JP2008208187A - Detergent composition containing specific polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition containing a specific polymer, and making reattachment of soot dirt and powder dirt difficult, in other word, preventing resoiling with dirt, and to provide a detergent composition preventing the resoiling with the dirt even when clothes, cotton towel or the like treated with a softening and finishing agent at a rinsing step. <P>SOLUTION: The detergent composition contains a copolymer having a constituent unit derived from N-vinylpyrrolidone and a constituent unit derived from vinyl acetate, and also having 5,000-70,000 weight average molecular weight. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laundry detergent composition.

  In recent years, a water-saving type washing machine, that is, a washing machine with a small amount of water used for washing, has become widespread due to an increase in environmental awareness. A prominent example is a washing machine generally called a drum type washing machine, which is widely accepted all over the world. However, the cleaning system that uses a small amount of water for the object to be cleaned has a problem that the object to be cleaned is darkened by washing. Although it is preferable to reduce washing water from the viewpoints of reducing environmental load and saving economy through energy saving, it is thought that “darkening” of objects to be cleaned is due to the fact that the amount of water used is small as described below. Therefore, improvement by the washing machine itself is a difficult task. Therefore, at the present time when water-saving type washing machines are becoming widespread, even in such a washing system with a small amount of water used, a detergent composition that not only exhibits high detergency but also can suppress darkening of the object to be washed, There is a strong demand.

  As a main factor of the phenomenon in which the object to be cleaned becomes darker every time washing is performed, a phenomenon in which coloring components such as dirt that has separated from the object to be cleaned in the cleaning process re-adheres to the object to be cleaned in the washing water. When the amount of washing water decreases, the concentration of dirt in the washing water increases, so that these redepositions easily occur. Even if the amount of water is reduced, the concentration of detergents and dispersants such as surfactants in the washing liquid as well as dirt becomes higher than the positive effect of preventing reattachment by these components, It can also be confirmed that since the negative influence of the increase in the concentration of dirt is large, the reattachment of dirt to the object to be cleaned is promoted.

  Further, among the stains in the washing liquid, typical examples of the coloring component include hydrophilic fine particles contained in mud and hydrophobic fine particles such as soot. In order to prevent darkening, there is a need for a detergent composition having a high anti-redeposition property against dirt particles having different physical properties.

  Conventionally, as a technique for preventing the reattachment of dirt, as disclosed in Patent Document 1, a technique for improving the dispersibility of dirt in a washing liquid using a dispersing agent such as a polymer is known.

  Further, as a technique based on a mechanism different from this, there is a technique for preventing the redeposition of dirt by changing the surface physical properties of the fiber by adsorbing a specific chemical species to the fiber. For example, Patent Document 2 describes that smectite-type clay minerals are adhered to fibers to improve the anti-reattachment property of dirt. However, in the case of Patent Document 2, there is no suggestion of a mechanism that stably disperses dirt particles in the washing liquid in the anti-redeposition mechanism in which an effect appears due to the adhesion of a chemical species. When the adhesion is not good, the effect hardly appears. In particular, since there is no suggestion regarding surfactants, particularly nonionic surfactants, the performance for preventing redeposition of soot-like hydrophobic fine particles which seems to be an important factor for preventing darkening is not sufficient. . In addition, this mechanism is not sufficient to prevent darkening in a high soil concentration solution in which blackening is recognized even after one washing because repeated washing is a necessary condition for manifesting the effect. .

  Moreover, as a technique using a smectite-type clay mineral, there is an example of using a clay mineral in order to improve the particle physical properties of a detergent composition containing a nonionic surfactant, as in Patent Document 3. However, in the case of Patent Document 3, since there is no technical idea to prevent darkening of the object to be cleaned, the content of the anionic surfactant is not sufficient, which is one of the causes of darkening. Such re-adhesion preventing property of hydrophilic fine particles is not sufficient.

  In addition, a technique for applying an amphoteric polymer having a cationic group and an anionic group to a detergent composition for clothing and performing an antifouling treatment in a washing machine washing process is also known (Patent Document 4). . However, although it has a high cleaning effect against sebum stains during washing, it does not have sufficient anti-reattachment properties for hydrophobic fine particles such as hydrophilic fine particles and soot contained in mud due to dirt in the washing liquid. .

Neither of these techniques is sufficient to prevent redeposition of dirt in washing water having an extremely increased dirt concentration due to the small amount of washing water as described above.
JP-A-62-253694 JP 56-167798 A Japanese Patent No. 3043976 Japanese Patent No. 3405941

  Laundry clothes that have been worn are washed with a laundry detergent and a fully automatic washing machine. Although it is a cycle, the oleophilicity of the fiber surface of the garment becomes stronger as the processing of the softener is repeated. Therefore, there is a problem that so-called “dirt re-contamination” is liable to occur, such as heel stains and dust stains that are once separated from the clothing.

  In recent years, fully automatic washing machines have been rapidly saving water, and as a result, the amount of water for clothes is low, that is, washing is performed at a low bath ratio, so the concentration of dirt increases, and these problems occur frequently. Cheap. In particular, the popularity of drum-type washing machines with a low bath ratio has been increasing year by year in the washing machine market, and complaints from users of drum-type washing machines have become prominent.

  It is an object of the present invention to provide a detergent composition containing a specific polymer that makes it difficult to re-attach soot and dust dirt, or prevents so-called soil re-contamination. Furthermore, it is an object of the present invention to provide a detergent composition that prevents recontamination of dirt even when clothes or cotton towels treated with a soft finish are used in the rinsing step.

That is, the present invention
[1] A detergent composition comprising a copolymer having a structural unit derived from N-vinylpyrrolidone and a structural unit derived from vinyl acetate and having a weight average molecular weight of 5,000 to 70,000,
[2] (a) A copolymer having a structural unit derived from N-vinylpyrrolidone and a structural unit derived from vinyl acetate, and having a weight average molecular weight of 5,000 to 70,000, 0.01 to 10% by mass,
(B) 1 to 30% by mass of clay granulated product, and (c) 10 to 50% by mass of surfactant,
A detergent composition containing [3], and a method of preventing soil recontamination by bathing a textile product with a detergent solution containing the copolymer according to [1] at a concentration of 1 to 500 ppm,
About.

  By using the detergent composition of the present invention, there is an effect that high stain recontamination prevention performance can be imparted when washing textile products and the like.

  The detergent composition of the present invention contains a copolymer having a structural unit derived from N-vinylpyrrolidone and a structural unit derived from vinyl acetate. In the present specification, hereinafter, it may be simply referred to as “N-vinylpyrrolidone / vinyl acetate copolymer”.

<(A) component: N-vinylpyrrolidone / vinyl acetate copolymer>
In the present invention, the final form of the N-vinylpyrrolidone (VP) / vinyl acetate (VA) copolymer is preferably a white powder or an aqueous solution such as an ethanol solution or an isopropanol solution. Examples of the method for producing the copolymer include a method for directly producing in an organic solvent, preferably an aliphatic hydrocarbon, more preferably cyclohexane or heptane, or a mixture thereof in the presence of a predetermined amount of a free polymerization initiator. Is mentioned. Suitable polymerization initiators include azyl peroxides such as diacetyl peroxide, dibenzoyl peroxide and dilauryl peroxide; peracid esters such as t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate; Peroxycarbonates such as dicyclohexyl peroxydicarbonate; and azo compounds such as 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4- Dimethylvaleronitrile), 1,1'-azobis (cyanocyclohexane), and 2,2'-azobis (methylbutyronitrile). Other polymerization initiators known to those skilled in the art can also be used.

  The amount of such a polymerization initiator can vary widely, and generally about 0.2 to 5.0% can be used based on the weight of all the structural units introduced. The reaction temperature can be varied over a wide range and generally the reaction mixture can be maintained preferably at 40-150 ° C, more preferably 60-70 ° C during the polymerization. The pressure is usually maintained at atmospheric pressure, although higher and lower pressures can be used as well. After the polymerization reaction starts, another polymerization initiator can be further introduced at a higher operating temperature (60 to 80 ° C.). The reason is that this polymerization initiator effectively reduces the content of residual VP and VA building blocks to less than 100 ppm in the product. Such a relatively high temperature polymerization initiator can be added to the system individually or mixed with a low temperature polymerization initiator. A preferred relatively high temperature polymerization initiator is 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Lupersol® 101). The total amount of the polymerization initiator including such a polymerization initiator can also be about 0.2 to 5.0% based on the weight of all the introduced structural units.

  The polymerization is carried out by first introducing a predetermined amount of an organic solvent, for example an aliphatic hydrocarbon solvent, into a suitable reactor, heating the solvent to the desired reaction temperature and simultaneously stirring vigorously under an inert gas atmosphere. be able to. Next, after introducing the polymerization initiator into the reactor, the constituent units derived from vinylpyrrolidone and vinyl acetate can be continuously introduced into the reactor by a syringe pump. The quantity ratio of each structural unit can be adjusted based on the ratio desired between the predetermined vinylpyrrolidone and vinyl acetate in the copolymer. Vinyl pyrrolidone is much more reactive than vinyl acetate during polymerization and it is desirable to provide a substantially uniform copolymer related to the distribution of building blocks on the polymer backbone. When the time is relatively short, it is usually 3 to 5 hours, and when the time for adding vinylpyrrolidone is relatively long, it is usually preferably 5 to 7 hours. Preferably, the reaction mixture is introduced into the reactor below the solvent level. The reaction mixture is further allowed to reach a high temperature polymerization initiator such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (for example) at a relatively high temperature (60-80 ° C.) for a certain time, usually 6-8 hours. Lupersol (R) 101) can be added and held to complete the polymerization. Finally, by cooling the reaction mixture to room temperature, filtering, washing with a solvent, and drying, the desired copolymer can be obtained in near quantitative yield. Alternatively, the reaction mixture can be directly dried to obtain a copolymer powder.

  When the glass transition temperature Tg indicating the state of the copolymer is higher than this temperature, the copolymer is in a viscous state or a rubber state; below this temperature, the copolymer is in a hard state or a glass state. . Tg is related to the amount of free end groups in the copolymer. The Tg of the obtained N-vinylpyrrolidone / vinyl acetate copolymer is preferably 50 to 130 ° C., more preferably 55 to 120 ° C., more preferably, in order to synthesize a normal copolymer that does not cause a crosslinking reaction. Is in the range of 70-110 ° C.

The weight average molecular weight of the N-vinylpyrrolidone / vinyl acetate copolymer is 5,000 to 70,000, preferably 8,000 to 50,000, more preferably 10,000 to 30,000, from the viewpoint of effectively enhancing the prevention of soil recontamination.
The weight average molecular weight is usually measured using gel permeation chromatography (GPC). DMF (N, N-dimethylformamide) is used as the solvent, and polyethylene glycol (PEG) is used as the standard substance. Examples include Showa Denko GPC (organic solvent column: Shodex Asahipac series GPC KD-803 or GPC KD-804), RI detector (RI-71,101 Showa Denko), UV detector (UV-41 Showa Denko), etc. Can be used to determine the weight average molecular weight.

  In the copolymer, the molar ratio [N-vinyl pyrrolidone / vinyl acetate] of the structural unit derived from N-vinyl pyrrolidone and the structural unit derived from vinyl acetate is 10 / It is preferably 90 to 50/50, more preferably 10/90 to 40/60, and even more preferably 10/90 to 30/70.

  The copolymer may be a copolymer containing structural units derived from vinyl alcohol in all the structural units.

  The following method is mentioned as a method of containing the structural unit derived from vinyl alcohol. In general, hydrolysis of polyvinyl acetate with a dilute acid or alkali gives polyvinyl alcohol. Vinyl alcohol (enol tautomer of acetaldehyde) has an unstable molecular structure and cannot be directly polymerized as a structural unit, so that vinyl alcohol can be contained via vinyl acetate.

  From the viewpoint of effectively enhancing the prevention of soil re-contamination, the copolymer is preferably a small amount, preferably 0 to 15 mol%, more preferably 0 to 10 in the total constitutional units. It contains in mol%, more preferably 0-5 mol%.

  In the present invention, from the viewpoint of preventing recontamination, the content of the component (a) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.00% in the detergent composition. It is 1-3 mass%. Within the above range, one or more kinds of the above copolymers may be used.

<(B) Component: Clay Granule>
The detergent composition preferably contains 1 to 30% by mass of a granulated granule as the component (b). In terms of softness and cleaning performance, the content of the component (b) in the detergent composition is more preferably 1 to 18% by mass, further preferably 5 to 16% by mass, and even more preferably 6 to 15% by mass. 7 to 14% by mass is particularly preferable.

  Since the clay granule contains impurities such as quartz, cristobalite, calcite, feldspar and the like, particularly when natural, the content of the component (b) may include those impurities.

  The clay mineral used in the clay granule of component (b) is talc, pyrophyllite, smectite (saponite, hectorite, saconite, stevensite, montmorillonite, beidellite, nontronite, etc.), vermiculite, mica (phlogopite) , Biotite, chinwald mica, muscovite, paragonite, celadonite, sea chlorite, etc.), chlorite (clinochlore, chamosite, nimite, penantite, sudite, dombasite, etc.), brittle mica (clinintite, margarite, etc.), Sulite, serpentine minerals (antigolite, lizardite, chrysotile, amicite, cronstedite, burcherin, greenerite, garnierite, etc.), kaolin minerals (kaolinite, dickite, nacrite, halloysite, etc.) . Among these, talc, smectite, swellable mica, vermiculite, chrysotile, kaolin mineral, and the like are preferable, smectite is more preferable, and montmorillonite is further preferable in terms of flexibility. These may be used alone or in appropriate combination of two or more.

In addition, as the component (b), the following general formula (1):
_{[Si 8 (Mg a Al b} ) O 20 (OH) 4] X- · Me X + (1)
(0 <a ≦ 6, 0 <b ≦ 4, preferably 0 <a <6, 0 <b <4, x = 12-2a-3b, Me is Na, K, Li, Ca, Mg and NH ₄ At least one)
It is preferable that a clay mineral represented by As an example of the clay mineral represented by the general formula (1), the form may be a powder or a granulated product, but “Round Rosil DGA212” and “Round Rosil PR414” manufactured by Sud Kemi Co., Ltd. , "Round rosyl DG214", "Round rosyl DGA powder", "Hulasoft-1 powder", "Detasoft GIS", "Detasoft GIB", "Detasoft GISW" manufactured by Raviossa, Pure bentonite, Standard bentonite, Premium manufactured by CSM Examples thereof include bentonite. Moreover, you may use what grind | pulverized these and made it powder.
Moreover, from the viewpoint of solubility, in the granulated granule containing the clay mineral represented by the general formula (1), the ratio of Na ions to Ca ions (Na / Ca) is preferably 1.0 or more, and 1.5 The above is more preferable, and 2.0 or more is more preferable. Here, the clay granulated product is preferably one containing 50% by mass or more of clay mineral as a main component.

  As a method for obtaining a clay granulated product having a high ratio of Na ions and Ca ions, if it is a natural product, the production area may be selected, or, for example, when a clay granulated product is produced, Na salt or the like is added. It is also possible to prepare it. Moreover, if it is a synthetic product, it can be arbitrarily prepared by a known method.

  As a method for producing a clay granulated product having a high ratio of Na ions and Ca ions, the following production method may be useful. A raw material clay ore (clay mineral) containing 20% or more of water is added with a sodium salt such as powdered sodium carbonate and mixed well, followed by drying, or a granulated clay mineral pulverized into powder Examples of the production method include a step of adding a powder of an Na salt such as sodium carbonate or an aqueous solution when granulating using a machine.

  The ratio of Na ions and Ca ions in the clay granule can be measured by the following method. After pulverizing the clay granule in a mortar, 0.1 g of the sample that passed through a sieve with an opening of 125 μm was decomposed with sulfuric acid-hydrogen peroxide using a microwave wet ashing device (automatic), and the volume was increased to 50 mL with a volumetric flask. Then, the amount of Na and Ca can be quantified and calculated with an ICP emission spectrometer.

In the case where the component (b) is a granulated granule containing clay mineral, the dissolution rate calculated by the following method is preferably 90% or more, and 93% or more from the viewpoint of expressing the flexibility effect on the laundry. More preferred is 95% or more.
When the mixture is stirred under the following stirring conditions and applied to a standard sieve (mesh size 74 μm) defined in JIS Z 8801, the dissolution rate can be calculated by the formula (2).
[Stirring conditions: 0.1 g of sample (clay granulated material) was added to 1 L of hard water (71.2 mg CaCO ₃ equivalent / liter, Ca / Mg molar ratio 7/3) at 5 ° C., and 1 L beaker (inner diameter 105 mm) For 10 minutes with a stirring bar (length 35 mm, diameter 8 mm), rotation speed 800 rpm]
Formula (2): Dissolution rate (%) = {1− (T ′ / S ′)} × 100
S ′: input weight (g) of clay granulated product,
T ′: When the aqueous solution obtained under the above stirring conditions is subjected to the sieve, the dry weight (g) of the dissolved residue of the sample (clay granulated product) remaining on the sieve

  In the detergent composition of the present invention, the mass ratio of the component (a) to the component (b) [(a) component / (b) component] is preferably 1 / from the viewpoint of effectively enhancing the prevention of soil recontamination. 100 to 1/1, more preferably 1/50 to 1/2, still more preferably 1/20 to 1/3.

  The moisture value of the clay granulated product is preferably 18% or less, more preferably 16% or less, and still more preferably 14% or less from the viewpoint of particle strength.

<(C) Component: Surfactant>
As the surfactant used in the detergent composition of the present invention, a conventionally known substance can be used. As the surfactant, an anionic surfactant and a nonionic surfactant are preferably used as the main surfactant.

  Examples of the anionic surfactant include linear alkylbenzene sulfonate having alkyl chain having 10 to 18 carbon atoms, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate salt, alpha sulfo fatty acid methyl ester salt, N-acyl. Amino acid surfactants, alkyl or alkenyl ether carboxylates, amino acid surfactants, alkali metal salts such as alkyl or alkenyl phosphate esters or salts thereof are preferred, and even if fatty acid salts derived from beef tallow or coconut oil are blended Good. Of these, linear alkylbenzene sulfonates, alkyl sulfate esters, and polyoxyalkylene alkyl ether sulfates are preferable, and sodium linear alkylbenzene sulfonate is particularly preferable. From the viewpoint of detergency against hydrophilic solid particle dirt such as mud, the content of the anionic surfactant in the detergent composition is preferably 5% by mass or more, more preferably 7% by mass or more, and 9% by mass or more. Is more preferable. Moreover, from a viewpoint of powder physical property, 40 mass% or less is preferable, 35 mass% or less is more preferable, 30 mass% or less is further more preferable, and 26 mass% or less is further more preferable.

  Further, as the nonionic surfactant, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoside, fatty acid glycerin monoester, polyoxyethylene alkyl ether can be used. Of these, polyoxyethylene alkyl ether is preferably used. Nonionic surfactants have good resistance to hard water, and have a remarkable detergency for oily dirt such as sebum dirt. From the viewpoint of foamability and rinsability, the content of the nonionic surfactant is preferably 1 to 15% by mass, more preferably 5 to 15% by mass in the detergent composition.

  The mass ratio of the polyoxyethylene alkyl ether type nonionic surfactant to the polyethylene oxide contained in the detergent composition (polyoxyethylene alkyl ether type nonionic surfactant / polyethylene oxide) is 20 or less. Preferably, 15 or less is more preferable, 10 or less is more preferable, and 3 to 6 is most preferable. Moreover, as a preferable alkyl chain, a linear chain is preferable, and it is preferable that carbon number has preferably 10-14, more preferably 12.

  In the detergent composition of the present invention, surfactants such as betaine amphoteric surfactants, phosphate ester surfactants, soaps, and cationic surfactants can be appropriately blended.

  The surfactant used in the detergent composition of the present invention may contain the anionic surfactant, nonionic surfactant and soap. In this case, the surfactant is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and further preferably 20 to 20% by mass in the detergent composition from the viewpoint of effectively expressing detergency and prevention of recontamination. Contains 40% by weight.

<(D) component: alkaline agent>
As the alkaline agent used in the present invention, it is preferable to blend a conventionally known alkaline agent into the detergent composition from the viewpoint of detergency. Examples of the alkali agent include alkali metal carbonates such as sodium carbonate collectively called dense ash and light ash, amorphous alkali metal silicates such as JIS No. 1, No. 2, No. 3 sodium silicate, and crystalline alkali. Examples include alkali metal salts such as metal silicates. From the viewpoint of increasing the detergency against oil stains such as sebum, the content of the alkaline agent in the detergent composition is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 7% by mass or more, and 10% by mass. % Or more is more preferable, 12 mass% or more is further more preferable, 15 mass% or more is further more preferable, and 20 mass% or more is especially preferable. Moreover, 40 mass% or less is preferable from a viewpoint of the balance of a mixing | blending, and 30 mass% or less is more preferable.

<(E) component: sequestering agent>
As a builder, it is very effective from the standpoint of detergency to mix a sequestering agent in the detergent composition and capture the hardness component in the wash water. In particular, it is more effective to add a sequestering agent having a calcium ion scavenging ability of 100 mgCaCO ₃ / g or more. Examples of the sequestering agent include crystalline aluminosilicate, crystalline sodium silicate, acrylic acid polymer, acrylic acid-maleic acid copolymer, sodium tripolyphosphate, ethylenediaminetetraacetic acid, and methylglycine diacetic acid. However, sodium carbonate and amorphous sodium silicate are not included in the sequestering agent in the present invention. The content of the sequestering agent in the detergent composition is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and even more preferably 20% by mass or more from the viewpoint of detergency. preferable. Moreover, from a viewpoint of the balance of a mixing | blending, 50 mass% or less is preferable, 40 mass% or less is more preferable, and 35 mass% or less is further more preferable. Specific examples of the component (e) include zeolite, BASF's Socalan CP-5, BASF's Socaran CP-7, and the like.

<(F) Component: Other Polymer>
In addition, the detergent composition of the present invention and the washing liquid (detergent solution) used in the present invention are conventionally known for the purpose of increasing the dispersibility of solid particle dirt, and preferably have a weight average molecular weight of less than 500,000. Preferably, an organic polymer having a weight average molecular weight of 1,000 to 100,000, for example, a carboxylic acid polymer, polyethylene glycol, carboxymethyl cellulose and the like can be blended.

<Carboxylic acid polymer>
Carboxylic acid polymers have a function of sequestering metal ions, and also have an effect of dispersing solid particle dirt in the washing liquid. The carboxylic acid polymer may be a homopolymer or copolymer such as acrylic acid, methacrylic acid, itaconic acid, and the copolymer is preferably a copolymer of the above monomer and maleic acid. Yes, those having a weight average molecular weight of 3000 to 20,000 are preferred. As the homopolymer, polyacrylic acid is preferred, and those having a weight average molecular weight of 3000 to 20,000 are preferred.

<Polyethylene glycol>
Polyethylene glycol has the effect of dispersing solid particle soil in the washing liquid. The weight average molecular weight is preferably 1000 to 20,000.

<Carboxymethylcellulose>
Carboxymethylcellulose has the effect of dispersing solid particle soil in the washing liquid. From the viewpoint of dispersibility, those having a weight average molecular weight of several thousand to several hundred thousand and an etherification degree of 0.2 to 1.0 are preferable.

<(G) component: other additives>
In the detergent composition of the present invention, enzymes, perfumes, fluorescent dyes, hydrogen peroxide releasing inorganic salts, pigments and the like can be appropriately blended.

  The present invention relates to a method for preventing soil recontamination by bathing a textile product with a detergent solution containing the copolymer at a concentration of 1 to 500 ppm.

  The concentration of the copolymer in the detergent solution is 1 to 500 ppm, preferably 1 to 100 ppm, more preferably 1 to 50 ppm, from the viewpoint of preventing soil recontamination.

  The present invention is a method for preventing soil re-contamination, further comprising bathing a textile product with a detergent solution containing a clay granule and having a total concentration of the copolymer and the clay granule of 1 to 500 ppm. May be.

  The total concentration of the copolymer and clay granulated product in the detergent solution is preferably 1 to 500 ppm, more preferably 10 to 300 ppm, and still more preferably 30 to 200 ppm, from the viewpoint of preventing soil recontamination. It is.

  In the present invention, the object for preventing recontamination of dirt is preferably a textile product, for example, a yarn bundle, clothing including a fabric, a bag, or the like, and more preferably clothing.

1. Preparation of treatment cloth The treatment to the test cloth is done by using laundry detergent (New Beads) at 0.083% by weight, and using the fully automatic washing machine / standard course for the test cloth, the cumulative washing treatment is performed 5 times. went. The treated cloth was dried and conditioned for 14 hours in a constant temperature room (25 ° C./40% RH). The size of each test cloth was 4 × 5 cm.
The bath treatment conditions were as follows: a fully automatic washing machine JW-Z20A manufactured by Haier Co., Ltd., standard course (15 minutes washing, 2 rinses, 5 minutes dehydration, water volume 15 L), water temperature 20 ° C., bath ratio 40 is there.

<Test cloth>
Cotton knitted fabric (fluorescent dye-undyed fabric), T / C broad (fluorescent dye-dyed fabric), and polyester knit were all obtained from Tanigami Shoten Co., Ltd.

2. Evaluation method of anti-recontamination effect The anti-contamination effect was evaluated using a round-ometer.
The detergent composition for clothing shown in Table 1 was dissolved in 100 mL of 72 mg / L (calculated in terms of CaCO ₃ ) of calcium hard water to prepare 0.15%. Next, 0.13 g of carbon is put in the detergent solution, and is ultrasonically irradiated for 15 minutes using a bathtub of an ultrasonic oscillator (model U0600PB-Y manufactured by Kokusai Electric Eltech Co., Ltd.). Transferred to a glass cup.

  Three kinds of treated cloths each having a size of 4 × 5 cm, one of which is a set of 5 sheets in a set of 15 sheets, put in a detergent solution in the cup, put at 25 ° C. for 30 minutes, pot rotation speed 40 ± 2 Washing was performed by rotating with a round-ometer at times / minute. After rinsing with 5 L of tap water, an iron press treatment was performed. Subsequently, the reflectance at 550 nm of the raw cloth before washing and the recontamination test cloth was measured with a spectral color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the recontamination prevention rate (%) was calculated from the following formula.

  Prevention rate of recontamination (%) = [Reflectance after cleaning / Reflectivity of fabric] × 100

3. Preparation of softness evaluation towel A commercially available cotton towel (100% cotton) was used in a mini washing machine ("N-BK2" manufactured by National), and the pre-treatment agent at that time was a nonionic surfactant ( 0.5 g of a mixture of a primary alcohol having 12 carbon atoms with an average of 6 moles of ethylene oxide added), crystalline silicate (pre-feed granule), and sodium carbonate mixed at 1: 1: 3 (weight ratio). Used at / L. After washing at a water temperature of 20 ° C. for 7 minutes, centrifugal dehydration, rinsing for 3 minutes, dehydration, rinsing for 3 minutes, and dehydration were repeated 5 times in total to remove the treatment agent.

4. Softness evaluation method 5.0 g of the detergent composition shown in Table 1 and 0.3 kg of cotton towel (4 pieces of 70 cm × 30 cm) were placed in 5 L of water at 20 ° C. and washed for 7 minutes. After dehydration, it was rinsed with 5 L of water for 3 minutes, dehydrated, rinsed for 3 minutes, dehydrated and air-dried.

Five testers made a sensory evaluation of the softness of the hand using a towel and a pretreated towel as a pair. When there is no difference and when it becomes hard, 0 points, when it becomes slightly softer, 1 point, when it becomes slightly softer, 2 points, when it becomes clear softly 3 points, the total points of 5 people are shown as follows It was. At this time, a grade of ○ or higher was regarded as an acceptable level.
Evaluation criteria ◎: Total 10 points or more ○: Total 6 points or more and less than 10 points △: Total 3 points or more and less than 6 points ×: Total less than 3 points

5. Composition Example of Detergent Composition A detergent base was obtained with clay granulates, enzymes, fragrances, and ingredients obtained by subtracting 3% by mass of the surface modifying zeolite from the amount of zeolite in Table 1. This was mixed with the remaining ingredients to obtain a detergent composition. The composition of the detergent composition is shown in Table 1.

All of the obtained detergent compositions have a pH range of 10 to 11 and a calcium capture amount of 50 CaCO ₃ mg / g to 200 CaCO ₃ mg as measured at 20 ° C. described in JIS K3362: 1998. / G range, average particle size was in the range of 300-800 μm, and apparent density was in the range of 700-980 g / L.

In the examples, the following were used as each component.
PVP / VA copolymer I: PVP / VA copolymer manufactured by International Specialty Products, Inc. Product name I-335 (weight average molecular weight 14000, Tg 71 ° C., PVP / VA = 30/70 molar ratio)
-PVP / VA copolymer II: PVP / VA copolymer product name I-535 manufactured by International Specialty Products (weight average molecular weight 20000, Tg 89 ° C., PVP / VA = 50/50 molar ratio)
-PVP / VA copolymer III: PVP / VA copolymer product name I-735 manufactured by International Specialty Products (weight average molecular weight 28000, Tg 108 ° C, PVP / VA = 70/30 molar ratio)
・ PVP homopolymer: Polyvinylpyrrolidone PVP K-30 (powder weight average molecular weight 38000) manufactured by International Specialty Products
Zeolite: “Zeo Builder” (Zeo Builder, median diameter: 3.0 μm)
・ Anionic surfactant: Sodium alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl group ・ Nonionic surfactant: A compound obtained by adding 6 moles of EO to a primary alcohol having 12 carbon atoms. 108 "(manufactured by Kao Corporation)
PEG: polyethylene glycol (weight average molecular weight 10,000)
・ Crystalline silicate: Pre-feed granule (manufactured by Tokuyama Siltech Co., Ltd.)
・ Oligomer D: Polyacrylic acid (weight average molecular weight 15,000; measured by GPC, converted to polyethylene glycol)
Enzyme: “Cellulase K” (described in JP-A 63-264699), “Cannase 24TK” (manufactured by Novo), “Sabinase 6.0T” (manufactured by Novo) in a mass ratio of 3: 1: 2. use

In addition, the following were used as clay granulated material (I)-(V) in an Example.
The manufacturing method of a clay granulated material is as follows.

  100 parts by weight of a bentonite clay mineral having a Na / Ca ratio of 0.6 and a water content of 25% and 3.55 parts by weight of sodium carbonate are charged into a 2 L Henschel mixer and mixed for 3 minutes at a rotational speed of 1600 rpm. The obtained mixture was granulated with an extrusion granulator (screen diameter: 2 mmφ). Next, the granulated product is dried to a moisture content of 8% with a dryer at 80 ° C. and pulverized with a mortar until it passes through a 125 μm sieve. 100 parts by weight of this pulverized product is put into a Henschel mixer, and 25 parts by weight of water is added during mixing at a rotational speed of 1600 rpm and mixed for 30 seconds. What dried this mixture to the moisture of 12.5% with the 80 degreeC dryer cuts oversize (1410 micrometers or more) and undersize (180 micrometers or less), and obtains a clay granule (I). This clay granulated product had a Na / Ca ratio of 2.5 and a dissolution rate of 96%.

  The method for producing the clay granulated product (II) is the same as the method for producing the clay granulated product (I) except that the amount of sodium carbonate added is 1.55 parts by weight. The clay granule had a water content of 12.6%, a Na / Ca ratio of 1.5, and a dissolution rate of 96%.

  The method for producing the clay granulated product (III) is the same as the method for producing the clay granulated product (I) except that the amount of sodium carbonate added is 0.98 parts by weight. The clay granule had a water content of 12.5%, a Na / Ca ratio of 1.2, and a dissolution rate of 96%.

  The method for producing the clay granulated product (IV) is in accordance with the method for producing the clay granulated product (I) except that the amount of sodium carbonate added is 0.027 parts by weight. The clay granule had a moisture content of 12.8%, a Na / Ca ratio of 0.7, and a dissolution rate of 93%.

The method for producing the clay granulated product (V) is as follows.
100 parts by weight of a bentonite clay mineral having a Na / Ca ratio of 0.04 and a moisture content of 25% and 0.87 parts by weight of sodium carbonate are added to a 2 L Henschel mixer and mixed at a rotational speed of 1600 rpm for 3 minutes. The obtained mixture was granulated with an extrusion granulator (screen diameter: 2 mmφ). Next, the granulated product is dried to a moisture content of 8% with a dryer at 80 ° C. and pulverized with a mortar until it passes through a 125 μm sieve. 100 parts by weight of this pulverized product is put into a Henschel mixer, and 25 parts by weight of water is added during mixing at a rotational speed of 1600 rpm and mixed for 30 seconds. The mixture is dried to 80.degree. C. to a moisture content of 12.3%, and the oversized (1410 .mu.m or more) and undersize (180 .mu.m or less) are cut to obtain a clay granulated product (V). The clay granulated product had a Na / Ca ratio of 0.5 and a dissolution rate of 91%.

From Table 1, when the detergent composition of the present invention is used, high dirt recontamination prevention performance can be imparted when washing textiles and the like.

Claims (6)

  A detergent composition comprising a copolymer having a structural unit derived from N-vinylpyrrolidone and a structural unit derived from vinyl acetate and having a weight average molecular weight of 5,000 to 70,000.   The copolymer has a molar ratio [N-vinylpyrrolidone / vinyl acetate] of a constituent unit derived from N-vinylpyrrolidone and a constituent unit derived from vinyl acetate of 10/90 to 50/50, and a constituent derived from vinyl alcohol. The detergent composition of Claim 1 which contains a unit 0-15 mol% in all the structural units. (A) A copolymer having a structural unit derived from N-vinylpyrrolidone and a structural unit derived from vinyl acetate, and having a weight average molecular weight of 5,000 to 70,000, 0.01 to 10% by mass,
(B) 1 to 30% by mass of clay granulated product, and (c) 10 to 50% by mass of surfactant,
A detergent composition.   The detergent composition according to claim 3, wherein the mass ratio of the component (a) to the component (b) [(a) component / (b) component] is 1/100 to 1/1.   A method for preventing soil recontamination, wherein the textile product is bath-treated with a detergent solution containing the copolymer according to claim 1 or 2 at a concentration of 1 to 500 ppm.   The method according to claim 5, wherein the fiber product is further bath-treated with a detergent solution containing a clay granule and having a total concentration of the copolymer and the clay granule of 1 to 500 ppm.