JP3157814B2 - Sheet laundry - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a sheet-like laundry article.

[0002]

2. Description of the Related Art There is known a sheet-like laundry article comprising a layer containing a detergent composition and a water-soluble substrate disposed on both sides of the layer.
No. 72599). However, the sheet-like laundry article is
Due to the sheet shape, the surface area is smaller than that of the powder detergent, and since the detergent components are compacted, the low-temperature solubility is still insufficient. Accordingly, an object of the present invention is to provide a sheet-like laundry article having significantly improved solubility.

[0003]

SUMMARY OF THE INVENTION The present invention provides a sheet-like laundry article comprising a layer containing a detergent composition and a water-soluble substrate bonded to both sides of the layer. 60μ diameter
The present invention relates to a sheet-like laundry article containing a group of water-soluble or water-disintegrable particles having a size of m to 2000 μm.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION [Water-soluble and / or water-disintegrable particles] The layer containing the detergent composition constituting the sheet-like laundry article of the present invention has a water-soluble or water-disintegrable particle having an average particle size of 60 µm to 2000 µm. Contains a group of conductive particles. Here, the term "water-soluble or water-disintegrable" refers to a 1L beaker (a cylindrical shape having an inner diameter of 105 mm and a height of 150 mm, for example, a 1L beaker of Iwaki Glass Co., Ltd.).
Inside, 0.5 g of the particle group was put into 1 L of water at 10 ° C., and the rotation speed was 800 with a stirrer (length 35 mm, diameter 8 mm).
This refers to the property of particles having less than 0.025 g of residue on the sieve when sieved with a 200 mesh metal sieve after stirring for 10 minutes at rpm. Preferred “water-soluble or water-disintegrable” means that the amount of the residue under the above conditions is less than 0.025 g within 7 minutes, particularly within 5 minutes.

The average particle size of the water-soluble or water-disintegrable particles determined from a standard sieve according to JIS Z8801 is 60 to 200.
0 μm, preferably 88 to 1410 μm, particularly preferably 125 to 1000 μm. Here, it is preferable that the amount of the particle group having a particle size smaller than the lower limit is less than 5% by weight in the whole particle group, and the amount of the particle group exceeding the upper limit is less than 5% by weight in the whole particle group. When the average particle size is less than 60 μm, the effect of improving the solubility is poor, and when it exceeds 2000 μm, it tends to remain in clothes or a washing machine after washing, which is not preferable.

[0006] The water-soluble or disintegrable particles according to the present invention preferably have the following properties and properties.

In the process of dissolving in water, 1 / of the particle diameter
To release bubbles having a diameter of 10 or more from the inside of the particles (particles that release bubbles are also referred to as “bubble releasing particles” hereinafter). Here, in the process of dissolving in water, first, when a small amount of water enters the inside of a particle, bubbles of a predetermined size are released from the inside of the particle, and then a large amount of water enters the inside of the particle. As a result, the particles themselves disintegrate (self-disintegration of the particles), meaning that not only dissolution near the surface but also dissolution and disintegration from inside the particles occur. Such a dissolution behavior is such that, when the bubble releasing detergent particles are dissolved in water, the particle size is at least 1/10, preferably 1/5 of the particle size of the particles.
Or more, more preferably 1/4 or more, still more preferably 1 /
Bubbles with a diameter of 3 or more (hereinafter referred to as bubbles of a predetermined size)
Can be confirmed with a digital microscope, an optical microscope, or the like. When the bubble releasing detergent particles are dissolved in water in a static state, bubbles of a predetermined size are preferably generated within 120 seconds.
0 seconds or less are more preferable, and 45 seconds or less are still more preferable.

The method for measuring the bubble diameter is as follows. A double-sided tape is attached to the center of the bottom of a glass Petri dish (50 mm in inner diameter). The group of water-soluble or disintegrable particles is adhered on a double-sided tape. First, the circle equivalent diameter (α) of each particle is obtained from an image obtained using a digital microscope.
μm). As the digital microscope, for example, VH-6300 manufactured by KEYENCE can be used. Subsequently, 5 mL of 20 ° C. ion-exchanged water is injected into the glass Petri dish, and the dissolution behavior of individual particles to be measured is observed. When air bubbles are released from the inside of the particles, the circle equivalent diameter (β μm) of the air bubbles is measured from an image at the moment when the air bubbles are separated from the particles. When a plurality of bubbles are released from the inside of the particle, the maximum value of the equivalent circle diameter measured for each bubble is set to β μm. Then, the ratio of the bubble diameter to the particle diameter (β / α) is determined for each particle. In addition, the bubble release detergent particles have 1/100 of the particle size inside.
It is preferable that pores having a diameter of 10/4/5, preferably 1/5/4/5 are present.

When charged in water at 5 ° C. and stirred for 60 seconds under the following stirring conditions and then subjected to a standard sieve specified by JIS Z 8801 (mesh size: 74 μm), the particle group calculated by the formula (1) Dissolution rate is 90% or more. Stirring conditions: 1 L of hard water (71.2 mg CaCO ₃ / L,
1 g of the particle group was added to a Ca / Mg molar ratio of 7/3),
In a 1L beaker (inside diameter 105mm), stirrer (length 35)
mm, diameter 8 mm), rotation speed 800 rpm, dissolution rate (%) = [1- (T / S)] × 100 (1) S: input weight of the particle group (g) T: under the above stirring conditions When the obtained aqueous solution is subjected to the above sieve, the dry weight (g) of the residue of the particles remaining on the sieve is preferably 94% or more, more preferably 97% or more.

Hereinafter, the stirring conditions will be described. 1 L of hard water (Ca / Mg molar ratio 7/3) equivalent to 71.2 mg CaCO ₃ / L cooled to 5 ° C. was poured into a 1 L beaker (a cylindrical type having an inner diameter of 105 mm and a height of 150 mm, such as a 1 L glass beaker manufactured by Iwaki Glass Co., Ltd.) ), While keeping the water temperature at 5 ° C. constant in a water bath, a stirrer (length 35 mm, diameter 8 mm, model: ADVANTE, for example)
C company, Teflon SA (round thin type)), the number of revolutions (800 rpm) at which the depth of the spiral with respect to the water depth becomes approximately 1/3
And stir. The particle group reduced and weighed so as to be 1.0000 ± 0.0010 g is charged and dispersed in water with stirring, and stirring is continued. After 60 seconds from the introduction, the particle group dispersion in the beaker was filtered through a standard sieve (diameter: 100 mm) having a mesh size of 74 μm and having a mesh size of JIS Z8801, and the water-containing particle group remaining on the sieve was removed. Collect with sieve in open container of known weight. The operation time from the start of filtration to the collection of the sieve is 10 ± 2 seconds. The collected residue of the particle group is dried for 1 hour using an electric dryer heated to 105 ° C., and then cooled in a desiccator (25 ° C.) containing silica gel for 30 minutes. After cooling, the total weight of the dried residue of the detergent, the sieve, and the collection container is measured, and the dissolution rate (%) of the particle group is calculated by the above equation (1).

In the present invention, the water-soluble or water-disintegrable particles are preferably contained in the detergent composition-containing layer in an amount of 10 to 90% by weight in view of the solubility of the detergent composition and the ease of preparation. , More preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight.

The water-soluble or water-disintegrable particles in the present invention are, specifically, particles comprising a water-soluble inorganic substance, a water-insoluble or hardly water-soluble inorganic substance, or a water-soluble organic substance.

As the water-soluble inorganic substance, sodium carbonate,
Carbonates such as potassium carbonate, sodium bicarbonate and potassium bicarbonate; sulfates such as sodium sulfate, potassium sulfate and sodium sulfite; and chlorides such as sodium chloride. As the water-soluble inorganic substance, for example, one that dissolves 0.1 to 50 g in 100 g of water at 20 ° C. (stirring speed: 800 rpm, stirring time: 10 minutes) can be used.

Examples of the water-insoluble or poorly water-soluble inorganic substance include hydrated silicates having a three-layer structure called smectite clay, such as montmorillonite, beederite, and the like.
Swellable clay minerals such as nontronite, hectorite, saponite and the like can be mentioned. For example, commercially available products such as Wenger (Toyojun Yokosha), Kunipia (Kunimine Kogyo), Smecton (Kunimine Kogyo), Laponite (Laporte) can be used. In addition, crystalline aluminosilicate (zeolite), crystalline silicate (for example, SKS-6 from Clariant Japan), Britesil (The PQ C
or inorganic materials having a primary particle size of 50 μm or less, such as an inorganic material. Less than 0.1 g of a poorly water-soluble inorganic substance is dissolved in, for example, 100 g of water at 20 ° C. (stirring speed: 800 rpm)
m, stirring time: 10 minutes).

Examples of the water-soluble organic substance include known surfactants, organic metal ion scavengers such as ethylenediaminetetraacetic acid and citrate, and polycarboxylic acid polymers such as acrylic acid-maleic acid copolymer salts (eg, BASF). Sokalan CP 5). As the water-soluble organic substance, for example, one that dissolves in an amount of 0.1 g or more in 100 g of water at 20 ° C. (stirring speed: 800 rpm, stirring time: 10 minutes) can be used.

The composite particles may be composed of the above-mentioned water-soluble inorganic substances and water-insoluble or poorly water-soluble inorganic substances, or, if necessary, with these water-soluble organic substances. Can be. In this case, particles (base particles) obtained by spray-drying a slurry containing these water-insoluble inorganic substances and the like are preferable. Further, as the composite particle group, a detergent particle group is also preferable. As the detergent particle group, a detergent particle group in which a surfactant is supported on a base particle group composed of a water-insoluble inorganic substance, a water-soluble polymer, and a water-soluble salt is also preferable.

The water-insoluble inorganic substance used in the base particles of the detergent particles has an average primary particle diameter of 0.1 to 0.1.
20 μm is preferable, and examples thereof include crystalline or amorphous aluminosilicates, clay compounds such as silicon dioxide, hydrated silicate compounds, pearlite, and bentonite, among which sequestering ability and oil absorption of surfactants are included. A crystalline aluminosilicate is preferred in terms of performance.

Examples of the water-soluble polymer used in the base particles of the detergent particles include carboxylic acid polymers, carboxymethylcellulose, soluble starch, and saccharides. Among them, sequestering ability of metal ions and dispersing ability of solid soil particles are included. A carboxylic acid polymer having a molecular weight of several thousands to 100,000 is preferable from the viewpoint of the ability to prevent re-contamination. In particular, a salt of an acrylic acid-maleic acid copolymer and a polyacrylate (such as an alkali metal salt, an ammonium salt, and an amine salt) are preferable.

The water-soluble salts used in the base particles of the detergent particles include alkali metal salts such as carbonates, hydrogencarbonates, sulfates, sulfites, hydrogensulfates, hydrochlorides, and phosphates, and ammonium salts. And water-soluble inorganic salts such as amine salts, and low-molecular-weight water-soluble organic salts such as citrate and fumarate. The inorganic salts are more preferable because bubbles from the detergent particles can be thermally expanded by heat of hydration and heat of dissolution generated by reaction with water, and disintegration of the particles can be promoted.

It is preferable that the base particles have an uneven distribution in which the water-soluble polymer and / or water-soluble salts are present more in the vicinity of the surface than in the inside. The base granules having this structure exhibit high-speed solubility by dissolving water-soluble components in the vicinity of the surface more quickly in water and exhibiting a dissolution behavior in which disintegration of the detergent particles from the particle surface is promoted. be able to. The most preferred embodiment for exhibiting high-speed solubility is uneven detergent properties, and moreover, bubbles releasing detergent particles.

In the composition of the base particles of the detergent particles, the content of the water-insoluble inorganic substance is preferably 20 to 90% by weight, more preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight. The water-soluble polymer is preferably 2 to 30% by weight, more preferably 3 to 20% by weight, particularly preferably 5 to 20% by weight.
-20% by weight. The water-soluble salts are preferably 5-78.
%, More preferably from 10 to 70% by weight, particularly preferably from 20 to 60% by weight. Within these ranges, the base granules are suitable for taking a structure in which the vicinity of the surface is coated with a water-soluble component, the coating layer on the particle surface is sufficiently formed, and sufficient particle strength is obtained. . It is also preferable in terms of solubility of the detergent composition. In addition to these three components, the base granules may contain known surfactants and auxiliary components such as fluorescent dyes, pigments and dyes.

Examples of the surfactant to be carried on the base particles of the detergent particles include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants. An ionic surfactant or a nonionic surfactant is used alone or in combination.

Examples of the anionic surfactant include a sulfate of an alcohol or an ethoxylate thereof, an alkylbenzene sulfonate, a paraffin sulfonate, an α-olefin sulfonate, an α-sulfofatty acid or an ester salt or a fatty acid salt thereof. Is preferred. In particular,
The alkyl chain has 10 to 14 carbon atoms, more preferably 1 carbon atom.
2 to 14 linear alkylbenzene sulfonates are preferred, and as counter ions, alkali metals and amines are preferred, and sodium, potassium, monoethanolamine and diethanolamine are particularly preferred.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, alkylene polyglycoside,
Preferred are polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene glycol fatty acid esters, polyoxyethylene polyoxypropylene block polymers, and polyoxyalkylene alkylolamides. In particular, an alcohol having 10 to 18 carbon atoms is added with 4 to 20 moles of an alkylene oxide such as ethylene oxide (hereinafter referred to as EO) or propylene oxide (hereinafter referred to as PO), and has an HLB value (calculated by the Griffin method) of 10.5-1.
5.0, especially 11.0-14.5 polyoxyalkylene alkyl ethers are preferred.

The amount of the surfactant is preferably from 5 to 80 parts by weight, more preferably from 5 to 60 parts by weight, further preferably from 10 to 60 parts by weight, based on 100 parts by weight of the base granules in terms of detergency. Preferably, 20 to 60 parts by weight is particularly preferable.

The other water-soluble or water-disintegrable particles include enzyme-containing granules, soft component-containing granules such as quaternary ammonium salts, foam control component-containing granules such as dimethyl silicone, and fragrance-containing particles. Granules and the like can be mentioned.

The water-soluble or water-disintegrable particles such as detergent particles are added to the surface of the layer containing the detergent composition in order to improve the solubility.
It is preferable that the number is 10 or more per cm ² .

Here, a method of separating the water-soluble or water-disintegrable particles from the detergent composition will be described. First, 10 g of the detergent composition is dispersed and dissolved in 1 L of ethanol (special grade) in a 1 L beaker (inner diameter: 105 mm). In addition, stirring is performed for 30 minutes using ultrasonic waves that do not destroy the particle group. After dispersing and dissolving, the mixture is filtered through a 200-mesh sieve, and dried at 105 ° C. for 1 hour using an electric drier. After drying, the particles are transferred to a desiccator and allowed to cool naturally for 2 hours, whereby the particle group can be separated.

[Detergent Composition] The detergent composition of the present invention is mainly composed of a surfactant and a builder component. When the detergent particles described above are used as water-soluble or water-disintegrable particles, A detergent composition is composed of the detergent particles and other components. When the composite particles obtained by spray-drying the water-insoluble inorganic substance or the like are used, a detergent composition is composed of the composite particles and a detergent component such as a surfactant.

As the surfactant, the same surfactant as that used for the base particles of the detergent particles can be used. The content of the surfactant is from 5 to 80% by weight, more preferably from 20 to 60% by weight, particularly preferably from 30 to 50% by weight in the detergent composition in terms of detergency. In particular,
A nonionic surfactant is preferable in terms of easy adjustment of sheet flexibility, and particularly, an alcohol having 10 to 16 carbon atoms,
O 5 to 10 mol adducts, EO 4 to 12 mols of alcohol having 10 to 16 carbon atoms and 0.1 to 4 mols of PO adducts (however, EO and PO may be either random polymerization or block polymerization) are preferred. Further, a form in which a nonionic surfactant and a polyalkylene glycol having a pour point of 40 ° C. or higher such as polyethylene glycol are used in combination is also preferable. The content of the polyalkylene glycol is preferably 0.3 to 30% by weight, more preferably 1.5 to 14% by weight. The weight ratio of the nonionic surfactant to the polyalkylene glycol is 98/2 to 70/30, preferably 95/5 to 80/2.
0. Further, the total content of the nonionic surfactant and the polyalkylene glycol is preferably 3 to 50% by weight, more preferably 6 to 30% by weight. It is also preferable to use a nonionic surfactant and an anionic surfactant in combination. In this case, the total of both is 50 to 50 in the surfactant component.
It is preferably 100% by weight, particularly preferably 70 to 100% by weight, from the viewpoint of cleaning performance. The weight ratio of the nonionic surfactant to the anionic surfactant is such that, in terms of solubility, nonionic surfactant / anionic surfactant = 100/0 to 10/9.
0, particularly preferably 90/10 to 50/50.

Examples of the builder include inorganic builders such as carbonates, crystalline aluminosilicates, amorphous aluminosilicates, crystalline silicates, amorphous silicates, phosphates and borates, and nitrilotriazoles. Alkali metal salts such as sodium and potassium such as organic builders such as acetate, ethylenediaminetetraacetate, tartrate, citrate, and acrylic acid (co) polymer. Particularly, a crystalline aluminosilicate is preferred in terms of sequestering ability. The content of the builder is preferably from 5 to 70% by weight in the detergent composition from the viewpoint of improving the detergency.
More preferably 10 to 60% by weight, particularly preferably 15% by weight.
~ 55% by weight.

The content ratio between the surfactant and the builder is as follows:
Surfactant / builder = 1/5 to 10/1 (weight ratio), more preferably 1/3 to 3/1, and particularly preferably 1 in terms of improving the detergency and flexibility of the sheet-like laundry article. / 2 to 3/2.

Further, the detergent composition of the present invention contains a bleaching agent (percarbonate, perborate, bleach activator, etc.) and a re-staining inhibitor (carboxymethylcellulose, etc.) which are known in the field of detergents for clothing. ), A softening agent, a reducing agent (such as a sulfite), a fluorescent whitening agent, a foam inhibitor (such as silicone), and a fragrance.

The water content of the cleaning composition of the present invention is preferably 0.1 to prevent blocking due to dissolution of a water-soluble substrate and to prevent drying of the cleaning composition.
-15% by weight, more preferably 1.5-10% by weight, particularly preferably 2-7% by weight. The water of crystallization such as zeolite, carbonate and citrate is excluded.

In the present invention, the layer of the cleaning composition comprises
It is preferably formed from a dough containing water-soluble or water-disintegrable particles and other components, particularly detergent particles and a binder component. When making a detergent composition into a dough, the penetration hardness at 25 ° C. is preferably 0.1 to 20 kg.
/ Cm ² , more preferably 0.5 to 15 kg / cm ² ,
Particularly preferably, it has a hardness of 1.5 to 10 kg / cm ² . Here, "dough" refers to a kneaded product of a powder composition and a fluid substance such as a liquid, paste, or gel composition. The substance having fluidity includes a substance having fluidity due to heating or stress. The penetration hardness is 25 ° C.
Rheometer (FUDO)
H RT-2010J-CW) (bottom area 1)
pressed cm circle ^2), the adapter can be determined by measurement of stress upon 2cm enters inside the 30 cm / min approach speed of the detergent composition. The dough is
It can be manufactured using a universal stirrer, kneader or the like suitable for high viscosity stirring. Further, by adding a polyalkylene glycol having a molecular weight of 2000 or more, a dough can be produced in a short time.

The viscosity of the doughy detergent composition (Tokyo Keiki DVM-B rotor No. 4, rotation speed 3 rpm,
25 ° C.) is 100,000 mPa · s or more, more preferably 2 mPa · s or more.
It is more than 100,000 mPa · s.

The thickness of the layer containing the detergent composition is preferably less than 1 cm, more preferably 0.03 to 0.8 cm, and particularly preferably 0.07, in view of low-temperature solubility and convenience.
~ 0.5 cm. The layer containing the cleaning composition in the present invention may be in a form other than a dough such as a paste.

[Water-soluble substrate] The water-soluble substrate of the present invention is bonded to both sides of the layer containing the detergent composition, and has a function of maintaining the shape of the sheet-like laundry article.

The water-soluble substrate of the present invention includes (i) a water-soluble film, (ii) a water-soluble nonwoven fabric or woven fabric, (iii) a water-soluble laminated substrate comprising the water-soluble film and the water-soluble nonwoven fabric or woven fabric, (Iv) Laminates formed from a water-soluble fiber web and a water-soluble film. In particular, (iv) is preferable in terms of prevention of blocking between sheet-like laundry articles due to moisture and simplicity.

The water-soluble substrate in the present invention includes, for example,
Polyvinyl alcohol (hereinafter referred to as PVA), polyvinylpyrrolidone, pullulan, polyacrylamide, polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, polyitaconic acid or a salt thereof, polyethylene oxide, polyvinyl methylene ether, xanthan gum, guar gum,
Examples include a water-soluble substrate containing an alkali-resistant water-soluble polymer compound such as collagen, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.

In particular, partially saponified PVA having a degree of saponification of less than 96 mol%, or a degree of saponification of 96 mol% or more, preferably 98 mol% or more, and an average degree of polymerization of 250 to 30
A saponified anion group-modified PVA having a molecular weight of 00, preferably 500 to 2500 is preferred. Examples of the monomer having an anionic group include acrylic acid, crotonic acid, maleic acid, fumaric acid, unsaturated carboxylic acids such as itaconic acid, unsaturated sulfonic acids, and esters or anhydrides thereof, and particularly maleic acid. Itaconic acid and 2-acrylamido-methylpropanesulfonic acid are preferred. The modification rate of the anionic group is 0.1 to 8 mol%, preferably 1 to 5 mol%, based on the total amount of monomer units in all molecules.

Other water-soluble substrates are described in
JP-A-725599, column 5, line 47 to column 6, line 31.

The water-soluble substrate of the present invention has processability,
Water-soluble substrates containing a polyhydric alcohol plasticizer such as ethylene glycol, propylene glycol or glycerin, or an anionic or cationic surfactant, in terms of flexibility, anti-blocking properties, and imparting hydrophilicity, may also be used. The thickness of the water-soluble substrate depends on the type, properties and amount of the detergent composition, but is preferably 5 to 20 in view of flexibility, flexibility and ease of use.
0 μm, especially 10 to 100 μm.

The laminated material formed of the water-soluble fiber web and the water-soluble film of (iv) is a water-soluble PVA having a melting point of at least 140 to 220 ° C.
Having a basis weight of 50 g, which is formed from a web composed of a base fiber and a water-soluble PVA-based film having a melting point of 140 to 220 ° C.
/ M ² or less (hereinafter sometimes referred to as a laminated material (iv)). Preferred examples of the fibers constituting the web of the laminated material (iv) include low-temperature water-soluble PVA-based fibers described in JP-A-8-118559. As the fiber, a partially saponified PVA-based fiber is more preferable from the viewpoint of solubility and economy after forming a laminated material.
Partially saponified PVA means that the degree of saponification is 70 mol% or more,
Less than 6 mol% means an average degree of polymerization of 250 to 3000, preferably 500 to 2500. Such PV
The stable obtained by crimping and cutting the A fiber can be opened with a card or the like to form a web. In addition, a web is preferable in terms of solubility compared with a nonwoven fabric.

As the water-soluble PVA-based film of the laminate (iv), various modified PVA-based films can be used. In particular, the contact surface of the detergent composition is preferably a completely saponified PVA-based film in that the water solubility of the laminate does not deteriorate even when the laundry article is stored for a long period of time, even if it comes into contact with detergent components. Here, fully saponified PVA
Has a saponification degree of 96 mol% or more, preferably 98 mol% or more.
Water-soluble ones can be used at mol% or more. In particular, the average degree of polymerization is 250 to 3000, preferably 500 to 2500.
The completely saponified anion group-modified PVA is preferable. The monomer forming the completely saponified anion group-modified PVA, that is, the monomer having an anion group is the same as in the case of the above-mentioned saponified anion-modified PVA.

The melting point of the fiber is measured by using a differential scanning calorimeter (DSC-20) of Mettler Co., Ltd., and measuring the temperature at which the temperature shows an endothermic peak when the temperature is raised at a rate of 10 ° C./min.

The laminate (iv) is formed from at least a web and a film. For example, a laminated material (iv) composed of a web and a film can be obtained by laminating a web and a film and performing thermocompression bonding in that state. In particular, the crimping area ratio is preferably 10 to 50%
The method of forming a laminated material by thermocompression bonding of a web and a film with a hot embossing roll can fix the fibers in the web and the entire web to the film at the same time. It is preferable in terms of economy and economy. The thermocompression bonding method described above is also preferable in that, in addition to workability, the feel when touched and the solubility resistance to wet hands are improved.

For the laminate (iv), another alkali-resistant water-soluble polymer may be used as a raw material as long as the effects of the present invention are not impaired.

The basis weight of the laminated material (iv) is 50 g / m ^2.
Hereinafter, it is preferably 10 to 50 g / m ² , particularly preferably 30 to 45 g / m ² . From the viewpoint of cold water solubility and production cost, the basis weight is preferably 50 g / m ² or less. Further, from the viewpoints of strength against wet hands and workability, the basis weight is desirably 10 g / m ² or more. The thickness of the laminated material depends on the type, properties and amount of the detergent composition, but is preferably from 5 to 200 μm, particularly from 10 to 10 from the viewpoint of flexibility and ease of use.
110 μm.

The laminated material (iv) is made of distilled water 1 at 10 ° C.
The laminated material (3 cm × 3 cm, 4 sheets) was put into L and mixed and stirred for 8 minutes (agitating at 550 rpm using a stirrer having a total length of 35 mm and a maximum diameter of 7.5 mm). It is preferable that the residue be passed through a sieve without any residue, or the residue be less than 2% by weight of the laminate. That is, the dissolution rate of the laminate is preferably 98% or more. Here, the laminated material (iv) may be provided with irregularities such as a lattice shape or a turtle shape by embossing or the like in terms of solubility and anti-blocking properties.

[Sheet-like laundry article] The sheet-like laundry article of the present invention comprises a layer containing a detergent composition and a water-soluble substrate bonded to both sides of the layer. The sheet-like laundry article has a detergent composition and an average particle size of 60 μm to 2000 μm.
And water-soluble or water-disintegrable particles are mixed to form a layer of the mixture, and a water-soluble substrate is bonded to both sides of the layer. A method in which a dough-shaped detergent composition is formed into a sheet shape in advance, and one or more water-soluble substrates are joined to both surfaces of the dough-shaped detergent composition.
A method of compression-molding with a roller or a press while supplying between two or more water-soluble substrates, a method of applying a dough-like detergent composition to a water-soluble substrate and bonding another water-soluble substrate And a method in which a water-soluble substrate is impregnated with a dough-like cleaning composition, and the water-soluble substrate is bonded to both sides thereof. Bonding is preferably performed over the entire surface, but may be performed partially as long as the shape and performance of the sheet-like laundry article are not impaired.

In a particularly preferred embodiment of the present invention, a water-soluble substrate is bonded to both sides of a layer containing a dough-like detergent composition comprising detergent particles, which are a group of water-soluble or water-disintegrable particles, and a binder component. This is a sheet-like laundry article.

The thickness of the sheet-like laundry article of the present invention is preferably 1 cm or less in terms of solubility, flexibility and ease of use.
It is more preferably 0.05 to 0.7 cm, still more preferably 0.1 to 0.5 cm, and its area density is preferably 0.005 to 1.8 g / cm ² , more preferably 0.02 g. / Cm ^{2 to} 0.7 g / cm ² .

In order to prevent the contents from being lost, the above-mentioned sheet-like laundry article seals around (for example, water-soluble substrates bonded to both sides of the layer containing the detergent composition) or breaks. Perforations may be applied for ease of use, or rolls may be loaded.

[0055]

EXAMPLES Examples 1 to 12 and Comparative Examples 1 and 2 [Preparation of water-soluble substrate] Average polymerization degree 1700, saponification degree 9
9.9% itaconic acid-modified PVA (degree of modification 3 mol%)
Was used to prepare a 15% by weight aqueous solution containing 2% by weight of glycerin, and then a 20 μm-thick water-soluble film (denoted as “film” in Table 2) was prepared by thin-film hot-air drying. In addition, a water-soluble nonwoven fabric having a basis weight of 30 g / m ² was prepared using the same PVA in accordance with Example 2 of JP-A-8-3848. The nonwoven fabric and the water-soluble film were laminated and subjected to a heat embossing treatment to obtain a laminated water-soluble substrate A (denoted as “laminate A” in Table 2). Further, instead of the itaconic acid-modified PVA, an average degree of polymerization of 1700,
Laminated water-soluble substrate B was prepared in the same manner except that maleic acid-modified PVA having a saponification degree of 97.0% (modification degree: 3 mol%) was used.
(Referred to as “Lamination B” in Table 2).

[Preparation of Base Granule Group] Water 465 at 55 ° C.
kg, 50% by weight of sodium dodecylbenzenesulfonate [Neoperex F65 (Kao Corporation), LA in Table 1
S-Na] 48 kg of aqueous solution, 40% by weight of sodium polyacrylate (average molecular weight 10,000, Table 1
135 kg of an aqueous solution (indicated as medium PPA-Na) were added. After stirring for 15 minutes, 120 kg of sodium carbonate (Dense Ash, Central Glass Co., Ltd.), 60 kg of sodium sulfate (anhydrous neutral), 9 kg of sodium sulfite, and 3 kg of a fluorescent dye (Tinopearl CBS-X manufactured by Ciba Geigy) were added. After further stirring for 15 minutes, 300 kg of zeolite 4A (average particle size: 3.5 μm, Tosoh Corporation) was added and stirred for 30 minutes to obtain a homogeneous slurry. The final temperature of this slurry was 58 ° C.

The slurry was supplied to a spray drying tower, and sprayed at a spray pressure of 25 kg / cm ² from a spray nozzle near the top of the tower to obtain a base granule group I. The composition (weight ratio) of the base granule group I is zeolite 50% by weight, sodium polyacrylate 9% by weight, sodium carbonate 20% by weight, sodium sulfate 10% by weight, sodium sulfite 1.5% by weight, dodecylbenzenesulfonic acid 4% by weight of sodium,
0.5% by weight of dye and 5% by weight of water. Base granule group I
In the same manner as described above, the base granules II
~ IV.

[0058]

[Table 1]

[Preparation of Detergent Particle Group] 100 parts by weight of the above-mentioned base granule group I was put into a Lodige mixer (Matsuzaka Giken Co., Ltd., capacity 20 L, with jacket), and heated to 50 ° C. while stirring the main shaft and the chopper. 23 parts by weight of an adduct of 7 mol of ethylene oxide of a secondary alcohol having 12 to 14 carbon atoms (Nippon Shokubai Co., Ltd., Sophthanol 70H) were charged in 2 minutes, and then stirred for 4 minutes and discharged. The average particle size of the obtained detergent particles was 230 μm,
0.1% by weight of particle group of 000 μm or more, particle diameter 60 μm
The particle group of less than 0.1% by weight. Further, 0.5 g of the detergent particles were put into 1 L of water at 10 ° C., and the number of rotation was 800
The mixture was stirred at rpm for 5 minutes and sieved with a 200-mesh sieve, and no residue on the sieve was observed.

[Preparation of Sheet-like Laundry Article] A detergent composition comprising the components shown in Table 2 was charged into a universal mixing stirrer (Dalton Co., Ltd., Model 5DM-03-r).
The mixture was stirred until a uniform dough-like detergent composition was obtained. Next, Dorsita (Saber Econom STM513)
A layered material having a thickness of 0.15 cm was prepared using
It was cut to 10 cm.

Here, by observing the surface of the layer containing the detergent composition, the presence of 20 detergent particles per 1 cm ² can be confirmed. Of the detergent particles was confirmed.

The above-mentioned layered material was sandwiched between two water-soluble films or two laminated water-soluble substrates A or B having a non-woven fabric on the outside, and heat-sealed to obtain a sheet-like laundry article. The average weight is 10 g and the average area density is 0.
It was ² g / cm ² . Next, the dissolution rate of the sheet-shaped laundry article was evaluated according to the following measurement method. Table 2 shows the results.

[Measurement method of dissolution rate] Sheet-like laundry article 1
0 g is put into a washing machine (Toshiba Ginga 3.6 (VH360S1)) containing 5 L of tap water and 30 L of tap water. "Strong rotation"
After dewatering and draining for 5 minutes. The detergent residue in the drain port equipped with a 500 μm sieve and the washing machine was collected, air-dried at room temperature, and the weight was measured. Dissolution rate (%) = [(weight before charging-residue weight) / (weight before charging)] × 100 In this test, the dissolution rate is desirably 50% or more.

Comparative Examples 1 and 2 A dough was prepared from the cleaning compositions shown in Table 2 in the same manner as in the Examples, and a sheet-like laundry article was obtained in the same manner as described above using two laminated water-soluble substrates A. The solubility was evaluated in the same manner as in the Examples. Table 2 shows the results.

[0065]

[Table 2]

(Note) • Nonionic surfactant I: secondary alcohol having 12 to 14 carbon atoms with an average of 7 mol added to EO. • Nonionic surfactant II: primary alcohol having 12 to 14 carbon atoms. EO average 5 mol, PO average 2 mol, EO average 3
Nonionic surfactants III: Primary alcohols having 12 to 14 carbon atoms added with an average of 7 moles of EO and an average of 3 moles of PO in this order Nonionic surfactants IV: LAS-MEA: linear alkyl (10 to 13 carbon atoms) obtained by adding an average of 7 moles of EO to a primary alcohol having 12 to 14 carbon atoms
Benzenesulfonic acid monoethanolamine salt • LAS-Na: straight-chain alkyl (10 to 13 carbon atoms) benzenesulfonic acid sodium salt • AS-Na: straight-chain alkyl (10 to 13 carbon atoms) sodium sulfate ester • PEG: polyethylene Glycol, average molecular weight 800
0

[0067]

The sheet-like laundry article of the present invention contains water-soluble or water-dispersible particles which dissolve or disintegrate in water, so that the surface area of the detergent composition is increased and the solubility is greatly improved. I do.

Continued on the front page (72) Inventor Hiroyuki Saijo 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Research Laboratory (72) Inventor Hiromitsu Hayashi 1334 Minato, Wakayama City Wakayama Prefecture Kao Corporation Research Laboratory (72) Inventor Hiroyuki Yamashita Wakayama Wakayama Prefecture 1334 Ichiminato Kao Corporation Laboratory (56) References JP-A-10-72593 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 17/04 CA (STN) CAOLD ( STN) REGISTRY (STN) WPIDS (STN)

Claims (5)

(57) [Claims] 1. A sheet-like laundry article comprising a layer containing a detergent composition and a water-soluble substrate bonded to both sides of the layer, wherein the layer contains a water-soluble inorganic substance, a water-insoluble substance or a water-insoluble substance.
Including one or more selected from soluble inorganic substances and water-soluble organic substances
And / or particles obtained by spray drying the slurry having
Is a detergent particle group in which a surfactant is supported on the particle group?
Ranaru, sheet laundry products having an average particle diameter contains water-soluble or water-disintegrable particles of 60Myuemu～2000myuemu. 2. A group of water-soluble or water-disintegrable particles is charged with 0.5 g of the particle group in 1 L of water at 10 ° C. and rotated at 800 rpm.
The residue on the sieve when sieving with a 200-mesh sieve after stirring at m for 10 minutes is less than 0.025 g.
A sheet-like laundry article as described. 3. The sheet-like laundry article according to claim 1, wherein the content of the water-soluble or water-disintegrable particles in the layer is 10 to 90% by weight. 4. A sheet-like washing article of any one of claims detergent composition is a dough-like material or a paste-like product 1-3. 5. A cleaning composition, a water-soluble inorganic substance, and water-insoluble
Selected from water-soluble or poorly water-soluble inorganic substances and water-soluble organic substances
Obtained by spray drying a slurry containing at least one
A particle group and / or a surfactant may be supported on the particle group.
Consisting of detergent particles having an average particle diameter of 60 μm to 2000 μm.
A method for producing a sheet-like laundry article, comprising mixing a water-soluble or water-disintegrable particle group of μm, forming a layer of the mixture, and bonding a water-soluble substrate to both sides of the layer.