and a binder solution on the surface of the film, and then drying. At this time, it is preferable to plasticize only the surface of the film or to mix a water-soluble water-soluble polymer and a plasticizer before the water-insoluble material is present on the film surface together with the binder.

The binder is previously dissolved or dispersed in water and / or an alcohol such as methanol, ethanol, propanol or butanol; or a petroleum such as hexane, heptane, tonolen, xylene or thinner, and then the water-insoluble material is dissolved or dispersed. Then, paint or ink (print) on a water-soluble film prepared in advance. That is, the water-insoluble material is fixed on the surface of the water-soluble film by coating or printing. For example, a water-insoluble material dispersed or dissolved in an organic solvent or the like is applied or printed on the surface of a previously prepared water-soluble film. To mix the water-insoluble material into the binder solution, a general mixer or disperser is used. As a method of causing the water-insoluble material to be present on the surface of the water-soluble film together with a binder, that is, as a coating or printing method, for example, spray coating, comma coater, lip coater, gravure coater 1. Coating methods such as mouth-coating, flow-coating, and kiss coating; printing methods such as gravure printing and flexographic printing are preferably used.

Examples of the binder for fixing the water-insoluble material to the surface of the water-soluble film include a water-soluble polymer, an alcohol-soluble polymer, and a petroleum-soluble polymer. In this case, the organic solvent is preferably one that does not dissolve the water-soluble film, and alcohols such as methanol, ethanol, and propanol, depending on the type of water-soluble polymer constituting the water-soluble film; Petroleum solvents such as hexane, heptane, octane, toluene and xylene are used. The amount of the organic solvent is 0.5 to 20 times the weight of the water-insoluble material.

These organic solvents are removed by a method such as drying after fixing the water-insoluble material on the surface of the water-soluble film.

Further, in the production method of the present invention, additives such as a thickener can be used to improve the dispersibility of the water-insoluble material in an organic solvent. Ethyl cellulose, hydroxypropyl cellulose or an oil-soluble polymer is preferably used as a thickener. The addition amount of such a thickener is preferably 0.1 to 10% by weight based on the water-insoluble tenacious material. Examples of these binders include polyvinyl alcohol and / or its derivatives (itaconic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, maleic acid-modified polyvinyl alcohol, etc.), poly (meth) acrylate alkali salt, ) Alkaline salt of acrylic acid / (meth) acrylic acid ester copolymer, alkali salt of (meth) acrylic acid Z maleic acid copolymer, polyvinylpyrrolidone, polyethylene oxide, polyamide, polyethylene terephthalate, polystyrene , Polyurethane, ethylene rubber, propylene rubber, styrene-butadiene rubber, butadiene rubber, silicone-based polymers, etc .; methylcenorellose, ethylethylenolose, sodium carboxymethylcellulose, hydroxya Semi-synthetic products such as ruquilcellulose and starch derivatives; natural polymers such as chitosan and Z or derivatives thereof, starch, gelatin, agar, seaweed, plant mucilage, proteins, etc .; polybutyl alcohol and / or derivatives thereof; Alkali salt of poly (meth) acrylic acid, alkali salt of poly (meth) acrylic acid / (meth) acrylic acid ester copolymer, polybutylpyrrolidone, polyethylene oxide, polyamide, cellulose Alternatively, derivatives thereof, starch and the like are preferably used.

In this case, the amount of the binder is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, based on 100 parts by weight of the water-insoluble material.

Since the film thus obtained contains water or a solvent, it is dried by a method such as a drum drying method, a belt drying method, or a hot air drying method.

Further, the film of the present invention can be provided with an embossed pattern on its surface by embossing. As a result, the feel when touching the hand can be further improved. In the embossing, the surface area of the concave portion on the film surface is preferably 40% or less. The thickness of the film after embossing is preferably at least 1.3 times the thickness of the film before embossing.

The film of the present invention may be scented, and may be scented on the surface and / or inside of the film. By perfuming the film surface and / or inside, the fragrance duration after opening the package can be freely controlled.

Examples of the method of perfumery include a method of dispersing or mixing a fragrance component and a fragrance-containing material into a water-soluble film, and a method of dispersing a fragrance component and a fragrance-containing material when a water-insoluble material is present on the surface of the water-soluble film. There is a method of mixing and making it exist on the surface of the water-soluble film.

As fragrances and fragrances, terpene-based hydrocarbons such as α-binene,] 3-binene, myrcene, limonene, 1,8-cineole, and hydrophobic fragrances such as amyl acetate and amyl probionet (for example, — No. 3,266,734, page 3, upper left column, line 19 to the same page lower left column, line 13). One or more of these can be used.

Other additive components>

In the film of the present invention, besides the plasticizer, a releasing agent, an anti-blocking agent, a solubility improving agent, a coloring component and the like may be used as additives.

Nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene phenols, polyoxypropylene propylene glycols, polyoxyethylene polyoxypropylene alkyl ethers, etc. , Alkyl trimethylammonium chloride, salt Cationic surfactants such as nickel are preferably used.

The amount of these release agents is 0.1 parts by weight or more based on 100 parts by weight of the water-soluble polymer from the viewpoint of release properties, and 5 parts by weight or less from the viewpoint of film-forming properties and strength of the water-soluble film. Is preferred.

As the antiblocking agent, inorganic substances such as bentonite, talc, kaolin, zeolite and the like, and organic substances such as starch and cellulose powder are preferably used. The amount of the anti-booking agent added is preferably 1 part by weight or less, particularly 0.1 part by weight, based on 100 parts by weight of the water-soluble polymer from the viewpoint of handling properties such as winding property and productivity. The following is preferred. '

As the solubility improver, a water-soluble inorganic salt, a water-soluble organic salt, a water-insoluble inorganic substance, and a water-insoluble organic substance are used. Examples of water-soluble inorganic salts include chlorides such as sodium chloride, potassium chloride, and magnesium chloride; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, and aluminum sulfate; carbonates such as sodium carbonate and sodium hydrogen carbonate. And water-soluble organic salts such as citrate, conodate, maleate, fumarate, and malate, fatty acid salts, ester phosphates, acylated amino acid salts, and the like. Examples include sulfosuccinates. Examples of the water-insoluble inorganic substance include inorganic substances such as bentonite, talc, kaolin, and zeolite. Examples of the water-insoluble organic substance include cellulose powder and starch.

The addition amount of these solubility improvers is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the water-soluble polymer in order to improve the solubility and obtain a uniform film.

As one application of the film of the present invention, a non-liquid detergent used for washing, a non-liquid bleaching agent | J, a non-liquid finishing agent, a washing composition such as a sizing agent is divided into this film and used as a laundry article. Can be offered. The laundry composition to be packaged can be in the form of tablets, powders, powders, and pastes. Pastes and doughs are more preferred in terms of feel. In the case of pastes and doughs, the contact area between the gas (especially oxygen) and the laundry composition can be reduced, which is also preferable from the viewpoint of improving the stability (deterioration such as discoloration and generation of an odor). Paste, the dough-like material, it enters the hardness 0 0 5 to 2 0 kg / cm ² is preferably at 2 5 ° C, 0 1~1 5 kg / cm:.. , More preferably, 0 5-10 kg / cm ² is more preferable.

Note entry hardness, with press special adapter rheometer foremost surface of the laundry composition maintained at 2 5 ° C (FUD OH RT- 20 1 0 J -C) ( circle bottom area 1 cm ^2), the adapter Can be determined by measuring the stress when penetrating 2 cm into the laundry composition at a penetration speed of 30 cm / min.

In the present invention, “dough” means a kneaded product of a powdery composition and a fluid substance such as a liquid, paste, or gel composition. And those having fluidity due to stress.

The dough can be produced using a universal stirrer, such as a universal stirrer suitable for high-viscosity stirring. By adding a polyalkylene glycol having a pour point of 40 ° C. or higher, a dough can be produced in a short time.

The viscosity of the laundry composition used in the present invention (Tokyo Keiki DVM—B-type rotor No. 4, rotational speed 3 rpm, 25 ° C.) is preferably 100,000 mPa's or more, and 200,000 mPas or more. mPas or more is more preferable.

The thickness of the packaged laundry composition is preferably 15 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less from the viewpoint of solubility. The thickness is preferably 1 mm or more, more preferably 2 mm or more, from the viewpoint of strength and ease of handling. From the viewpoint of the convenience of use, it is preferable to use one packaged for each use. The laundry composition to be packaged is preferably from 10 to 100 g, more preferably from 15 to 50 g.

The water content in the laundry composition of the present invention is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, particularly preferably 0.5 to 10% by weight, from the viewpoint of preventing blocking and drying. Preferably, it is 2.3 to 7% by weight. The water content excludes water of crystallization such as zeolite, carbonate and citrate.

The non-liquid detergent among the laundry compositions used in the present invention mainly contains a surfactant and a builder. Examples of the surfactant include a higher alcohol or an ethylene oxide thereof (hereinafter referred to as “EO”), a sulfate salt of an adduct, an alkyl benzene sulfone salt, and a no. Anionic surfactants such as rough-insolephonic rooster salt, α-olefinsorephonic salt, α-sulfofatty acid salt, _α -sulfofatty acid alkyl ester salt or fatty acid salt; ΕΟ / propylene Oxide (hereinafter referred to as "PII") adducts, nonionic surfactants such as fatty acid alcohol amides and alkylpolyglycosides; amphoteric surfactants; cation surfactants and the like. In particular, amine salts of straight-chain alkyl benzene sulfonic acids having an alkyl chain of 10 to 14 carbon atoms, and amine salts of ester sulfates of higher alcohols having 12 to 18 carbon atoms are preferred in terms of detergency and foam properties. E05 ~ 10 mole adducts of alcohols having 10 to 16 carbon atoms and E〇4 ~ l 2 moles of E レ 0 ~ 1 moles of alcohols having 10 ~ 16 carbon atoms. POO. 1-4 mol adducts ( However, EO and P〇 may be either random polymerization or block polymerization) from the viewpoints of removing sebum stains, hard water resistance, and biodegradability. The content of the surfactant is preferably 5 to 80% by weight, more preferably 20 to 60% by weight in the non-liquid detergent in terms of detergency. /. Particularly preferred is 30-50 weight. /. It is. It is also preferable to use a combination of a nonionic surfactant and an anionic surfactant. In this case, the total of both is 50 to 100% by weight, particularly 70 to 100% by weight in the surfactant, and the detergency is good. It is preferred in that respect. The weight ratio of the nonionic surfactant to the anionic surfactant is expressed in terms of solubility as follows: nonionic surfactant Z anionic surfactant = 100/0 to 10/90, particularly θ θΖΐ Ζΐδ θΖδ Ο is preferred.

Examples of builders include inorganic builders such as carbonates, crystalline or amorphous aluminosilicates, crystalline or amorphous silicates, phosphates, and phosphates, and tri-triacetates, and ethylenediaminetetraacetic acid. Examples thereof include sodium such as organic builder such as salt, tartrate, citrate, acrylic acid polymer and copolymer, and alkali metal salt such as potassium. In particular, a crystalline aluminosilicate is preferred in terms of the ability to capture polyvalent metal ions such as calcium ions and the ability to absorb oil to nonionic surfactants. The content of the builder is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, and particularly preferably 15 to 55% by weight in the non-liquid detergent from the viewpoint of improving the detergency. /. It is.

Further, the content ratio of the surfactant and the builder is preferably from 1Ζ5 to 10Ζ1 (weight ratio), more preferably from the viewpoint of producing a dough having detergency and flexibility. 1/3 to 3/1, particularly preferably lZ2 to 3/2.

Further, the non-liquid detergent in the present invention includes a bleaching agent (percarbonate, perborate, bleach activator, etc.), a re-staining inhibitor (carboxymethyl cellulose, etc.), which are known in the field of clothing detergents. Softener, reducing agent (sulfite, etc.), fluorescent whitening agent, foam inhibitor (silicone Etc.) and fragrances and the like. Here, the bleaching agent and the softening agent are respectively less than 20% by weight, preferably less than 2% and less than 4% by weight in the non-liquid detergent.

As a non-liquid finish in the laundry composition used in the present invention, a softening agent such as an amine salt or a quaternary ammonium salt can be used. In particular, a quaternary ammonium salt of a di-long-chain alkyl type is preferable, and the alkyl group contains a linking group such as one CO—, —C—, —NHC—, or one CONH— in the alkyl group. You may. The softener content is 4 to 70% by weight in the non-liquid finish. /. It is. Further, as an optional component, in addition to the surfactant and the builder used in the non-liquid detergent, a fragrance, a pigment, a silicone compound, an antibacterial agent, a solvent, a water-soluble salt, and the like may be contained. As the non-liquid bleaching agent in the laundry composition used in the present invention, an oxygen-based bleaching agent is suitable. The oxygen-based bleach contains a compound containing a peroxide that generates hydrogen peroxide in water. As such peroxide, sodium peroxide, Tripoli-phosphate sodium peroxide adduct, sodium pyrophosphate-hydrogen peroxide adduct, urea-hydrogen peroxide _{adduct, 4 N a S 0 4 ·} 2 H 2 N · NaC1, sodium perborate · monohydrate, sodium perborate, tetrahydrate, sodium peroxide, sodium peroxide, calcium peroxide, etc. Sodium sodium borate monohydrate and sodium perborate tetrahydrate are preferred. The bleach content is 2 to 90% by weight, preferably 20 to 90% by weight, in the non-liquid bleach. Also, if necessary, a compound having an appropriate leaving group, tetraacetylethylenediamine, acetooxybenzenesulfonate, JP-A-59-22999, JP-A- Bleaching of a metal catalyst or the like in which an organic peracid precursor or a transition metal is stabilized with a sequestering agent described in JP-A-6-316840, JP-A-6-316700 It may be contained as an activator. The content of bleach activator is 0 to 30% by weight, preferably 1 to 20% by weight in the non-liquid bleach. Furthermore, in addition to surfactants, builders, and softeners used in non-liquid detergents or non-liquid finishes, p-toluenesulfonate, xylenesulfonate, alkenylsuccinate, urea, etc. It may contain a solubilizer, a penetrant, a suspending agent such as clay, an abrasive, a chelate, a pigment, a dye, a fragrance, and the like. Among the laundry compositions used in the present invention, the sizing agent is described in JP-B-48-239. No. 94, JP-A-59-686384, JP-A-62-117876, and alpha-monoesterized starch, acetalized CMC (carboxymethylcellulose), copolymer A spray-dried product of the combined emulsion can be used. Example

The percentages and parts in the examples are based on weight unless otherwise specified.

Example 1

T-330 (maleic acid-modified polyvinyl alcohol, Nippon Synthetic Chemical Industry Co., Ltd.) 150 g, water 850 g, and glycerin 15 g as a plasticizer are dissolved, defoamed, and put on a polyethylene terephthalate film. It was applied to a thickness of 200 μm using an applicator. Next, after spraying zeolite powder (average particle size: 7.6 m, manufactured by Kao Corporation), drying it with hot air at 110 ° C for 10 minutes, the release film was removed, and the film (F — 1) was obtained. The thickness of the film 3 0 / m, Zeorai preparative composite weight: 1. One is 4 g / m ² 7 this.

Examples 2-3

Using the water-soluble polymer, water-insoluble material and additives shown in Table 1, a film was prepared in the same manner as in Example 1. The abbreviations in the table have the following meanings.

K-60: polyvinylpyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd.

A-55: Solfalex A-55, hydroxyalkyl starch, manufactured by Matsutani Chemical Co., Ltd.

W—100 G: Cellulose powder, average fiber length 150 m, manufactured by Nippon Paper Industries Co., Ltd.

Kaolin: average particle size 4.2 m, manufactured by Wako Pure Chemical Industries, Ltd.

Example 4

KM-118 (carboxylic acid-modified polybutyl alcohol, manufactured by Kuraray Co., Ltd.) at 150 g, water at 800 g, polyethylene glycol as plasticizer (PEG # 400, Wako Pure Chemical Industries, Ltd.) 2000 g, Emulgen 135 (nonionic surfactant, manufactured by Kao Corporation) 15 g as a release agent, TSA732 (silicone-based defoamer) as a defoamer 0.75 g was dissolved and defoamed. While casting on a 0 ° C drum, the film was dried with hot air at 140 ° C (drying residence time: 2 minutes) to obtain a long water-soluble film having a film thickness of 40. Separately, while unwinding this film, apply 5 gZm ² rolls of ethylene glycol / ethanol (50/50 by weight) and immediately apply corn starch (starch powder (average particle size: 25 μπι), Matsutani Chemical) Industrial Co., Ltd.) was sprayed. After spraying, the film was dried with hot air at 100 ° (: 10 seconds) to obtain a film. The composite amount of corn starch in this film was 0.8 g / m ² .

Example 5

100 g of T-330 was added to 100 g of glycerin to give a water-soluble film (A) having a basis weight of 35 g Zm ² .

After dissolving 20 g of polyethylene oxide (Alcox E-30, manufactured by Meisei Chemical Co., Ltd.) as a binder in 300 g of ethanol, calcium carbonate (Sunlight SL-25) was used as a water-insoluble material. 0 0 (average particle size 0.4 zm), Takehara Chemical Industry Co., Ltd.) 100 g, and DL Limonene 3 g as a fragrance for the purpose of perfuming, homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) ) To obtain a paint (a). The surface of the water-soluble film (A) is coated with a coating (a) using a comma coater (manufactured by Hirano Tecseed Co., Ltd.), dried for 10 seconds in a hot air dryer at 60 ° C, and wound up. Obtained. The composite amount of calcium carbonate, binder and fragrance in this film is 7.1 g / m "C S.

Example 6

After dissolving 500 g of polyvinylpyrrolidone (K-90, manufactured by Wako Pure Chemical Industries, Ltd.) as a binder in 100 g of isopropyl alcohol at 60 ° C., a water-insoluble material was obtained. High-pressure homogenizer with 250 g of Sunlight SL-250 000 and 250 g of JR 301 (titanium oxide (average particle size: 0.5 m), manufactured by Tika Co., Ltd.) (Specialty Chemical Industry Co., Ltd.) and dispersed as paint (b). The paint (b) was applied to the surface of the water-soluble film (A) prepared in the same manner as in Example 5 using a Daravia printing machine (manufactured by Hirano Teksid Co., Ltd.), and dried at 60 ° C with hot air. The film was dried for 1 second for 2 seconds to obtain a wound film. The composite amount of calcium carbonate and titanium oxide in this film was 4.2 g / m ² . Example 7

After dissolving 20 g of water-soluble polyamide (AQ nylon, manufactured by Toray Industries, Inc.) in 270 g of methanol and 30 g of water, 149 g of JR301 and phthalocyanine blue (average particle size) are used as water-insoluble materials. 0.1 m) Add lg and disperse it with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain ink (c).

A gravure printing machine (a picture printed on a Mary's backsheet, Kao Corporation) was used as a gravure printing machine on the surface of the film obtained by compounding the carbonated titanium oxide and titanium oxide obtained in Example 6 with a binder. The film was obtained by overprinting with ink (c) using The composite amount of titanium oxide and lid mouth cyanine blue in this film was 0.3 g / m ² .

Comparative Example 1

A film was prepared in the same manner as in Example 1 except that the film was prepared without spraying the zeolite powder.

Comparative Example 2

A film was prepared in the same manner as in Example 1, except that a water-soluble salt (manufactured by Naikai Salt Industry Co., Ltd.) was used instead of the water-insoluble zeolite powder. The amount of complexed salt was 1.4 g Zn.

Table 1 shows the compositions of the films obtained in Examples 1 to 7 and Comparative Examples 1 and 2, and Table 2 shows the results of evaluation by the following methods.

Evaluation method>

(1) 5 ° C solubility

Cut the film into 5 cm squares, sandwich it between two slide glasses, and use it as a measurement sample. A 1 L beaker was charged with 1 L of ion-exchanged water, adjusted to 5 ° C, and the measurement sample was immersed with gentle stirring, and the time when the film began to be broken by visual observation was defined as the bag breaking time. In addition, the time when the film was completely dissolved by visual observation or the time when at least a part of the water-insoluble component was completely dispersed or disintegrated was defined as the complete dissolution time.

(2) Touch test

After storing the film in an environment of 25 ° C and 50% RH for 1 day, fill the entire palm. Touched the touch panel and evaluated the response. The rating is based on a five-point scale with five people rounding off the first decimal place of the average.

5: Extremely good feel

4: Good feel

3: Medium

2: Slightly sticky

1: Sticky large

(3) Blocking test

Assuming a situation where the film is individually wrapped, store it in a 25 ° C, 50% RH environment for one day, cut the film to 8 x 12 cm, and overlap the air surfaces when making the film. After applying a load of kg / cm ² for 10 seconds, the blocking property between the films was evaluated.

5: No blocking at all

4: Slight noise is generated when the film is peeled off, but there is no blocking. 3: Very slight (about 5% in area ratio).

2: Area ratio 10 to 50. /. Blocking

1: Blocking throughout

table

* 1: The amount of compounding of the water-insoluble materials in Examples 5 to 7 includes the weight of the fragrance and the fragrance.

* 3: Weight% based on water-soluble polymer Table 2

Example 8: Production of a packaged detergent

25 g of dodecyldimethylamine oxide from which water has been removed in advance using a microwave oven, “Nonidet R-7” [polyoxyethylene (7) alkyl (C _{12 to} C ₁₅ ) ether] manufactured by Mitsubishi Chemical Corporation Sulfuric oxide (Na salt) 10 g, “Sophthanol EP 7045” manufactured by Nippon Shokubai Chemical Industry Co., Ltd. [C ₁₂ -C ₁₄ secondary alcohol polyoxyethylene (7) polyoxypropylene (4.5) glycol ] 5 g, A4 Zeolite 40 g from Toyo Soda Co., Ltd., Acrylic acid-maleic acid copolymer K salt (molecular weight 6000 0) 4 g, soda ash 8 g, polypropylene glycol (molecular weight 1 000) 2.5 g 3 g of “Thixorex 25” manufactured by Kofran Chemical Co., Ltd. 2 g of d-limonene 0.9 g of protease, "AP I-21" manufactured by Showa Denko KK, 0.9 g of cellulase ("Selzym 1.0T" manufactured by Novo Industry Co., Ltd.), 0.9 g of amylase (Novo Industry Co., Ltd.) 0.5 g, Lipase (Novoindustry Co., Ltd., "Ribola 100 100"), 0.2 g, Fluorescent dye (Ciba-Geigy, Inc. "Tinopearl CB S-X") 0.2 g was mixed by hand to obtain a dough.

The obtained dough is stretched to a thickness of 2 mm, cut into 7 cm × 13 cm, and placed between two sheets of the film (F-1) obtained in Example 1 (with the zeolite composite surface facing outside). It was sandwiched and heat-sealed to obtain a packaging detergent for clothing.

30 pieces of the obtained packaging detergent were stacked in a bar and stored for 14 days in an environment of 30 ° (:, 80% RH. There was no change in appearance before and after storage and no blocking. The film had no stickiness at the time and was excellent in the touch surface, and was washed with tap water at 5 ° C in accordance with the solubility measurement method described in JP-A-11-124600 (hereinafter simply referred to as a washing test). As a result, the film residue was unseen.

Example 9: Production of packaging detergent

8 g of EO average adduct of lauryl alcohol 8 g, 7 mol of EO average of secondary alcohol having 12 to 14 carbon atoms (Nippon Shokubai Co., Ltd. 70%) 4 g, of 12 and 14 carbon atoms Alcohol mixture (4: 1 weight ratio) EO average 3 mol, P 〇 average 2 mol, E 〇 average 3 mol block adduct 8 g, alcohol mixture of 12 and 13 carbon atoms (1: 1 by weight) ) Average 6.5 mol adduct (Nonidet manufactured by Mitsubishi Chemical Corporation) 8 g, polyethylene glycol (molecular weight 6000) 2 g, alcohol mixture of 12, 14 and 16 carbon atoms (weight ratio 1: 1: 1) ) Sulfate monoethanolamine salt 2 g, crystalline aluminosilicate (Synthetic Zeolite, Toyo Builder manufactured by Tosoh Corporation) 36 g, sodium carbonate 15 g, crystalline sodium silicate (clearant Japan) SKS-6) 5 g, Na polyacrylate (So ka 1 an PA40) 2.5 g, acrylate / maleic acid copolymer Na (Sokalan CP 5 manufactured by BASF) 2.5 g, mixture (enzyme (sabinase 18.0 T Type White, lipolase) A mixture of 100 Τ, Serzim 0.1 Τ, Termamyl 60 Τ (both manufactured by Novo Nordisk) in a weight ratio of 1: 1: 1 1%, fluorescent dye (Whytex SA (manufactured by Sumitomo Chemical Co., Ltd.), Tinopearl CBS (manufactured by Ciba-Geigy Corporation) at a weight ratio of 1: 1) 0.5%, Na sulfite 1%, aminoalkyl-modified silyl 0.25% of corn oil, 0.25% of perfume and 100% of the total amount of Glauber's salt) 5g and 2g of water were mixed by hand to obtain a dough.

The obtained dough is stretched to a thickness of 2 mm, cut into 7 cm × 13 cm, and between the two films (F-1) obtained in Example 1. (The zeolite composite surface is the outer surface) And heat-sealed to obtain a packaging detergent for clothing.

Thirty pieces of the obtained separated detergents were stacked in a bar and stored for 14 days in an environment of 30 ° C. and 80% RH. There was no change in appearance before and after storage, and no blocking was observed. There was no stickiness when touched by hand, and it was an excellent film on the touch surface. As a result of the washing test, no film residue was observed.

Example 10: Production of divided bleach

Sodium carbonate, hydrogen peroxide adduct 15%, Emulgen 120 (manufactured by Kao Corporation) 44%, Polyethylene glycol (molecular weight 6000) 33%, fatty acid with 20 carbon atoms 2%, gel with 16 carbon atoms AS (sodium alkyl sulfate, hereinafter referred to as “AS”) 2%, octanoyloxybenzenecarboxylic acid 2%, fragrance 5%, and water 1.5% were mixed to obtain a paste. The obtained paste is stretched to a thickness of 2 mm, cut into 7 cm × 13 cm, and the film (F-1) obtained in Example 1 is placed between two sheets (the zeolite composite surface is applied to the outer surface). And heat-sealed to obtain a packaged bleach for clothing.

Thirty pieces of the obtained bleaching agents were stacked in a bar and stored for 14 days in an environment of 30 ° C and 80% RH. There was no change in appearance before and after storage, and no blocking was observed. There was no stickiness when touched by hand, and it was an excellent film on the touch surface. As a result of the washing test, no film residue was observed.

Example 11 1: Production of packaging finish

Japanese Patent Application Laid-Open No. 06-306769 discloses 15% of the softener composition of Example 1, 46% of Emargen 120 (manufactured by Kao Corporation), 33% of polyethylene glycol (molecular weight: 6000), 33%, and 20% of carbon atoms. A paste was obtained by mixing 2% of fatty acid, 2% of Gerbe AS having 16 carbon atoms, 0.5% of fragrance, and 1.5% of water. 2 m of paste obtained Stretched to a thickness of 7 m, cut to 7 cm x 13 cm, sandwiched between two sheets of the film (F-1) obtained in Example 1 (with the zeolite composite surface as the outer surface), and heat-sealed. A packaging finish for clothing was obtained.

Thirty obtained packaging finishes were stacked in a bar and stored for 14 days in an environment of 30 ° C. and 80% RH. There was no change in appearance before and after storage, and no blocking was observed. There was no stickiness when touched by hand, and it was an excellent film on the touch surface. As a result of the washing test, no film residue was observed.

Example 12 2: Production of packaging paste

A suspension consisting of 100 parts of starch, 2 parts of mono-tallow alkyltrimethylammonium chloride, and 10 parts of water was alpha-solidified with a 150 ° C heating roller, dried, crushed, and sieved. 25%, Emalgen 120 (manufactured by Kao Corp.) 40%, polyethylene glycol (molecular weight 6000) 30%, carbon number 20 A paste was obtained by mixing 1.5% of fatty acid, 1.5% of Gerbe AS having 16 carbon atoms, 0.5% of flavor and 1.5% of water. The obtained paste is stretched to a thickness of 2 mm, cut into 7 cm × 13 cm, and the film (F-1) obtained in Example 1 is placed between two sheets (the zeolite composite surface is removed). On the outer surface) and heat sealed to obtain a packaging paste for clothing.

Thirty obtained pastes were stacked in a bar and stored for 14 days in an environment of 30 ° C. and 80% RH. There was no change in appearance before and after storage, and no blocking was observed. There was no stickiness when touched by hand, and it was an excellent film on the touch surface. As a result of the washing test, no film residue was observed.

Production example (production of water-soluble film)

1500 g of T-330 (maleic acid-modified polyvinyl alcohol, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 8500 g of water, 200 g of glycerin as plasticizer (manufactured by Wako Pure Chemical Industries, Ltd.), and emulgen 135 as a release agent After dissolving 15 g of nonionic surfactant (Kao Corporation), degassing, and drying on a drum at 120 ° C, drying with hot air at 140 ° C (drying time: 2 minutes) A long water-soluble film (F-2) having a thickness of 30 m and a long water-soluble film (F-3) having a thickness of 20 im were obtained.

Example 13 While unwinding the water-soluble film (F-2), cellulose powder (W-400G, average fiber length 27 μη, Japan, using a Daravia coating machine (Hirano Rexid Co., Ltd., gravure roll 200 mesh) was used. While stirring a dispersed solution of 50 g of papermaking (manufactured by K-200 Cures), 10 g of ethylcellulose (manufactured by K-200 Cures), 890 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.), and 50 g of water Worked. Subsequently, hot air drying was performed at 110 ° C for 20 seconds. As a result, a film in which cellulose powder (W-400G) was composited with the water-soluble film was obtained. The compounded amount of W-400G was ^2.5 g Zm ² .

Example 14

While unwinding the water-soluble film (F-3), a gravure printing machine (Hirano Lecce Co., Ltd., gravure roll 100 mesh) is used to make a cellulose fiber yarn PLUS (W-50G, average fiber length 300 111, Nippon Paper Industries) 100 g of hydroxypropyl cellulose (MFG, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 g, ethyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) 740 g Coated. Subsequently, hot air drying was performed at 110 ° C for 20 seconds. As a result, a film in which the cellulose fiber (W-50G) was composited with the water-soluble film was obtained. The amount of W-50G complexed in this product was 8.5 g Zm ² .

Example 15

In Example 14, 100 g of cellulose fiber (W-50G) was changed to 100 g of Zeolite (manufactured by Kao Corporation), and the same operation as in Example 14 was performed to combine zeolite with a water-soluble film. The obtained film was obtained. The zeolite composite amount of this product was 4.5 g Zm ² .

Example 16

While unwinding the water-soluble film (F-2), using a gravure coating machine (Hirano Rexid Co., Ltd., gravure roll 500 mesh), a silicone coating agent (Tosugad 510, effective content 15%, (Manufactured by Toshiba Silicone Co., Ltd.). Subsequently, hot air drying was performed at I00 ° C for 30 seconds. As a result, a film in which a silicone was combined with a water-soluble film was obtained. The compounding amount of Tosgard 510 was 2.0 g / m ² .

Comparative Example 3

The water-soluble film (F-2) was used as a comparative sample as it was.

The films obtained in Example 13 and Comparative Example 3 were compared with those of Example 17 and Comparative Example 3. Evaluation was performed in the same manner as in Comparative Examples 1-2. Table ₃ shows the results.

(2) In the feel test, it is assumed that the film is individually wrapped.

Table 3

*: Ratio to water-soluble polymer

The film of the present invention is one in which the film is dissolved or hydrolyzed by contact of the film with water or the like, and the contents packaged in the film function. When used, the contents of foods, agricultural chemicals, household goods, etc. can be easily and conveniently taken out. This film is excellent in water solubility and water dissolvability, not only enables long-term storage and storage in high humidity environments, but also has no stickiness when touched by hand and is excellent in the touch surface.

Claims

The scope of the claims

(1) A film in which a water-insoluble material is present on the surface of a water-soluble film, wherein the used amount of the water-insoluble material is 0.1 to 80 parts by weight with respect to 100 parts by weight of the water-soluble film, A film in which the water-insoluble material is a powder having an average particle size of 500 μm or less.

(2) A film in which a water-insoluble material is present on the surface of a water-soluble film, wherein the used amount of the water-insoluble material is 0.1 to 80 parts by weight with respect to 100 parts by weight of the water-soluble film, A film in which the water-insoluble material has a fibrous form with a fiber length of 10 μm to 6 mm.

3. The film according to claim 1, wherein the water-soluble film contains a plasticizer.

4. The finolem according to claim 1, having an embossed pattern on the surface.

5. The film according to any one of claims 1 to 4, which is perfumed.

6 A film in which a water-insoluble material is fixed to a film surface by a binder, wherein the binder is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the water-insoluble material. The film of any one of the above items.

7 A film in which a water-insoluble material is present on the surface of a water-soluble film, and the amount of the water-insoluble material used is 0.1 to 80 parts by weight with respect to 1 part by weight of the water-soluble film. A film in which the water-insoluble material has a powdery form having an average particle diameter of 500 μm or less or a fibrous form having a fiber length of 10 μm to 6 mm.

8 A method for producing a film in which a water-insoluble material is present on the surface of a water-soluble film, wherein the water-insoluble material is fixed on the surface of the water-soluble film by coating or printing.

9 Water-insoluble material is powder with an average particle diameter of 500 m or less or water-insoluble material is fiber length 1 Ομπ! 9. The method according to claim 8, wherein the method has a fibrous form which is hidden.

100 Water-soluble film surface Film containing 100 parts by weight and 0.1 to 80 parts by weight of water-insoluble material, wherein the water-insoluble material is powder or fiber having an average particle size of 500 μm or less. A process for producing a film that has a fibrous morphology of 10 μm to 6 mm in length and has a water-insoluble material coated or printed on the surface of the water-soluble film and fixed.

1 1 Moisture content is 50 weight. /. A method for producing a film in which a water-insoluble material is present on the surface of the thin film of the water-soluble polymer and then dried.

1 2 A method for producing a film in which a mixture of a water-insoluble material and a binder solution is present on the surface of a water-soluble film and then dried.

13 Moisture content is 50 weight. /. A water-insoluble material is present on the surface of the thin film of the water-soluble polymer, and then dried to obtain a film. The amount of the water-insoluble material used is 0.1 to 100 parts by weight of the thin film of the water-soluble polymer. 80 parts by weight, wherein the water-insoluble material has a powdery form having an average particle diameter of 500 μm or less or a fibrous form having a fiber length of 10 / im to 6 mm.The film according to claim 7, wherein Recipe.

14 A mixture of a water-insoluble material and a binder solution is present on the surface of the water-soluble film, and then dried to obtain a film.

0.1 to 80 parts by weight with respect to 0 parts by weight, and the water-insoluble material is powder or fiber having an average particle diameter of 500 μm or less 10 μππ! The method for producing a film according to claim 7, wherein the film has a fibrous form of from 6 to 6 mm.

A laundry article packaged with the film according to any one of claims 1 to 7.