JP2638405B2 - Packaged detergent using water-soluble film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention can suppress the exudation of a nonionic surfactant by unit-packing a detergent containing a large amount of a nonionic surfactant using a water-soluble film. , Unit packaging detergent.

[0002]

2. Description of the Prior Art Generally, there are two types of cleaning agents, liquid type and granular type. Conventional powder detergents for clothing have a bulk density of 0.2 to 0.4 g / cm ³ obtained by the spray drying method and a standard use amount of about 40 g per 30 liters of water per wash. 100 capacity
～200Cm ³ to a mainstream those 60-100 batch instrumentation in paper box, or square one directly tub lifting per box during the washing, a common practice is to put into the washing tub measures approximately in amounts such as a cup Was. These conventional detergent products have problems such as being bulky and not easy to carry, insufficient or insufficient in weighing, and scattering of detergent powder at the time of weighing or detergent introduction.

Therefore, recent detergents have a bulk density of 0.7 g / cm ³ or more, and the problem of carrying around has been improved. However, there still remains a problem regarding scattering of the detergent powder generated at the time of measurement or when the detergent is charged. One-pack detergents have been proposed in which detergent powder per wash is previously packaged with a water-insoluble, water-permeable or water-soluble material in order to solve the problem of scattering of detergent powder which occurs at the time of measurement or detergent introduction. For example, JP-A-63-84
No. 96, JP-A-63-8497, JP-A-63-124
No. 66, JP-A-63-12467 and JP-A-2-15
No. 5999, bulk density 0.5 to 1.2 g / cm
³ of the detergent with a water-soluble film packing and one-pack detergent comprising, as a one-pack detergent made by sachet paste detergent water-soluble film, packaging the detergent in the water-soluble material, a water-soluble film Several one-pack detergents have been proposed.

[0004] However, the main detergent of the one-pack detergent proposed so far mainly comprises an anionic surfactant, contains a large amount of a nonionic surfactant, and one-pack detergent as the main detergent is still proposed. Had not been. This is because it is difficult to powder the nonionic surfactant with a high content, and there are problems such as solubility at low temperature, seepage of the nonionic surfactant to the outside of the film, and further problems such as caking of detergent. Because there was.

[0005]

Means for Solving the Problems The present inventors have proposed a packaging detergent containing a nonionic surfactant as a main detergent, a nonionic surfactant and a porous oil-absorbing carrier, and a nonionic surfactant and a non-ionic surfactant. A cleaning composition containing the porous oil-absorbing carrier and the oil-absorbing carrier in such a manner that the relationship between the content of the porous oil-absorbing carrier and the pore volume of the oil-absorbing carrier has a specific ratio, and further containing a crystalline aluminosilicate, The present inventors have found that packaging with a conductive film dissolves quickly at a low temperature, does not exude, and provides a packaged packaging detergent excellent in caking resistance, thereby completing the present invention.

That is, the present invention relates to the following components: (a) 5 to 80% by weight of a nonionic surfactant (b) 5 to 60% by weight of a porous oil-absorbing carrier (c) 10 to 60% by weight of a crystalline aluminosilicate (A) the content of the nonionic surfactant is M% by weight, (b) the content of the porous oil-absorbing carrier is m% by weight, and (b) the pore volume of the porous oil-absorbing carrier is Vcc / g. Where M / (m
× V) is to provide a packaged detergent obtained by packaging a detergent composition having a numerical value of 2.0 g / cc or less in a water-soluble film having a film thickness of 10 to 150 μm. is there.

As the nonionic surfactant (a) used in the present invention, those which are in a liquid or slurry state at 40 ° C. or lower, that is, those having a melting point of 40 ° C. or lower are preferable in terms of washing. . (a) Specific examples of the component include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester,
Polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl Glycoside, alkylamine oxide and the like can be mentioned. Particularly preferred nonionic surfactants include those having 10 to 1 carbon atoms.
8, preferably 12 to 14 linear or branched primary or secondary alcohols with ethylene oxide having an average addition mole number of 5
To 16, preferably 6 to 10, polyoxyethylene alkyl ether. The component (a) is incorporated in the entire detergent composition in an amount of 5 to 80% by weight, preferably 10 to 50% by weight. If the amount of the nonionic surfactant is less than 5% by weight, sufficient cleaning performance cannot be obtained,
On the other hand, if it exceeds 80% by weight, problems such as exudation of the nonionic surfactant from the unit packaging detergent packaged with the water-soluble film are not preferred.

The porous oil-absorbing carrier as the component (b) in the detergent composition according to the present invention has a pore volume of 0.50 to 7.0 cc / g, preferably 2.0 to 6.0 cc, as measured by a mercury intrusion method.
It is preferably in the range of cc / g and the dispersion having a pH of 9 or more according to the method of JIS K 6220 is preferred. Of the dispersion
When the pH is less than 9, the solubility may decrease. As the porous oil-absorbing carrier, a silica-based carrier is generally used, and amorphous silica, amorphous aluminosilicate, crystalline calcium silicate, and the like are commercially available. Examples of the amorphous silica include those commercially available under the trade names of Toksir (Tokuyama Soda Co., Ltd.) and White Carbon (Cofuran), oil-absorbing amorphous aluminosilicate and oil-absorbing amorphous. Examples of calcium silicate include those marketed under the trade name of Fluorite (Tokuyama Soda Co., Ltd.). As the oil-absorbing carrier of component (b), one or more selected from oil-absorbing amorphous silica, oil-absorbing amorphous aluminosilicate and oil-absorbing amorphous calcium silicate are used. particularly porous oil-absorbing carrier in the invention of the general formula _{x (M 2 O) · y} (MeO) · Al 2 O 3 · z (SiO 2) wherein, M is an alkali metal atom, Me is an alkaline earth metal The atoms x, y, and z represent the molar ratio of each component, and 0.2 ≦ x ≦ 2.
0, preferably 0.7 ≦ x ≦ 1.5, 0 ≦ y ≦ 0.1, preferably 0.005 ≦ y ≦ 0.07, 1.5 ≦ z ≦ 8.0, preferably
1.5 ≦ z ≦ 4.8. It is preferable to use an amorphous aluminosilicate represented by the formula [1], and by including Ca, the pore volume can be further increased.

In the step of producing the amorphous aluminosilicate, one or more acid agents selected from inorganic acids, organic acids and acid salts are added during the reaction between the alkali metal aluminate and the alkali metal silicate. By adjusting the pH of the reaction system to 8 to 14, the formation of water-insoluble substances at a high water temperature can be suppressed.

Among the inorganic acids, organic acids and acid salts used as the acid agent, the inorganic acids include sulfuric acid, hydrochloric acid, nitric acid,
Examples of carbonic acid and phosphoric acid include organic acids such as formic acid, acetic acid, butyric acid, caproic acid, acrylic acid, oxalic acid, succinic acid, adipic acid, benzoic acid, and citric acid. Examples of the acidic salt include salts of the above-mentioned inorganic or organic acids, and include incompletely neutralized salts such as sodium phosphate, sodium citrate, and sodium succinate, but are not limited thereto. One type or a mixture of two or more types may be used. In particular, it is more preferable that the salt after neutralization, such as sulfuric acid, carbonic acid, phosphoric acid, or citric acid, has no problem when incorporated into the detergent.

Further, the pH of the reaction system for reacting the alkali metal aluminate and the alkali metal silicate is 9.5.
~ 13.5 is more desirable.

Unlike a general powder detergent, a packaged packaging detergent containing a large amount of a nonionic surfactant is difficult to disperse when placed in a water tank, so that it gels at a high water temperature, easily agglomerates, and easily produces a water-insoluble matter. In the present invention, a more preferable porous oil-absorbing carrier can be obtained by using the following reaction conditions and steps in addition to the above steps. Regarding the temperature, reaction time and aging temperature, the temperature at which the alkali metal aluminate and the alkali metal silicate are reacted is preferably from 15 ° C to 60 ° C, particularly preferably from 30 ° C to 50 ° C. The reaction time is desirably 3 to 120 minutes. After the reaction, it is preferable to ripen at a temperature between 15 and 100 ° C. for 1 minute or more, preferably 30 minutes or more.

Further, the pH of the slurry after the reaction may be adjusted to at least one acid side from the pH at the time of the reaction by using at least one acid agent selected from inorganic acids, organic acids and acidic salts to adjust the pH to 5 to 13. desirable. The acid agent used here can be the same as the acid agent added during the reaction.Specifically, examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, and the like. Examples include formic acid, acetic acid, butyric acid, caproic acid, acrylic acid, oxalic acid, succinic acid, adipic acid, benzoic acid, citric acid and the like. Also, as the acid salt,
Salts of the above-mentioned inorganic or organic acids, including incompletely neutralized salts such as sodium phosphate, sodium citrate, and sodium succinate, but are not limited thereto, and one or more of these may be used. A mixture of In particular, it is more preferable that the salt after neutralization, such as sulfuric acid, carbonic acid, phosphoric acid, or citric acid, has no problem when incorporated into the detergent. The amorphous aluminosilicate obtained in this manner has improved solubility at higher water temperatures, and has high oil absorption.

In the present invention, more preferably, a water-soluble and solubility parameter (CMHansen,
J. Paint Tech., 39 , 104 (1967)), and a solvent having an SP value of 7.5 to 20) is added to the reaction system in an amount of 0.5 to 50% by weight for reaction. As a result, an amorphous aluminosilicate having a higher oil absorbing ability can be obtained. Such a solvent may be added to each solution before the reaction, or may be added to the solution at the time of the reaction. Preferred as such a solvent are methanol, ethanol, isopropanol, acetone, ethyl acetate, ethylene glycol and the like.

In the packaging detergent of the present invention, the amount of the porous oil-absorbing carrier is 5 to 60% by weight, preferably 5 to 30% by weight, based on the whole composition. If the amount of the porous oil-absorbing carrier is less than 5% by weight, not only a sufficient amount of the nonionic surfactant, which is an essential component of the present invention, cannot be compounded, but also a nonionic surfactant when the powder detergent is individually mounted. It is not preferable because it causes problems such as stains of the agent.

The detergent composition according to the present invention may further comprise a nonionic surfactant content of M% by weight, a porous oil-absorbing carrier content of m% by weight, a porous oil-absorbing agent, in addition to the contents described above. When the pore volume of the carrier is Vcc / g, M / (m × V)
Is 2.0 g / cc or less, preferably 1.5 g
/ Cc or less. When this value exceeds 2.0 g / cc, the nonionic surfactant exudes outside the water-soluble film.

As the crystalline aluminosilicate (zeolite) which is the component (c) of the present invention, synthetic zeolites having an average primary particle diameter of 0.1 to 10 μ such as A-type and X-type zeolites are preferably used. The zeolite is blended as zeolite agglomerated dry particles obtained by drying the powder and / or the zeolite slurry. (C) Component is present in the total composition at 10%.
-60% by weight, preferably 20-60% by weight, particularly preferably 30-50% by weight.

It is desirable to add an alkali agent to the cleaning composition according to the present invention. As the alkaline agent,
Although not particularly specified, carbonates and silicates generally used as detergent components, for example, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate and the like can be mentioned. The alkaline agent is blended in the composition in an amount of 5 to 35% by weight, preferably 5 to 25% by weight. When using sodium carbonate, the average particle size is 10-2000μ, preferably 100-1000
μ.

The detergent composition according to the present invention may further contain polyethylene glycol having a molecular weight of 4000 to 20000.
By adding 5% by weight, preferably 1 to 3% by weight, powder properties during long-term storage are further improved.

The powder detergent composition according to the present invention contains, in addition to the above components, an inorganic electrolyte such as sodium sulfate, an organic chelating agent such as aminopolyacetate and polyacrylate, and a carboxylate, which are usually added to the detergent. A re-contamination inhibitor such as methylcellulose, an enzyme such as protease, lipase, cellulase, and amylase, an antioxidant, a fluorescent dye, a bluing agent, and a fragrance may be blended. Incidentally, sodium silicate interacts with zeolite to increase the water-insoluble content and may cause a problem of cloth non-adhesion. Therefore, the amount of sodium silicate is preferably 5% by weight or less. When used as a bleaching detergent, a bleaching agent such as sodium percarbonate, sodium perborate mono- or tetrahydrate, a peroxide stabilizer such as magnesium silicate, a bleaching activator and the like can be blended. Further, when a soft detergent is used, a small amount of a cationic surfactant or the like may be blended, and when it is desired to increase mud dirt cleaning power, a small amount of an anionic surfactant or the like may be blended.

The method for producing the powder detergent composition of the present invention is not particularly limited, but the porous oil-absorbing carrier and other powder components (crystalline aluminosilicate, alkali agent, etc.) are placed in a batch kneader, and the mixture is placed in a liquid state. Are gradually added or sprayed and uniformly mixed. The thus obtained detergent composition is filled into a water-soluble film using a vertical type packaging machine or the like, so that the packaging detergent of the present invention can be easily produced.

The water-soluble film material used in the present invention includes polyvinyl alcohol (PVA), carboxymethylcellulose, methylcellulose, polyvinylpyrrolidone and the like. Among them, PVA having a saponification degree of 80% or more and an average polymerization degree of 200 to 3000 or a modified product thereof is preferable. In particular, itaconic acid-modified PVA having a degree of modification of 1 to 6 mol% and a degree of saponification of 95% or more exhibits excellent solubility and anti-exudation properties. PVA film with low degree of saponification or a modified product thereof, or a modification rate of 6 mol%
When using itaconic acid-modified PVA film exceeding
When stored for a long time at high temperature and high humidity, the film may be deteriorated and the nonionic surfactant may seep out to the outside of the film.

The thickness of the water-soluble film is in the range of 10 to 150 μ, preferably 15 to 50 μ in order to satisfy the required mechanical strength and dissolution rate. The breaking strength of the water-soluble film is desirably 10 kg / mm ² or less. Furthermore, in order to perform packaging at low cost and efficiently, it is desirable that the material be thermoplastic so that heat sealing can be performed. Further, in the present invention, the water-soluble film may be smooth, but providing unevenness to the film by embossing or the like imparts an anti-blocking effect on the long-term stability of the product, and also provides a feeling when touched by hand during use. It is also effective in improving the quality. There is no particular limitation on the method of providing the film with unevenness, and the film may be cast on a support having an uneven surface, or a flat film may be formed by post-processing using an embossing calendar.

[0024]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Raw materials for a powder detergent shown in Table 1 were put into a batch kneader (Ile Shokai, Bench Kneader PNV-1), and while keeping the temperature at 40 ° C., a liquid nonionic surfactant and then polyethylene glycol were gradually introduced. A dense and homogeneous mixture was obtained. Using a water-soluble film of various thicknesses made of polyvinyl alcohol or itaconic acid-modified polyvinyl alcohol by 25 g each, using a vertical type separate packaging machine, a three-side seal automatic packaging machine manufactured by Topak K-10 Co., Ltd. The package was divided and packaged so that the size per unit package would be 80 mm x 80 mm (bag portion 75 mm x 70 mm), and the solubility, exudation property and caking property test were performed for each. Table 1 shows the results.

[Evaluation Method] (1) Solubility Into a two-tub washing machine Toshiba Galaxy 3.0 (VH-300S1), 30 liters of water at 20 ° C. is put. Into a tub with high stirring strength, put the separately packaged detergent and break the package, and check the time when the detergent elutes and starts foaming in the tub in the washing machine. The longer the bag breaking time,
Poor film solubility. For the solubility test, a temperature of 30 ° C,
A sample stored for 28 days in a variable room having a humidity of 40% RH to 80% RH was used. (2) Exudation property Leave the detergent packaged and packaged on filter paper in a variable temperature environment at a temperature of 30 ° C and a humidity of 40% RH to 80% RH, and exude nonionic surfactant on the filter paper due to wetness. The properties were evaluated. The exuding property of the nonionic surfactant from the packaged detergent was judged from the degree of wetting on the filter paper. Exudation is preserved
28 days after the sample was examined. (3) Cakeability test A carton with a bottom of 80 mm x 80 mm and a height of 50 mm is made from a 1 mm thick acrylic plate, and 5 bags of packing and packaging detergent are placed in the carton in parallel with the bottom, and 90 mm x 90 mm After covering with acrylic plate, every carton, temperature 30 ℃, humidity 40% RH ~
Stored for 28 days in an environment variable room at 80% RH. After storage, carefully remove the third bag from the top of the carton, open it, and place the contents above the mesh screen of 5 mm x 5 mm screen.
When the detergent was left on the sieve when dropped vertically from a place of 10 cm, the evaluation was evaluated as x, and when it did not, the evaluation was evaluated as o. [Variable program of environment variable room] Each sample is set at a temperature of 30
After standing in an environment-variable room at 40 ° C and a humidity of 40% RH for 16 hours, the humidity is raised to 80% RH at a constant speed over 16 hours. Thereafter, these conditions (temperature 30 ° C., humidity 80% RH) are maintained for 48 hours, and the humidity is adjusted to 40% RH at a constant speed over 16 hours. This operation was one cycle. That is, one cycle requires four days (96 hours).

[0027]

[Table 1]

Note) * 1 Nonionic surfactant; primary synthetic alcohol ethoxylate (C ₁₂ -C ₁₄ , average ethylene oxide addition mole number 10, melting point 22 ° C.) * 2 No. 3, 6, 7 and 8 are compared Example * 3 B: Approximate amount of balance to make the whole 100 * 4 Divided packaging film A: Polyvinyl alcohol (average degree of polymerization 2000, saponification degree 80%) * 5 Divided packaging film B: Itaconic acid-modified polyvinyl alcohol (Average degree of polymerization 1500, degree of modification 2 mol%, degree of saponification 95%).

Synthesis Example 1 Sodium carbonate was dissolved in ion-exchanged water to prepare a 6% aqueous solution. 55 g of this aqueous solution, 51.04 g of aqueous sodium aluminate solution and 25 g of ethanol were put into a 1000 cc reaction tank equipped with baffles. No. 3 water glass diluted with twice the water in the solution 26
8.5 g and calcium chloride dihydrate 0.5 g under strong stirring at 40 ° C
A drop reaction was performed in 20 minutes. During the reaction, the pH was controlled to 11 with citric acid. After the reaction, the mixture was aged at 40 ° C. for 30 minutes, and then CO ₂ gas was blown in to neutralize excess alkali (pH = 9.8). This neutralized slurry was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.). A part of the filter cake is washed with water 1000 times and filtered and dried (105 ° C,
(300 torr, 10 hours), and the remainder was dried under the same conditions. After further crushing, an amorphous aluminosilicate powder of the present invention was obtained. As a result of atomic absorption analysis and plasma emission analysis, the composition of the obtained powder was as follows: Al ₂ O ₃ = 29.3% by weight, SiO ₂ = 52.2%
% By weight, Na ₂ O = 17.7% by weight, CaO = 0.8% by weight
(0.99 Na ₂ O · 0.05 CaO · Al ₂ O ₃ · 3.03 SiO ₂ ). The pore volume was 3.6 cc / g.

Comparative Synthesis Example 1 51.04 g of an aqueous sodium aluminate solution was added to 55 g of ion-exchanged water.
The reaction solution was placed in a reaction vessel equipped with a 1000 cc baffle plate, and 268.5 g of No. 3 water glass diluted with twice the amount of water was added dropwise to this solution with vigorous stirring at 40 ° C for 20 minutes. After the reaction, the mixture was heated to 50 ° C. and aged for 30 minutes, and the reaction slurry was filtered, dried and crushed in the same manner as in Synthesis Example 1.
As a result of atomic absorption analysis and plasma emission analysis, the composition of the obtained powder was as follows: Al ₂ O ₃ = 29.8% by weight, SiO ₂ = 52.5% by weight,
Na ₂ O = 17.7% by weight (0.98 Na ₂ O.Al ₂ O ₃ .3.00 Si
O ₂ ). The pore volume was 1.4 cc / g.

Example 2 Using the amorphous aluminosilicate obtained in Synthetic Example 1 and Comparative Synthetic Example 1, a packaging detergent was produced in the same manner as in Example 1 from the powder detergent raw materials shown in Table 2. did. This was tested for solubility, exudation and caking properties in the same manner as in Example 1.
Within seconds, no exudation was observed, and the cakeing resistance was also good. Next, the state of generation of water-insoluble matter at a high water temperature was examined by the following method. [Evaluation method] (1) Generation test of water-insoluble matter at high water temperature The packaged detergent is allowed to stand at 30 ° C. and 70% RH for 3 days. After standing, throw the heater into the two-tank washing machine Toshiba Ginga 3.0 (VH-300S1), put the heater, water volume 30 liters, water temperature 40 ℃,
A packaged detergent is put into a washing tub with a high stirring intensity. After 10 minutes, the water was drained and filtered at a drain outlet with a 200-mesh wire net, and the residual filtration ratio (%) after drying was determined. Table 2 shows the results.

[0032]

[Table 2]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuichi Sakamoto 4-1 Kinryuji-cho, Wakayama-shi, Wakayama Prefecture Kao Kiwadoryo (72) Inventor Kiyofumi Kida 283-12 Hatage, Iwade-cho, Naga-gun, Wakayama Prefecture (56) References JP-A-63-150396 (JP, A) JP-A-63-8496 (JP, A) JP-A-64-24900 (JP, A)

Claims (9)

(57) [Claims] Claims 1. A composition comprising: (a) 5 to 80% by weight of a nonionic surfactant; (b) 5 to 60% by weight of a porous oil-absorbing carrier; and (c) 10 to 60% by weight of a crystalline aluminosilicate. When (a) the content of the nonionic surfactant is M% by weight, (b) the content of the porous oil-absorbing carrier is m% by weight, and (b) the pore volume of the porous oil-absorbing carrier is Vcc / g, M / (m
× V) A packaged detergent obtained by packaging a detergent composition having a numerical value of 2.0 g / cc or less in a water-soluble film having a film thickness of 10 to 150 μm. 2. The packaged detergent according to claim 1, wherein the nonionic surfactant has a melting point of 40 ° C. or lower. 3. The packaged detergent according to claim 1, wherein the nonionic surfactant is a polyoxyethylene alkyl ether. 4. The nonionic surfactant according to claim 3, wherein the nonionic surfactant is a polyoxyethylene alkyl ether having an average addition mole number of ethylene oxide of 5 to 16 and an average carbon number of an alkyl group portion of 10 to 18. Packaging detergent. 5. The packaged detergent according to claim 1, wherein the porous oil-absorbing carrier is a water-insoluble amorphous silica-based inorganic substance. 6. An amorphous silica-based inorganic substance represented by the following general formula x (M ₂ O) · y (MeO) · Al ₂ O ₃ .z (SiO ₂ ) [wherein M is an alkali metal atom, Me Is an alkaline earth metal atom, x, y, z represent the molar ratio of each component, 0.2 ≦ x ≦ 2.
0, 0 ≦ y ≦ 0.1, 1.5 ≦ z ≦ 8.0. The packaged packaging detergent according to claim 5, which is an amorphous aluminosilicate represented by the formula: 7. An amorphous aluminosilicate is produced by adding one or more acid agents selected from inorganic acids, organic acids and acid salts during the reaction between an alkali metal aluminate and an alkali metal silicate. 7. The packaged detergent according to claim 6, which is obtained by adjusting the pH of the reaction system to 8 to 14. 8. The water-soluble film having an average degree of polymerization of 200 to 200.
The packaged packaging detergent according to any one of claims 1 to 7, which is polyvinyl alcohol having a saponification degree of 80% or more at 3000 and a modified product thereof. 9. A Lee itaconic acid-modified polyvinyl alcohol modified ratio of 1～6Mol% polyvinyl alcohol modified product, sachets detergent according to claim 8, wherein a saponification degree of 95% or more.