JP2015172125A - detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition which has excellent anti-resoiling properties for both hydrophilic fibers and hydrophobic fibers.SOLUTION: The detergent composition contains 0.05-20 mass% of a cellulose acetate having a total degree of substitution of acetyl groups of 0.4-1.2, based on the total amount (100 mass%) of the detergent composition. Preferably, the detergent composition further contains 5-20 mass% of an α-sulfofatty acid alkyl ester salt and 3-10 mass% of soap based on the total amount (100 mass%) of the detergent composition.

Description

  The present invention relates to a detergent composition. More specifically, the present invention relates to a detergent composition having excellent anti-recontamination property (anti-contamination ability).

  In detergent compositions, α-sulfo fatty acid alkyl ester salts that are excellent in detergency, have good biodegradability, and are derived from plants and have a low environmental impact are widely used. When this α-sulfo fatty acid alkyl ester salt is used as a detergent, soap is often used for the purpose of improving productivity. Soap has many advantages such as good biodegradability and good rinsability, but has a tendency to degrade the anti-recontamination property of the detergent. The “recontamination preventing property” of the detergent is a performance that suppresses or prevents the soil component from reattaching to the fiber or the like during washing.

  Examples of the detergent composition include a detergent composition using α-sulfo fatty acid alkyl ester salt, soap, alkyl or alkenyl ether sulfate (AES) (see Patent Documents 1 to 3); α-sulfo fatty acid alkyl ester salt, A detergent composition using soap, hydroxypropylmethylcellulose (HPMC) (see Patent Document 4) is known, but any detergent composition can be used as a hydrophilic fiber such as cotton and polyester. It has been difficult to exhibit excellent anti-recontamination properties for both hydrophobic fibers.

  As a means for solving the above-mentioned problem of preventing recontamination, Patent Document 5 discloses a method of using AES and HPMC together, and according to the method, it is good for both cotton cloth and polyester cloth. It is possible to exhibit re-contamination prevention. However, AES is a compound having various problems and concerns from the viewpoint of environmental load. The environmental impact of AES has been reported, for example, by the Japan Soap and Detergent Industry Association (see Non-Patent Document 1), and has skin irritation depending on the concentration, and 14 days under the conditions of the Chemical Substances Control Law. It has been reported that the degree of degradation based on the biochemical oxygen demand (BOD) of the product remains below 60%. For this reason, the present condition is that development of the detergent composition in which the environmental load was further reduced is calculated | required.

JP-A-6-279794 Japanese Patent Laid-Open No. 7-197080 JP-A-8-302398 Japanese Patent Laid-Open No. 9-302395 JP 2009-155560 A

“Risk assessment results on human health effects and environmental effects of polyoxyethylene alkyl ether sulfate (AES)”, December 2011, Japan Soap Detergent Industry Association

Accordingly, an object of the present invention is to provide a detergent composition having excellent anti-staining properties for both hydrophilic fibers and hydrophobic fibers.
Another object of the present invention is to provide a detergent composition having a reduced environmental load.

  As a result of intensive studies to achieve the above object, the present inventors have found that a detergent composition containing a specific amount of cellulose acetate having a specific total degree of acetyl group substitution is superior to both hydrophilic and hydrophobic fibers. Further, it has been found that by replacing AES with cellulose acetate, it is possible to reduce the environmental burden in addition to obtaining the above-mentioned recontamination prevention property. Completed.

  That is, this invention is a detergent composition, Comprising: 0.05-20 of cellulose acetate whose acetyl group total substitution degree is 0.4-1.2 on the basis of the whole quantity (100 mass%) of this detergent composition. Provided is a detergent composition characterized by containing% by mass.

  Furthermore, the said detergent composition further containing 5-20 mass% of alpha-sulfo fatty-acid alkylester salt and 3-10 mass% of soap is provided on the basis of the whole quantity (100 mass%) of a detergent composition.

  Since the detergent composition of the present invention has the above-described configuration, it has excellent anti-staining properties for both hydrophilic fibers such as cotton fibers and hydrophobic fibers such as polyester fibers. Moreover, in obtaining the above-mentioned recontamination prevention property in the detergent composition of the present invention, AES is replaced with cellulose acetate having a total acetyl group substitution degree of 0.4 to 1.2 which is derived from a plant and excellent in biodegradability. Therefore, according to the detergent composition of the present invention, the environmental burden can be further reduced.

<Detergent composition>
The detergent composition of the present invention contains cellulose acetate having an acetyl group total substitution degree (DS) of 0.4 to 1.2 (hereinafter sometimes referred to as “low-substituted cellulose acetate”) as an essential component, The content of the low-substituted cellulose acetate is 0.05 to 20% by mass based on the total amount (100% by mass) of the detergent composition.

[Cellulose acetate having an acetyl group total substitution degree of 0.4 to 1.2]
The low-substituted cellulose acetate is cellulose acetate (cellulose acetate) and has a total acetyl group substitution degree (DS) of 0.4 to 1.2.

(Total substitution degree of acetyl group)
The low-substituted cellulose acetate has a high water solubility because the total acetyl group substitution degree (average substitution degree; sometimes simply referred to as “substitution degree” or “DS”) is 0.4 to 1.2. Moreover, it interacts specifically with clothing fibers and soil components, respectively, and can exhibit an excellent anti-recontamination action for the detergent composition. Such recontamination prevention action is expressed by the fact that the low-substituted cellulose acetate has the same chemical structure as (i) cellulose, which is the main component of clothing cotton cloth, but is soluble in water. (Ii) Among them, it has one of the highest surface energies, and it is thermodynamically stable to perform an interaction such as enclosing other substances such as dirt substances, (iii) In particular, it accounts for a large proportion of dirt substances There is a Lewis acid-Lewis base interaction between the protein and the low-substituted cellulose acetate, and the two are in close contact and form an interface because it is thermodynamically stable. Among these, the low-substituted cellulose acetate is preferably cellulose acetate having an acetyl group total substitution degree of 0.5 to 1.1 from the viewpoint of developing a higher anti-recontamination action, and the acetyl group total substitution degree is preferably It is more preferably 0.5 to 1.0 cellulose acetate, and particularly preferably cellulose acetate having an acetyl group total substitution degree of 0.6 to 0.9.

  The total acetyl group substitution degree of the low-substituted cellulose acetate can be measured by a known titration method in which cellulose acetate is dissolved in water and the cellulose acetate substitution degree is determined. The total degree of acetyl group substitution can also be measured by NMR after propionylating the hydroxyl group of low-substituted cellulose acetate (see the method described later) and dissolving in deuterated chloroform.

The acetyl group total substitution degree of the said low substituted cellulose acetate converts the acetylation degree calculated | required according to the measuring method of the acetylation degree in ASTM: D-817-96 (test methods, such as a cellulose acetate) by following Formula. Is required. This is the most common method for determining the degree of substitution of cellulose acetate.
DS = 162.14 × AV × 0.01 / (60.052-42.037 × AV × 0.01)
DS: Degree of total acetyl group substitution AV: Degree of acetylation (%)
First, 500 mg of dried low-substituted cellulose acetate (sample) was precisely weighed and dissolved in 50 ml of a mixed solvent of ultrapure water and acetone (volume ratio 4: 1), and then 50 ml of 0.2N sodium hydroxide aqueous solution. And saponify for 2 hours at 25 ° C. Next, 50 ml of 0.2N hydrochloric acid is added, and the amount of acetic acid released is titrated with a 0.2N sodium hydroxide aqueous solution (0.2N sodium hydroxide normal solution) using phenolphthalein as an indicator. In addition, a blank test (a test without using a sample) is performed by the same method. Then, AV (degree of acetylation) (%) is calculated according to the following formula.
AV (%) = (A−B) × F × 1.201 / sample weight (g)
A: Titration amount of 0.2N sodium hydroxide normal solution (ml)
B: Titration of 0.2N sodium hydroxide normal solution in blank test (ml)
F: Factor of 0.2N sodium hydroxide normal solution

(Composition distribution index: CDI)
The composition distribution of the low-substituted cellulose acetate (distribution of acetyl group substitution degree between molecules) is not particularly limited. For example, the composition distribution index (CDI) is preferably 1.0 to 2.0, more Preferably it is 1.0-1.8, More preferably, it is 1.0-1.6, Most preferably, it is 1.0-1.5. The smaller the composition distribution index (CDI) of the low-substituted cellulose acetate (the closer it is to 1.0), the more uniform the composition distribution (intermolecular acetyl group substitution degree distribution), and the higher the anti-recontamination effect of the detergent composition. Tend to be. This is presumed to be because the low-substituted cellulose acetate has a uniform composition distribution, so that its solubility is improved and specific interaction with soil components such as proteins is likely to occur. In addition, when the composition distribution of the low-substituted cellulose acetate is uniform, there is a tendency that water solubility can be ensured in a range where the total degree of acetyl group substitution is wider than usual, which also contributes to an improvement in the effect of preventing recontamination. Presumed to be.

  Here, the compositional distribution index (CDI) is the ratio of the measured value to the theoretical value of the composition distribution half width [(actual value of the composition distribution half width) / (theoretical value of the composition distribution half width)]. Defined. The half width of the composition distribution is also referred to as “intermolecular acetyl group substitution degree half width” or simply “substitution degree distribution half width”.

  In order to evaluate the intermolecular uniformity of the degree of acetyl group substitution of the above low-substituted cellulose acetate (the degree of fluctuation of the degree of substitution between molecules), half of the maximum peak of the intermolecular acetyl group substitution distribution curve of cellulose acetate The magnitude of the price range (also referred to as “half-value width”) can be used as an index. Note that the half-value width is that of the chart at half the height of the peak of the chart, where the acetyl group substitution degree is on the horizontal axis (x axis) and the abundance at this substitution degree is on the vertical axis (y axis). It is a width and is an index representing a standard of variation in distribution. The half value width of the substitution degree distribution can be determined by high performance liquid chromatography (HPLC) analysis. In addition, the method of converting the horizontal axis (elution time) of the cellulose ester elution curve in HPLC into the substitution degree (0 to 3) is described in JP-A No. 2003-201301 (paragraphs 0037 to 0040).

ｍ：酢酸セルロース（低置換度酢酸セルロース）１分子中の水酸基とアセチル基の全数
ｐ：酢酸セルロース（低置換度酢酸セルロース）１分子中の水酸基がアセチル置換されている確率
ｑ＝１−ｐ
ＤＰｗ：重量平均重合度（ＧＰＣ−光散乱法による）
重量平均重合度（ＤＰｗ）の測定法は後述する。 (Theoretical value of the half width of composition distribution)
The theoretical distribution of the half value width of composition distribution (substitution degree distribution half width) can be calculated stochastically. That is, the theoretical value of the composition distribution half width is obtained by the following equation (1).

m: Total number of hydroxyl groups and acetyl groups in one molecule of cellulose acetate (low-substituted cellulose acetate) p: Probability that hydroxyl groups in one molecule of cellulose acetate (low-substituted cellulose acetate) are acetyl substituted q = 1−p
DPw: weight average polymerization degree (by GPC-light scattering method)
A method for measuring the weight average degree of polymerization (DPw) will be described later.

ＤＳ：アセチル基総置換度
ＤＰｗ：重量平均重合度（ＧＰＣ−光散乱法による）
重量平均重合度（ＤＰｗ）の測定法は後述する。 Formula (1) is the half width of the composition distribution that inevitably occurs when all hydroxyl groups of cellulose are acetylated and deacetylated with the same probability, and is derived according to the so-called binomial theorem. Furthermore, when the theoretical value of the composition distribution half width is represented by the substitution degree and the polymerization degree, it is expressed as follows. The following formula (2) is a defining formula for obtaining the theoretical value of the composition distribution half width.

DS: Total substitution degree of acetyl group DPw: Weight average polymerization degree (by GPC-light scattering method)
A method for measuring the weight average degree of polymerization (DPw) will be described later.

  By the way, in the formula (1) and the formula (2), the polymerization degree distribution should be taken into account more strictly. In this case, the “DPw” in the formula (1) and the formula (2) represents the polymerization degree. Substituting a distribution function, the entire equation should be integrated from 0 to infinity. However, as long as DPw is used, equations (1) and (2) give theoretical values with approximately sufficient accuracy. If DPn (number average degree of polymerization) is used, the influence of the degree of polymerization distribution cannot be ignored, so DPw should be used.

(Measured value of composition distribution half width)
The above-mentioned actual value of the composition distribution half width is the composition distribution half obtained by HPLC analysis of cellulose acetate propionate obtained by propionylating all remaining hydroxyl groups (unsubstituted hydroxyl groups) of low-substituted cellulose acetate (sample). The price range.

  The measured half-width of the low-substituted cellulose acetate composition distribution (substitution degree distribution half-width) is obtained by derivatizing the residual hydroxyl groups in cellulose acetate as a pretreatment before HPLC analysis and then performing HPLC analysis. . The purpose of this pretreatment is to convert the low-substituted cellulose acetate into a derivative that is easily dissolved in an organic solvent to enable HPLC analysis. That is, the residual hydroxyl group in the molecule is completely propionylated, and the fully derivatized cellulose acetate propionate (CAP) is subjected to HPLC analysis to determine the composition distribution half width (actual value). Here, the derivatization is completely carried out, there should be no residual hydroxyl groups in the molecule, and only acetyl and propionyl groups must be present. That is, the sum of the acetyl group total substitution degree (DSac) and the propionyl group total substitution degree (DSpr) is 3. This is because the relational expression: DSac + DSpr = 3 is used to create a calibration curve for converting the horizontal axis (elution time) of the HPLC elution curve of CAP to the total degree of acetyl group substitution (0 to 3). .

  Complete derivatization of low-substituted cellulose acetate can be carried out by reacting propionic anhydride with N, N-dimethylaminopyridine as a catalyst in a pyridine / N, N-dimethylacetamide mixed solvent. More specifically, a mixed solvent [pyridine / N, N-dimethylacetamide = 1/1 (v / v)] as a solvent is 20 parts by weight with respect to low-substituted cellulose acetate (sample), and anhydrous as a propionylating agent. Propionic acid is 6.0 to 7.5 equivalents relative to the hydroxyl group of the low-substituted cellulose acetate, and N, N-dimethylaminopyridine as the catalyst is 6.5 to 8. Propionylation is carried out using 0 mol% under conditions of a temperature of 100 ° C. and a reaction time of 1.5 to 3.0 hours. And after reaction, fully derivatized cellulose acetate propionate is obtained by making it precipitate using methanol as a precipitation solvent. More specifically, for example, at room temperature, 1 part by weight of the reaction mixture is added to 10 parts by weight of methanol to precipitate, and the resulting precipitate is washed 5 times with methanol and vacuum dried at 60 ° C. for 3 hours. Thus, fully derivatized cellulose acetate propionate (CAP) can be obtained. The polydispersity (Mw / Mn) and weight average degree of polymerization (DPw) described below were also measured by using low-substituted cellulose acetate (sample) as a fully derivatized cellulose acetate propionate (CAP) by this method. It is.

  In the above HPLC analysis, a plurality of cellulose acetate propionates having different degrees of total acetyl group substitution are used as standard samples, HPLC analysis is performed with a predetermined measuring device and measurement conditions, and the analysis values of these standard samples are used. From the calibration curve [the curve showing the relationship between the elution time of cellulose acetate propionate and the total substitution degree of acetyl group (0 to 3), usually a cubic curve], the composition distribution half-width of the low substituted cellulose acetate (sample) (Actual measurement value) can be obtained. What is required by HPLC analysis is the relationship between the elution time and the distribution of acetyl group substitution degree of cellulose acetate propionate. This is the relationship between the elution time of the substance in which all the remaining hydroxy groups in the sample molecule have been converted to propionyloxy groups and the acetyl group substitution degree distribution. It is essentially the same as what you want.

The conditions for the above HPLC analysis are as follows.
Equipment: Agilent 1100 Series
Column: Waters Nova-Pak phenyl 60Å 4 μm (150 mm × 3.9 mmΦ) + guard column Column temperature: 30 ° C.
Detection: Varian 380-LC
Injection volume: 5.0 μL (sample concentration: 0.1% (wt / vol))
Eluent: A solution; MeOH / H ₂ O = 8/1 (v / v), B solution; CHCl ₃ / MeOH = 8/1 (v / v)
Gradient: A / B = 80/20 → 0/100 (28 min); Flow rate: 0.7 mL / min

  Substitution degree distribution curve obtained from the calibration curve [Substitution degree distribution curve of cellulose acetate propionate with the abscissa representing the amount of cellulose acetate propionate and the abscissa representing the degree of acetyl group substitution] ("Intermolecular substitution degree distribution For the maximum peak [E] corresponding to the total degree of acetyl group substitution, the half-value width of substitution degree distribution is determined as follows. The base [A] on the low substitution degree side of the peak [E] and the base line [AB] in contact with the base [B] on the high substitution degree side are drawn, and from this peak, the maximum peak [E] is drawn. Take a vertical line on the horizontal axis. An intersection point [C] between the perpendicular line and the baseline [AB] is determined, and an intermediate point [D] between the maximum peak [E] and the intersection point [C] is obtained. A straight line parallel to the base line [AB] is drawn through the intermediate point [D], and two intersection points [A ′, B ′] with the intermolecular substitution degree distribution curve are obtained. A perpendicular line is drawn from the two intersections [A ′, B ′] to the horizontal axis, and the width between the two intersections on the horizontal axis is defined as the half-value width of the maximum peak (that is, the half-value width of the substitution degree distribution).

The half-value width of the substitution degree distribution depends on the degree of acetylation of the hydroxyl chain of each glucose chain constituting the molecular chain of cellulose acetate propionate in the sample. (Retention time) is different. Therefore, ideally, the holding time width indicates the width of the composition distribution (in units of substitution degree). However, there are tube portions (such as a guide column for protecting the column) that do not contribute to the distribution in HPLC. Therefore, depending on the configuration of the measurement apparatus, the width of the holding time that is not caused by the width of the composition distribution is often included as an error. As described above, this error is affected by the length and inner diameter of the column, the length from the column to the detector, the handling, and the like, and varies depending on the apparatus configuration. For this reason, the half value width of the substitution degree distribution of cellulose acetate propionate can be usually obtained as the correction value Z based on the correction formula represented by the following formula. By using such a correction formula, even if the measurement apparatus (and measurement conditions) are different, a more accurate substitution degree distribution half-value width (actual measurement value) can be obtained as the same (substantially the same) value.
Z = (X ² −Y ² ) ^1/2
[In the formula, X is the half-value width (uncorrected value) of the substitution degree distribution obtained with a predetermined measuring apparatus and measurement conditions. Y = (a−b) x / 3 + b (0 ≦ x ≦ 3). Here, a is the half-value width of the substitution degree distribution of cellulose acetate having a total substitution degree of 3 determined using the same measuring apparatus and measurement conditions as X, and b is the total substitution degree of 3 determined using the same measuring apparatus and measurement conditions as X above. It is a half value width of substitution degree distribution of cellulose propionate. x is the total acetyl group substitution degree of the measurement sample (0 ≦ x ≦ 3)]

  The cellulose acetate (or cellulose propionate) having a total substitution degree of 3 is a cellulose ester in which all of the hydroxyl groups of cellulose are esterified, and (ideally) the half-width of the substitution degree distribution. (Ie, the substitution degree distribution half-width 0) cellulose ester.

  In the present invention, the actually measured value of the composition distribution half width (substitution degree distribution half width) of the low-substituted cellulose acetate is not particularly limited, but is preferably 0.12 to 0.34, more preferably 0.13 to 0. .25.

  The substitution degree distribution theoretical formula (formula for obtaining a theoretical value of the composition distribution half width) described above is a stochastic calculation value that assumes that all acetylation and deacetylation proceed independently and equally. That is, the calculated value according to the binomial distribution. Such an ideal situation is not realistic. Special device for hydrolysis reaction of cellulose acetate or post-treatment after reaction (more specifically, composition of hydrolysis reaction of cellulose acetate approaches ideal random reaction and / or post-treatment after reaction Unless special measures are taken to generate fractionation, the distribution of substitution degree of cellulose ester is much broader than that stochastically determined by the binomial distribution. In particular, low-substituted cellulose acetate tends to have a particularly wide substitution degree distribution because the number of partial deacetylation reactions is large in the production process.

  In producing low-substituted cellulose acetate, as one of the special measures for the reaction, for example, it is conceivable to maintain the system under the condition where deacetylation and acetylation are balanced. However, in this case, the decomposition of cellulose proceeds with an acid catalyst, which is not preferable. Another special contrivance for the reaction is to employ reaction conditions in which the deacetylation rate is slow for low substitution products. However, conventionally, such a specific method is not known. In other words, no special device for the reaction is known that controls the substitution degree distribution of the cellulose ester to follow the binomial distribution according to the reaction probability theory. Furthermore, various circumstances such as non-uniformity of acetylation process (cellulose acetylation process) and partial and temporary precipitation due to water added stepwise in aging process (cellulose hydrolysis process) It works in the direction to make the substitution degree distribution wider than the binomial distribution, avoiding all of these, and realizing the ideal condition is impossible in practice. This is similar to the fact that an ideal gas is an ideal product, and the behavior of an actual gas is more or less different.

  In the synthesis and post-treatment of conventional low-substituted cellulose acetate, little attention has been paid to the problem of such substitution degree distribution, and substitution degree distribution has not been measured, verified, or considered. For example, according to the literature (Journal of the Textile Society of Japan, 42, p25 (1986)), it is argued that the solubility of low-substituted cellulose acetate is determined by the distribution of acetyl groups to the glucose residues 2, 3, and 6. The composition distribution is not considered at all.

  According to the study by the present inventors, as described later, the substitution degree distribution of cellulose acetate can be surprisingly controlled by devising the post-treatment conditions after the cellulose acetate hydrolysis step. Literature (CiBment, L., and Rivibre, C., Bull. SOC. Chim., (5) 1, 1075 (1934), Sookne, AM, Rutherford, HA, Mark, H., and Harris, M. J. Research Natl. Bur. Standards, 29, 123 (1942), AJ Rosenthal, BB White Ind. Eng. Chem., 1952, 44 (11), pp 2693-2696.) In the precipitation fractionation of cellulose acetate No. 3, fractionation depending on the molecular weight and slight fractionation accompanying the substitution degree (chemical composition) occur, and the substitution degree (chemical composition) as found by the present inventors. There is no report that a remarkable fraction can be produced. Furthermore, it has not been verified that the substitution degree distribution (chemical composition) can be controlled by dissolution fractionation or precipitation fractionation for low-substituted cellulose acetate.

  Another device for narrowing the substitution degree distribution found by the present inventors is a hydrolysis reaction (aging reaction) of cellulose acetate at a high temperature of 90 ° C. or higher (or higher than 90 ° C.). Conventionally, although detailed analysis and consideration have not been made on the degree of polymerization of a product obtained by a high-temperature reaction, it has been considered that decomposition of cellulose is preferred in a high-temperature reaction at 90 ° C. or higher. This idea can be said to be a belief (stereotype) based solely on the consideration of viscosity. When the present inventors hydrolyze cellulose acetate to obtain low-substituted cellulose acetate, it is in a large amount of acetic acid at a high temperature of 90 ° C. or higher (or higher than 90 ° C.), preferably in the presence of a strong acid such as sulfuric acid. It was found that when the reaction was carried out with the above, the degree of polymerization was not lowered, but the viscosity was lowered with a decrease in CDI. That is, it has been clarified that the viscosity decrease due to the high temperature reaction is not due to a decrease in the degree of polymerization but is based on a decrease in structural viscosity due to a narrow substitution degree distribution. When cellulose acetate is hydrolyzed under the above conditions, not only forward reaction but also reverse reaction occurs, so the product (low-substituted cellulose acetate) has a very small CDI, and the solubility in water is significantly improved. On the other hand, when cellulose acetate is hydrolyzed under conditions where reverse reaction is unlikely to occur, the substitution degree distribution becomes wide due to various factors, and cellulose acetate and acetyl groups having a total degree of substitution of less than 0.4 acetyl groups that are difficult to dissolve in water. The content of cellulose acetate exceeding the total substitution degree 1.2 increases, and the solubility in water as a whole decreases.

(Standard deviation of substitution degree at 2, 3, 6 position)
The degree of acetyl group substitution at the 2, 3, and 6 positions of the glucose ring of the low-substituted cellulose acetate can be measured by NMR according to the method of Tezuka (Carbohydr. Res. 273, 83 (1995)). That is, the free hydroxyl group of a low-substituted cellulose acetate sample is propionylated with propionic anhydride in pyridine. The obtained sample is dissolved in deuterated chloroform, and a ¹³ C-NMR spectrum is measured. The carbon signal of the acetyl group appears in the order of 2, 3, 6 from the high magnetic field in the region of 169 ppm to 171 ppm, and the signal of the carbonyl carbon of the propionyl group appears in the same order in the region of 172 ppm to 174 ppm. From the abundance ratio of the acetyl group and propionyl group at the corresponding positions, the degree of substitution of each acetyl group at the 2, 3, 6 positions of the glucose ring in the original low-substituted cellulose acetate can be determined. In addition, the sum of the substitution degree of each acetyl group at the 2, 3, and 6 positions thus obtained is the total substitution degree of acetyl group, and the total substitution degree of acetyl group can be obtained by this method. The total substitution degree of acetyl group can be analyzed by ¹ H-NMR in addition to ¹³ C-NMR.

The standard deviation σ of the substitution degree of acetyl groups at the 2, 3, 6 positions is defined by the following formula.

  The standard deviation of the acetyl group substitution degree at the 2, 3 and 6 positions of the glucose ring of the low substituted cellulose acetate is not particularly limited, but is preferably 0.08 or less (0 to 0.08). The low-substituted cellulose acetate having a standard deviation of 0.08 or less is evenly substituted at positions 2, 3, and 6 of the glucose ring, and is more water-soluble and exhibits higher anti-recontamination properties. Tend.

(Polydispersity (Mw / Mn))
In the present invention, the polydispersity (dispersion degree, Mw / Mn) of the molecular weight distribution and polymerization degree distribution of the low-substituted cellulose acetate is obtained by propionylating all remaining hydroxyl groups of the low-substituted cellulose acetate (sample). It is the value calculated | required by GPC-light-scattering method using acetate propionate.

  The polydispersity (dispersity, Mw / Mn) of the low-substituted cellulose acetate is not particularly limited, but is preferably in the range of 1.2 to 2.5. A low-substituted cellulose acetate having a polydispersity Mw / Mn in the above range tends to be more excellent in water solubility and exhibit higher anti-staining properties.

The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw / Mn) of the low-substituted cellulose acetate can be determined by a known method using HPLC. In the present invention, the polydispersity (Mw / Mn) of the low-substituted cellulose acetate is determined by the same method as that for obtaining the measured half-value width of the composition distribution in order to make the measurement sample soluble in an organic solvent. After the cellulose (sample) is completely derivatized cellulose acetate propionate (CAP), it is determined by performing size exclusion chromatography analysis under the following conditions (GPC-light scattering method).
Equipment: GPC “SYSTEM-21H” manufactured by Shodex
Solvent: Acetone Column: 2 GMHxl (Tosoh), same guard column Flow rate: 0.8 ml / min
Temperature: 29 ° C
Sample concentration: 0.25% (wt / vol)
Injection volume: 100 μl
Detection: MALLS (multi-angle light scattering detector) (manufactured by Wyatt, “DAWN-EOS”)
MALLS correction standard substance: PMMA (molecular weight 27600)

(Weight average degree of polymerization (DPw))
In the present invention, the weight average polymerization degree (DPw) of the low-substituted cellulose acetate is GPC-light scattering using cellulose acetate propionate obtained by propionylating all remaining hydroxyl groups of the low-substituted cellulose acetate (sample). It is a value obtained by the law.

  The weight average polymerization degree (DPw) of the low-substituted cellulose acetate in the present invention is preferably in the range of 50 to 800. If the weight average degree of polymerization (DPw) is too low, the polymer properties may be impaired, and the effect of enveloping the soil component and preventing recontamination may be impaired. Moreover, when the weight average degree of polymerization (DPw) is too high, the filterability tends to deteriorate. The weight average polymerization degree (DPw) is preferably 55 to 700, and more preferably 60 to 600.

  As with the polydispersity (Mw / Mn), the weight average degree of polymerization (DPw) is the same as the method for obtaining the measured value of the half-value width of the composition distribution. It is calculated | required by making size-exclusion chromatography analysis after setting it as a hydrogenated cellulose acetate propionate (CAP) (GPC-light-scattering method).

  As described above, the molecular weight (polymerization degree) and polydispersity (Mw / Mn) of the low-substituted cellulose acetate excellent in water solubility are measured by GPC-light scattering method (GPC-MALLS, GPC-LALLS, etc.). The Note that detection of light scattering is generally difficult with an aqueous solvent. This is because aqueous solvents generally have a large amount of foreign matter and are easily contaminated by secondary contamination once purified. In addition, in the case of aqueous solvents, the spread of molecular chains may not be stable due to the influence of ionic dissociation groups present in a trace amount, and if water-soluble inorganic salt (for example, sodium chloride) is added to suppress this, it will dissolve. The state may become unstable, and an aggregate may be formed in an aqueous solution. One effective method for avoiding this problem is to derivatize low-substituted cellulose acetate so that it is dissolved in an organic solvent that is less contaminated and less susceptible to secondary contamination. Is to do. Propionylation is effective as the derivatization of low-substituted cellulose acetate for this purpose, and the specific reaction conditions and post-treatment are as described in the explanation of the measured value of the half width of the composition distribution.

(6% viscosity)
Although 6% viscosity of the said low substituted cellulose acetate is not specifically limited, 5-500 mPa * s is preferable, More preferably, it is 6-300 mPa * s. If the 6% viscosity is too high, filterability may deteriorate. On the other hand, if the 6% viscosity is too low, the polymer properties may be impaired, and the effect of wrapping a dirt component and preventing recontamination may be impaired.

The 6% viscosity of the low-substituted cellulose acetate can be measured by the following method.
Add 3.00 g of dry sample to a 50 ml volumetric flask and add distilled water to dissolve. The obtained 6 wt / vol% solution is transferred to a predetermined Ostwald viscometer mark and temperature-controlled at 25 ± 1 ° C. for about 15 minutes. Measure the flow-down time between the time marks and calculate the 6% viscosity by the following formula.
6% viscosity (mPa · s) = C × P × t
C: Sample solution constant P: Sample solution density (0.997 g / cm ³ )
t: The number of seconds that the sample solution flows down The sample solution constant is the same as described above using a standard solution for viscometer calibration [manufactured by Showa Oil Co., Ltd., trade name “JS-200” (based on JIS Z 8809)]. Measure the flow-down time and obtain it from the following formula.
Sample solution constant = {Standard solution absolute viscosity (mPa · s)} / {Standard solution density (g / cm ³ ) × Standard solution flow down seconds}

(Production of low-substituted cellulose acetate)
The low-substituted cellulose acetate is, for example, (a) a medium to high-substituted cellulose acetate hydrolysis step (aging step), (b) a precipitation step, and (c) a washing and neutralization step performed as necessary. It can manufacture by the method containing.

[(A) Hydrolysis step (aging step)]
In this step, medium to high-substituted cellulose acetate (hereinafter sometimes referred to as “raw cellulose acetate”) is hydrolyzed. The total acetyl group substitution degree of the medium to high substitution cellulose acetate used as a raw material is not particularly limited, but is preferably 1.5 to 3, more preferably 2 to 3. Examples of the raw material cellulose acetate include commercially available cellulose diacetate (for example, cellulose acetate having an acetyl group total substitution degree of 2.27 to 2.56) and cellulose triacetate (for example, an acetyl group total substitution degree of more than 2.56 to 3). Cellulose acetate) can be used.

  The hydrolysis reaction can be performed by reacting raw material cellulose acetate and water in an organic solvent in the presence of a catalyst (aging catalyst). Examples of the organic solvent include acetic acid, acetone, alcohol (such as methanol), and mixed solvents thereof. Among these, a solvent containing at least acetic acid is preferable. As the catalyst, a catalyst generally used as a deacetylation catalyst can be used. As the catalyst, sulfuric acid is particularly preferable.

  Although the usage-amount of an organic solvent (for example, acetic acid) is not specifically limited, 0.5-50 weight part is preferable with respect to 1 weight part of raw material cellulose acetate, More preferably, it is 1-20 weight part, More preferably, it is 3 -10 parts by weight.

  The amount of catalyst (for example, sulfuric acid) used is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.02 with respect to 1 part by weight of raw material cellulose acetate. -0.3 parts by weight. If the amount of the catalyst is too small, the hydrolysis time becomes too long, which may cause a decrease in the molecular weight of the low-substituted cellulose acetate. On the other hand, when the amount of the catalyst is too large, the degree of change in the depolymerization rate with respect to the hydrolysis temperature increases, the depolymerization rate increases even if the hydrolysis temperature is low to some extent, and low-substituted cellulose acetate having a certain degree of molecular weight. It becomes difficult to obtain.

  The amount of water in the hydrolysis step is not particularly limited, but is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 2 to 7 parts by weight with respect to 1 part by weight of raw material cellulose acetate. Part. The amount of the water is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 2 parts by weight, and still more preferably 0.5 to 5 parts by weight with respect to 1 part by weight of the organic solvent (eg, acetic acid). 1.5 parts by weight. Although all amounts of water may be present in the system at the start of the reaction, in order to prevent precipitation of cellulose acetate, a part of the water to be used is present in the system at the start of the reaction, and the remaining water is removed. It may be added to the system in 1 to several times.

  Although the reaction temperature in a hydrolysis process is not specifically limited, 40-130 degreeC is preferable, More preferably, it is 50-120 degreeC, More preferably, it is 60-110 degreeC. In particular, when the reaction temperature is 90 ° C. or higher (or a temperature exceeding 90 ° C.), preferably when a strong acid such as sulfuric acid is used as a catalyst and acetic acid is used excessively as a reaction solvent, a positive reaction (hydrolysis reaction). As a result, a reverse reaction (acetylation reaction) occurs, and as a result, the substitution degree distribution becomes narrow, and a low-substituted cellulose acetate having an extremely small composition distribution index (CDI) can be obtained without any special ingenuity in the post-treatment conditions. Can do. Even when the reaction temperature is 90 ° C. or lower, as described later, in the precipitation step, precipitation is performed using a mixed solvent containing two or more solvents as the precipitation solvent, precipitation separation and / or dissolution. By performing the fractionation, a low-substituted cellulose acetate having a very small composition distribution index (CDI) can be obtained.

[(B) Precipitation step]
In this step, after completion of the hydrolysis reaction, the temperature of the reaction system is cooled to room temperature, and a precipitation solvent is added to precipitate low-substituted cellulose acetate. As the precipitation solvent, an organic solvent miscible with water or an organic solvent having high solubility in water can be used. Examples include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and isopropyl alcohol; esters such as ethyl acetate; nitrogen-containing compounds such as acetonitrile; ethers such as tetrahydrofuran; and mixed solvents thereof.

  When a mixed solvent containing two or more kinds of solvents is used as the precipitation solvent, the same effect as the precipitation fractionation described later can be obtained, the composition distribution (intermolecular substitution degree distribution) is narrow, and the low substitution with a small composition distribution index (CDI). Degree cellulose acetate can be obtained. Preferred examples of the mixed solvent include a mixed solvent of acetone and methanol, a mixed solvent of isopropyl alcohol and methanol, and the like.

  Further, by performing precipitation fractionation (fractional precipitation) and / or dissolution fractionation (fractional dissolution) on the low-substituted cellulose acetate obtained by precipitation, the composition distribution (intermolecular substitution degree distribution) is narrow, Low substituted cellulose acetate having a very small composition distribution index (CDI) can be obtained.

  For precipitation fractionation, for example, low-substituted cellulose acetate (solid matter) obtained by precipitation is dissolved in water to obtain an aqueous solution having an appropriate concentration (for example, 2 to 10% by weight, preferably 3 to 8% by weight). Then, a poor solvent is added to this aqueous solution (or the above aqueous solution is added to the poor solvent), and kept at an appropriate temperature (for example, 30 ° C. or lower, preferably 20 ° C. or lower) to precipitate low-substituted cellulose acetate, This can be done by collecting the precipitate. Examples of the poor solvent include alcohols such as methanol and ketones such as acetone. The amount of the poor solvent used is preferably, for example, 1 to 10 parts by weight, and more preferably 2 to 7 parts by weight with respect to 1 part by weight of the aqueous solution.

  For the dissolution fractionation, for example, the low-substituted cellulose acetate (solid matter) obtained by the precipitation or the low-substituted cellulose acetate (solid matter) obtained by the precipitation fractionation is mixed with water and an organic solvent (for example, acetone or the like). A mixed solvent of ketone, alcohol such as ethanol) and stirring at an appropriate temperature (for example, 20 to 80 ° C., preferably 25 to 60 ° C.), and then separated into a concentrated phase and a diluted phase by centrifugation, A precipitation solvent (for example, a ketone such as acetone or an alcohol such as methanol) is added to the diluted phase, and the precipitate (solid matter) is recovered. The concentration of the organic solvent in the mixed solvent of water and organic solvent is preferably, for example, 5 to 50% by weight, and more preferably 10 to 40% by weight.

[(C) Washing and neutralization step]
The precipitate (solid matter) obtained in the above-described (b) precipitation step is preferably washed with an organic solvent (poor solvent) such as an alcohol such as methanol or a ketone such as acetone. It is also preferable to wash and neutralize with an organic solvent containing a basic substance (for example, alcohol such as methanol, ketone such as acetone). The neutralization step may be provided immediately after the hydrolysis step. In that case, it is preferable to add a basic substance or an aqueous solution thereof to the hydrolysis reaction bath.

  Examples of the basic substance include alkali metal compounds (for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal carbonates such as sodium hydrogen carbonate) Hydrogen salts; alkali metal carboxylates such as sodium acetate and potassium acetate; sodium alkoxides such as sodium methoxide and sodium ethoxide), alkaline earth metal compounds (for example, alkaline earth such as magnesium hydroxide and calcium hydroxide) Metal hydroxides; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkaline earth metal carboxylates such as magnesium acetate and calcium acetate; alkaline earth metal alkoxides such as magnesium ethoxide, etc.) can be used. . Among these, alkali metal compounds such as potassium acetate are particularly preferable.

  By washing and neutralization, impurities such as a catalyst (such as sulfuric acid) used in the hydrolysis step can be efficiently removed.

  The low-substituted cellulose acetate thus obtained can be adjusted to a specific particle size range by pulverizing, sieving, or granulating as necessary.

  In the detergent composition of the present invention, the low-substituted cellulose acetate can be used singly or in combination of two or more.

  The content (blending amount) of the low-substituted cellulose acetate in the detergent composition of the present invention is 0.05 to 20% by mass based on the total amount (100% by mass) of the detergent composition, preferably 0.00. It is 5-20 mass%, More preferably, it is 1-10 mass%, More preferably, it is 1-7 mass%. If the amount of the low-substituted cellulose acetate is too small, the effect of preventing recontamination is not exhibited. When there is too much said low substituted cellulose acetate, the washing | cleaning capability of (alpha) -sulfo fatty-acid alkylester salt and soap will be impaired.

[Α-sulfo fatty acid alkyl ester salt]
The detergent composition of the present invention may further contain an α-sulfo fatty acid alkyl ester salt for the purpose of obtaining a recontamination preventing effect and a detergency improving effect. The α-sulfo fatty acid alkyl ester salt in the detergent composition of the present invention is not particularly limited, and any α-sulfo fatty acid alkyl ester salt used in a general detergent composition can be preferably used. . Examples of α-sulfo fatty acid alkyl ester salts include methyl, ethyl, or propyl ester salts of saturated or unsaturated α-sulfo fatty acids having 10 to 22 carbon atoms, and in particular, JP-A-2009-155560. The α-sulfo fatty acid alkyl ester salt disclosed in paragraph 0007 can be preferably used. In the detergent composition of the present invention, the α-sulfo fatty acid alkyl ester salt can be used alone or in combination of two or more.

  The content (blending amount) of the α-sulfo fatty acid alkyl ester salt in the detergent composition of the present invention is not particularly limited, but is preferably 5 to 20% by mass based on the total amount (100% by mass) of the detergent composition, More preferably, it is 7-15 mass%. By controlling the content of the α-sulfo fatty acid alkyl ester salt within the above range, there is a tendency that a recontamination preventing effect and a detergency improving effect are obtained at a higher level.

[Soap]
The detergent composition of the present invention may further contain soap for the purpose of obtaining a detergency improving effect. The kind of soap in the detergent composition of the present invention is not particularly limited, and any soap used in general detergent compositions can be preferably used. As the soap used in the detergent composition of the present invention, for example, an alkali metal salt or an alkaline earth metal salt of a fatty acid having an average carbon number of 10 to 20 (preferably a higher fatty acid having 12 to 18 carbon atoms), preferably Alkali metal salts, more preferably sodium salts or potassium salts. The alkyl group of the fatty acid is preferably primary. Either a single chain length or a mixture of two or more chain lengths can be preferably used. In addition, soap can also be used individually by 1 type in the detergent composition of this invention, and can also be used in combination of 2 or more type.

  The soap content (blending amount) in the detergent composition of the present invention is not particularly limited, but is preferably 3 to 10% by mass, more preferably 5 to 10%, based on the total amount (100% by mass) of the detergent composition. It is 5 mass%, More preferably, it is 5-8 mass%. By setting the soap content to 3% by mass or more, there is a tendency that more sufficient detergency and anti-recontamination property can be exhibited. On the other hand, when the soap content is 10% by mass or less, there is a tendency that sufficient detergency can be exhibited without deteriorating the recontamination prevention property.

[Hydroxypropyl methylcellulose (HPMC)]
The detergent composition of the present invention may further contain hydroxypropylmethylcellulose (HPMC) for the purpose of obtaining a better anti-recontamination effect. The kind of hydroxypropylmethylcellulose in the detergent composition of the present invention is not particularly limited, and any of the hydroxypropylmethylcellulose used in general detergent compositions can be preferably used. Although the weight average molecular weight of the hydroxypropyl methylcellulose used for the detergent composition of this invention is not specifically limited, 20000 or more are preferable, More preferably, it is 100,000 or more, More preferably, it is 300000 or more, Especially preferably, it is 350,000 or more. On the other hand, from the viewpoint of solubility, the upper limit of the weight average molecular weight is preferably 1000000, more preferably 500000. By setting the weight average molecular weight of hydroxypropyl methylcellulose to 20000 or more, there is a tendency that desired recontamination preventing property can be expressed. The molecular weight of hydroxypropylmethylcellulose can be measured with a gel filtration chromatography (GPC) -multi-angle laser light scattering detector (MALLS) system, for example, under the following apparatus and operating conditions.
(apparatus)
Liquid feed pump: ShodexDS-4 (manufactured by Showa Denko)
Degasser: ERC3115 (manufactured by ERC)
Column: Shodex SB-806MHQ (manufactured by Showa Denko)
Light scattering detector: DOWN (manufactured by Wyat Technology)
Concentration detector: Shodex RI-71 (manufactured by Showa Denko)
(Operating conditions)
Eluent: 0.1 M NaNO ₃ aqueous solution 1.0 ml / min
Sample: Sample concentration 0.02-0.03% by weight, solvent is 0.1M NaNO ₃ aqueous solution, injection amount: 200 μm

  Specific examples of hydroxypropylmethylcellulose include, for example, “60SH4000”, “60SH10000”, “60SH30000”, “65SH400”, “65SH1500” sold by Shin-Etsu Chemical Co., Ltd. under the trade name “Metroze”. , “65SH4000”, “65SH15000”, “90SH400”, “90SH4000”, “90SH15000”, “90SH30000”, “90SH100000”, and the like can be used. Among these, the 60SH series and 65SH series are particularly preferable. In addition, in the detergent composition of the present invention, hydroxypropylmethylcellulose can be used alone or in combination of two or more.

  The content (blending amount) of hydroxypropylmethylcellulose in the detergent composition of the present invention is not particularly limited, but is preferably 0.1 to 10.0 mass%, more preferably based on the total amount (100 mass%) of the detergent composition. Is 0.1 to 5.0 mass%, more preferably 0.1 to 2.5 mass%. By controlling the content of hydroxypropylmethylcellulose within the above range, there is a tendency that more sufficient detergency and anti-recontamination property can be exhibited.

[Other ingredients]
In addition to the above components, the detergent composition of the present invention further contains the following anionic surfactants, nonionic surfactants, detergency builders, fluorescent brighteners, enzymes, enzyme stabilizers, polymers, It may contain other optional components used in known or commonly used detergent compositions such as an anti-caking agent, an antifoaming agent, a reducing agent, a metal ion scavenger, a pH adjuster, a fragrance, a dye, water, an organic solvent, etc. Good.

(Anionic surfactant)
In the detergent composition of the present invention, known or commonly used anionic surfactants (anionic surfactants other than α-sulfo fatty acid alkyl ester salts) can be used, and are not particularly limited. Can be used. In the detergent composition of the present invention, the anionic surfactants other than the α-sulfo fatty acid alkyl ester salt can be used alone or in combination of two or more.
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(6) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(7) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(8) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.

  The content (blending amount) of the anionic surfactant in the detergent composition of the present invention is not particularly limited, but is 0.1 to 10.0% by mass based on the total amount (100% by mass) of the detergent composition. Preferably, it is 0.5 to 5.0 mass%. By controlling the content of the anionic surfactant within the above range, sufficient detergency tends to be exhibited.

(Nonionic surfactant)
In the detergent composition of the present invention, a known or conventional nonionic surfactant can be used, and is not particularly limited. For example, the following can be used. In the detergent composition of the present invention, the nonionic surfactant can be used alone or in combination of two or more.
(1) A polyoxyalkylene alkyl (or an average of 3 to 30 mol (preferably 5 to 20 mol) of an alkylene oxide having 2 to 4 carbon atoms added to an aliphatic alcohol having 6 to 22 carbon atoms (preferably 8 to 18 carbon atoms) (or Alkenyl) ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate represented by, for example, the following general formula (I) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
R ¹ CO (OA) _n OR ² (I)
[Wherein R ¹ CO represents a fatty acid residue having 6 to 22 (preferably 8 to 18) carbon atoms. OA represents an addition unit of an alkylene oxide having 2 to 4 carbon atoms (preferably 2 to 3 carbon atoms) such as ethylene oxide or propylene oxide. n represents the average number of added moles of alkylene oxide, and is generally 3 to 30, preferably 5 to 20. R ² represents an optionally substituted lower (1-4 carbon atoms) alkyl group which may have a substituent having 1 to 3 carbon atoms. ]
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.

  Among the nonionic surfactants, the nonionic surfactant of the above (1) is preferable, and in particular, polyoxyethylene having an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms added to an aliphatic alcohol having 12 to 16 carbon atoms. Alkylene alkyl (or alkenyl) ethers are preferred. A polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and an HLB of 9 to 16, a polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, a fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to a fatty acid methyl ester, Fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to fatty acid methyl ester can be particularly preferably used. The HLB of the nonionic surfactant in the present invention is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991). , Page 234). The melting point in the present invention is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical products”.

  The content (blending amount) of the nonionic surfactant in the detergent composition of the present invention is not particularly limited, but is preferably 0.1 to 10.0% by mass based on the total amount (100% by mass) of the detergent composition. More preferably, it is 0.5-5.0 mass%. By controlling the content of the nonionic surfactant within the above range, sufficient detergency tends to be exhibited.

(Detergency builder)
In the detergent composition of the present invention, a known or conventional detergency builder can be used, and is not particularly limited. For example, an inorganic builder or an organic builder can be used. Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate; alkali metal sulfites such as sodium sulfite and potassium sulfite; crystalline alkali metal silicates [for example, crystals Layered sodium silicate, trade name “Na-SKS-6” (δ-Na ₂ O.2SiO ₂ ) and the like manufactured by Clariant Japan Ltd.]; amorphous alkali metal silicate; sulfate such as sodium sulfate and potassium sulfate; Alkali metal chlorides such as sodium chloride and potassium chloride; phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate; crystalline aluminosilicate; amorphous alumino Silicate; a complex of sodium carbonate and amorphous alkali metal silicate (eg, Rhod a trade name "NABION15"), and the like. Among the inorganic builders, sodium carbonate, aluminosilicate, or potassium salts (potassium carbonate, potassium sulfate, etc.) or alkali metal chlorides (potassium chloride, sodium chloride, etc.) are preferred as having the effect of improving solubility. As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, and crystalline aluminosilicate is preferable from the viewpoint of cation exchange ability. As the crystalline aluminosilicate, A-type, X-type, Y-type, P-type zeolite and the like can be preferably used, and the average primary particle diameter is preferably 0.1 to 10 μm. The content (blending amount) of the crystalline aluminosilicate in the detergent composition of the present invention is not particularly limited, but is preferably 1 to 40% by mass based on the total amount (100% by mass) of the detergent composition, and washed. From the viewpoint of powder properties such as performance and fluidity, 2 to 30% by mass is particularly preferable. When potassium carbonate is used, its content (blending amount) is not particularly limited, but from the viewpoint of the effect of improving solubility, 1 to 15% by mass is based on the total amount (100% by mass) of the detergent composition. More preferably, it is 2-12 mass%, More preferably, it is 5-12 mass%. When using an alkali metal chloride, the content (blending amount) is not particularly limited, but 1 to 10 masses based on the total amount (100 mass%) of the detergent composition from the viewpoint of improving the solubility. % Is preferable, more preferably 2 to 8% by mass, and still more preferably 3 to 7% by mass. When the crystalline alkali metal silicate is used, its content (blending amount) is not particularly limited, but from the viewpoint of cleaning performance, it is 0.5 to 40 based on the total amount (100% by mass) of the detergent composition. The mass% is preferable, more preferably 1 to 25 mass%, still more preferably 3 to 20 mass%, and particularly preferably 5 to 15 wt%.

  Examples of the organic builder include nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, iminodisuccinate, and the like; serine diacetate, hydroxyimino Hydroxyaminocarboxylates such as disuccinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, Cyclocarboxylates such as benzopolycarboxylates and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; Acrylate, salt of acrylic acid-allyl alcohol copolymer, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid such as polyglyoxylic acid, hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Salt of acrylic acid polymer or copolymer such as polymer; salt of polymer or copolymer such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid; starch, Examples thereof include polysaccharide oxides such as cellulose, amylose and pectin, and polysaccharide derivatives such as carboxymethylcellulose. Among the organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, polyacrylate, polyglyoxyl having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) Polyacetal carboxylates such as acids (for example, those described in JP-A-54-52196) are preferred. Although the content (blending amount) of the organic builder in the detergent composition of the present invention is not particularly limited, it is preferably 1 to 20% by mass, more preferably 1 to 20% by mass based on the total amount (100% by mass) of the detergent composition. It is 10 mass%, More preferably, it is 2-5 mass%.

  In the detergent composition of the present invention, the detergency builder can be used alone or in combination of two or more. Among the detergency builders, the detergency and dirt dispersibility in the washing liquid are improved, so citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid copolymer It is preferable to use an organic builder such as a salt of a coalescence or a salt of polyacetal carboxylic acid in combination with an inorganic builder such as zeolite. The content (total amount) of the detergency builder in the detergent composition of the present invention is not particularly limited, but is 10 to 80 on the basis of the total amount (100% by mass) of the detergent composition from the viewpoint of providing sufficient cleaning performance. % By mass is preferable, and more preferably 20 to 75% by mass.

(Fluorescent brightener)
In the detergent composition of the present invention, a known or conventional fluorescent brightening agent can be used, and is not particularly limited. For example, 4,4′-bis (2-sulfostyryl) -biphenyl salt, 4,4 '-Bis (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4'-bis (triazol-2-yl) stilbene derivative, bis (triazinylaminostilbene) ) Disulfonic acid derivatives and the like can be used.

  In the detergent composition of the present invention, the optical brightener can be used alone or in combination of two or more. Commercially available products can be used as the fluorescent whitening agent. Specifically, for example, Whiteex SA, Whiteex SKC (above, trade name, manufactured by Sumitomo Chemical Co., Ltd.); Chino Pearl AMS-GX, Chino Pearl DBS -X, Chino Pearl CBS-X (trade name, manufactured by Ciba Specialty Chemicals); Lemonite CBUS-3B (trade name, manufactured by Khyati Chemicals) and the like are preferable. Of these, chinopearl CBS-X and chinopearl AMS-GX are more preferable.

  The content (blending amount) of the optical brightener in the detergent composition of the present invention is not particularly limited, but is preferably 0.001 to 1% by mass based on the total amount (100% by mass) of the detergent composition.

(enzyme)
In the detergent composition of the present invention, known or conventional enzymes can be used, and are not particularly limited. For example, when classified from the reactivity of the enzyme, hydrolases, oxidoreductases, lyases, transferases, And isomerases, and any of them can be applied in the present invention. Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable. Specific examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promeline, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like. Examples of the commercially available products include sabinase, alcalase, cannase, everase, deozyme (above, trade name, manufactured by Novozymes); API21 (trade name, manufactured by Showa Denko KK); Genencore); protease K-14 or K-16 (protease described in JP-A-5-25492) and the like. Specific examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like. Specific examples of the lipase include commercially available lipases such as lipolase, Lipex (trade name, manufactured by Novozymes) and liposome (trade name, manufactured by Showa Denko KK). Examples of cellulases include commercially available cellzymes (trade name, manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K-539, alkaline cellulase K-577, and alkaline cellulase K. -425, alkaline cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline cellulase K-522, CMCase I, CMCase II, alkaline cellulase-II, and alkaline cellulase E -III (cellulase described in JP-A-63-264699) and the like. Specific examples of amylase include commercially available Termamyl, Duramil (trade name, manufactured by Novozymes) and the like. In the detergent composition of the present invention, the enzyme can be used alone or in combination of two or more. In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).

  The content (blending amount) of the enzyme in the detergent composition of the present invention is not particularly limited, but is preferably 0.001 to 3 mass% based on the total amount (100 mass%) of the detergent composition. By controlling the content of the enzyme within the above range, there is a tendency that sufficient detergency can be expressed.

(Enzyme stabilizer)
In the detergent composition of the present invention, known or conventional enzyme stabilizers can be used, and are not particularly limited, and examples thereof include calcium salts, magnesium salts, polyols, formic acid, and boron compounds. Of these, sodium tetraborate, calcium chloride and the like can be preferably used. In the cleaning composition of the present invention, one type of enzyme stabilizer can be used alone, or two or more types can be used in combination. The content (blending amount) of the enzyme stabilizer in the detergent composition of the present invention is not particularly limited, but is preferably 0.05 to 2% by mass based on the total amount (100% by mass) of the detergent composition.

(Polymers)
The detergent composition of the present invention has an average as a binder or a powder property modifier used when densifying the detergent composition particles, or to impart a recontamination preventing effect on hydrophobic fine particles (dirt). Polyethylene glycol having a molecular weight of 200 to 200,000, a salt of acrylic acid and / or maleic acid polymer having a weight average molecular weight of 1,000 to 100,000, a cellulose derivative such as polyvinyl alcohol and carboxymethyl cellulose can be blended. Moreover, a copolymer or a terpolymer of a repeating unit derived from terephthalic acid and a repeating unit derived from ethylene glycol and / or propylene glycol can be blended as a soil release agent. Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer. In the detergent composition of the present invention, the above polymers can be used alone or in combination of two or more. The content (blending amount) of the above polymers in the detergent composition of the present invention is not particularly limited, but is preferably 0.05 to 5% by mass based on the total amount (100% by mass) of the detergent composition.

(Anti-caking agent)
In the detergent composition of the present invention, a known or conventional anti-caking agent can be used, and is not particularly limited. For example, paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, Fine powder silica, clay, magnesium oxide and the like can be used. In the detergent composition of the present invention, the anti-caking agent can be used alone or in combination of two or more. The content (blending amount) of the anti-caking agent in the detergent composition of the present invention is not particularly limited, and can be appropriately selected from a well-known and usual range according to the desired effect.

(Defoamer)
Examples of antifoaming agents that can be used in the detergent composition of the present invention include conventionally known silicone / silica antifoaming agents. Moreover, as an antifoamer, you may use the antifoamer granulated material etc. which are obtained with the following manufacturing method, for example.
First, 100 g of maltodextrin (trade name, manufactured by Nissho Chemical Co., Ltd .; enzyme-modified dextrin) is added with 20 g of silicone (compound type, product name: PS Antifoam, manufactured by Dow Corning) as an antifoam component and mixed. To obtain a homogeneous mixture. Next, after mixing 50 mass% of the obtained homogeneous mixture, polyethylene glycol (PEG-6000, melting point 58 ° C.) 25 mass%, and neutral anhydrous sodium sulfate 25 mass% at 70-80 ° C., an extrusion granulator ( Granulation is carried out by model EXK S-1, manufactured by Fuji Powder Co., Ltd., to obtain a defoamer granulated product (see JP-A-3-186307).

  In the detergent composition of the present invention, one type of antifoaming agent can be used alone, or two or more types can be used in combination. The content (blending amount) of the antifoaming agent in the detergent composition of the present invention is not particularly limited, and can be appropriately selected from a well-known and usual range according to the desired effect.

(Reducing agent)
In the detergent composition of the present invention, a known or commonly used reducing agent can be used, and is not particularly limited. For example, sodium sulfite, potassium sulfite and the like can be used. In the detergent composition of the present invention, the reducing agents can be used singly or in combination of two or more. The content (blending amount) of the reducing agent in the detergent composition of the present invention is not particularly limited, and can be appropriately selected from a well-known and conventional range depending on the desired effect.

(Metal ion scavenger)
The metal ion scavenger in the detergent composition of the present invention is a component that has the effect of capturing trace metal ions and the like in tap water and suppressing the adsorption of metal ions to fibers (objects to be washed). In the detergent composition of the present invention, a known or conventional metal ion scavenger can be used, and is not particularly limited. In addition to those included in the detergency builder, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid. Aminopolyacetic acids such as glycol ethylenediamine 6 acetic acid; 1-hydroxyethane-1,1-diphosphonic acid (HEDP-H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane -1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyl Iminodi (methylenephosphonic acid), hexamethylenediaminetetra (methyl) Nhosuhon acid), diethylenetriamine penta (methylene phosphonic acid) organic phosphonic acid derivative or a salt thereof and the like; diglycolic acid, citric acid, tartaric acid, oxalic acid, organic acids or salts thereof such as gluconic acid or the like can be used.

  In the detergent composition of the present invention, the metal ion scavenger can be used singly or in combination of two or more. In addition, the content (blending amount) of the metal ion scavenger in the detergent composition of the present invention is not particularly limited, but is preferably 0.1 to 5% by mass based on the total amount (100% by mass) of the detergent composition. More preferably, it is 0.5-3 mass%. By setting the content of the metal ion scavenger to 0.1% by mass or more, the effect of capturing metal ions in tap water is improved. On the other hand, when the content of the metal ion scavenger is 5% by mass or less, the effect of capturing metal ions can be sufficiently obtained.

(PH adjuster)
The pH of the detergent composition of the present invention is not particularly limited, but from the viewpoint of cleaning performance, the pH in a 1% by mass aqueous solution of the detergent composition of the present invention is preferably 8 or more, and the pH in the 1% by mass aqueous solution is Is more preferably 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.

  As a technique for controlling the pH of the detergent composition of the present invention, a method of adjusting pH with an alkaline agent is usually used. Examples of such an alkali agent include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, sodium hydroxide, potassium hydroxide and the like in addition to the alkali agents described in the detergency builder. Specifically, for example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, Rhodia Co., Ltd.), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio). Are preferably used.

  Moreover, in order to prevent the pH of the detergent composition of the present invention from becoming too high, the pH can be adjusted to the above range using an acid or the like. Examples of such acids include the above metal ion scavengers, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or their polycarboxylic acids, citric acid. Sodium bicarbonate, sulfuric acid, hydrochloric acid and the like.

  Further, it is possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from fiber dirt during washing.

  In the detergent composition of the present invention, the above-described component for adjusting pH (pH adjuster) can be used alone or in combination of two or more. Moreover, content (blending amount) of the above-mentioned pH adjuster can be suitably selected according to the desired pH of the detergent composition, and is not particularly limited.

(Fragrance)
As the fragrance that can be used in the detergent composition of the present invention, those generally used in detergents can be used, and are not particularly limited, and examples thereof include fragrances composed of a fragrance component, a solvent, a fragrance stabilizer, and the like. It is done. As such a fragrance | flavor, the thing as described in Unexamined-Japanese-Patent No. 2002-146399 and Unexamined-Japanese-Patent No. 2003-89800 etc. can be used, for example. In addition, the fragrance | flavor can also be used individually by 1 type in the detergent composition of this invention, and can also be used in combination of 2 or more type. Further, the content (blending amount) of the fragrance in the detergent composition of the present invention is not particularly limited, but is preferably 0.001 to 2 mass%, more preferably based on the total amount (100 mass%) of the detergent composition. Is 0.01-1 mass%.

(Dye)
In the detergent composition of the present invention, various dyes such as dyes and pigments can be used to improve the appearance of the detergent composition. Among these, pigments are preferable from the viewpoint of storage stability, and those having oxidation resistance are particularly preferable. Examples of such a dye include oxides, and preferable examples include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine blue, bitumen, cyanine blue, and cyanine green. In addition, the pigment | dye can also be used individually by 1 type in the detergent composition of this invention, and can also be used in combination of 2 or more type. Moreover, the content (blending amount) of the pigment in the detergent composition of the present invention can be appropriately selected according to the desired appearance of the detergent composition, and is not particularly limited.

  The content of alkyl or alkenyl ether sulfate (AES) in the detergent composition of the present invention is not particularly limited, but is less than 3% by mass (for example, 0% by mass) based on the total amount of the detergent composition (100% by mass). Or more, less than 3% by mass), preferably less than 1% by mass, and more preferably less than 0.5% by mass. In particular, it is preferable that the detergent composition of the present invention does not substantially contain AES. By setting the AES content to less than 3% by mass, the environmental load is greatly reduced. Since the detergent composition of the present invention contains a specific amount of low-substituted cellulose acetate, even if the AES content is reduced to 0, an excellent anti-recontamination effect can be exhibited. For this reason, this invention is positioned as what can replace the conventional detergent composition containing AES with large environmental load, and is a technical idea which contributes greatly to reduction of environmental load.

  The detergent composition of the present invention may be a solid detergent composition or a liquid detergent composition. The shape in the case of a solid detergent composition is not specifically limited, A tablet shape, granular form (for example, granular form), a powder form etc. are mentioned. In the case of a liquid detergent composition, usually, in addition to the above-described components (for example, as the remainder of the above-mentioned components), water or an organic solvent (for example, an organic solvent miscible with water such as alcohol or ether) is included. .

  The manufacturing method of the detergent composition of the present invention is not particularly limited, and the detergent composition of the present invention can be manufactured by a generally used manufacturing method. Examples of cases where the detergent composition is in powder form include, for example, a method of dispersing and dissolving a surfactant and other raw materials in water and spray drying, kneading / extrusion, stirring granulation, rolling rolling It can be produced by a method such as kneading, granulation, compression molding, etc., and further pulverizing if necessary. Moreover, when the detergent composition of this invention is a liquid detergent composition, it can manufacture by mixing each component collectively or sequentially, for example.

  The detergent composition of the present invention can be used without particular limitation as various detergent compositions. For example, detergents for textile products (for example, detergents for textile products (clothing, sheets, etc.) that can be washed with water, etc.), household detergents , Industrial detergents (for example, industrial detergents used in the textile industry), hard surface detergents, detergents used in specific applications such as bleaching detergents or partial washing detergents that enhance one of its components It can be used for various purposes.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  The detergent compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were prepared by the preparation methods (Steps A to C) and post-treatment shown below with the compositions of the detergent compositions shown in Tables 1 to 5. In addition, the kind of WSCA (low substituted degree cellulose acetate) shown in Table 4 used in each detergent composition of Examples 1-12 is as showing in Table 6. Next, the prepared detergent composition was used for washing cotton cloth and polyester jersey, and the anti-staining property was evaluated. In the following examples, unless otherwise specified, “%” in the composition represents mass%.

(Method for preparing detergent composition)
・ Process A
Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. Here, α-sulfo fatty acid alkyl ester salt, LAS-Na, soap, and alkyl or alkenyl ether sulfate (AES; only in Comparative Examples 1 and 3) were added and stirred for 10 minutes. Subsequently, MA agent (acrylic acid / maleic acid copolymer sodium salt) was added. After further stirring for 10 minutes, powder A-type zeolite, sodium carbonate, potassium carbonate, and sodium sulfate were added. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%, and then spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain spray dried particles having a moisture content of 5%.
In addition, the quantity of each component used in the process A is as having shown in the column of the process A of Tables 1-5 (the sum total of the component shown in Tables 1-5 used in process AC and a post-processing is 100 mass. Parts (100 parts by mass), and the ratio (parts by mass, mass%) to this).

・ Process B
α-sulfo fatty acid alkyl ester salt aqueous slurry (water concentration 25%) (or a mixture of the aqueous slurry and alkyl or alkenyl ether sulfate water-soluble slurry (water concentration 35%); Comparative Examples 1 and 3 Only), a nonionic surfactant (25% with respect to the α-sulfo fatty acid alkyl ester salt) is added, and the solution is concentrated under reduced pressure with a thin-film dryer until the water content becomes 11%. Mixed concentrate of ester salt and nonionic surfactant (or mixed concentrate of α-sulfo fatty acid alkyl ester salt, alkyl or alkenyl ether sulfate and nonionic surfactant; only in Comparative Examples 1 and 3 )
Subsequently, the spray-dried particles obtained in Step A, the mixed concentrate obtained above, A-type zeolite, nonionic surfactant, fluorescent whitening agent, and water were continuously kneaded (manufactured by Kurimoto Steel Works, KRC). -S4 type) and kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a mixture containing 6% of water containing a surfactant.
In addition, the quantity of each component used in the process B is as having shown in the column of the process B of Tables 1-5 (the sum total of the component shown in Tables 1-5 used in process AC and a post-processing is 100 mass. Parts (100 parts by mass), and the ratio (parts by mass, mass%) to this).

・ Process C
The mixture obtained in step B was cut with a cutter while extruding it using a pelleter double (Fuji Paudal Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm (cutter peripheral speed was 5 m / s). ), Pellets having a length of about 5 to 30 mm were obtained.
Subsequently, particulate A-type zeolite (average particle size 180 μm) as a grinding aid was added to the obtained pellets, and Fitzmill (Hosokawa Micron (Hosokawa Micron (10), arranged in series in the presence of cold air (10 ° C., 15 m / s)) was added. Co., Ltd., DKA-3) (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: 1st stage / 2nd stage / 3rd stage All were 4700 rpm) to obtain a powder.
In addition, the amount of the particulate A-type zeolite used in Step C is as shown in the column of Step C in Tables 1 to 5 (total of components shown in Tables 1 to 5 used in Steps A to C and post-treatment) Is 100 parts by mass (100% by mass), and the ratio (parts by mass, mass%) to this).

(Post-processing)
The powder obtained in the above step C, coated inorganic particles (coated sodium carbonate particles), sodium sulfite, hydroxypropyl methylcellulose (Comparative Examples 1 and 2 and Examples 1 to 12 only), and low-substituted cellulose acetate (WSCA) ( Examples 1 to 13) were replaced with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, baffle plate having a clearance of 20 mm from the inner wall surface and a height of 45 mm on the inner wall surface of the drum of the vessel 131.7L. In addition, under the conditions of a filling rate of 30% by volume, a rotation speed of 22 rpm, and 25 ° C., finely powdered A-type zeolite is further added, and the surface is modified by rolling for 1 minute while spraying nonionic surfactant and fragrance. Particles were obtained.
In order to color a part of the particles obtained above, the particles are transported on a belt conveyor at a speed of 0.5 m / s (the surfactant-containing particle layer on the belt conveyor is 30 mm high and the layer width is 300 mm). ), And a 20% aqueous dispersion of the pigment was sprayed on the surface (average particle size 500 μm, bulk density 0.84 g / cm ³ ).
Next, with a horizontal cylindrical rolling mixer (having two baffle plates with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a clearance of 20 mm between the inner wall surface and a height of 45 mm on the drum inner wall surface of the container 131.7L), Under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C., the particles obtained above and the enzyme were added and mixed for 5 minutes to obtain a detergent composition.
In addition, the amount of each component used in the post-treatment is as shown in the column of the post-treatment in Tables 1 to 5 (the total of the components shown in Tables 1 to 5 used in the steps A to C and the post-treatment is 100 mass Parts (100 parts by mass), and the ratio (parts by mass, mass%) to this).

The detail of each component shown to Tables 1-5 is as follows.
-Α-sulfo fatty acid alkyl ester salt As the α-sulfo fatty acid alkyl ester salt, the following α-sulfo fatty acid methyl ester salt (MES C1618) was used. A fatty acid ester obtained by transesterifying palm oil with methyl alcohol is fractionated, and a C16 fatty acid ester fraction and a C18 fatty acid ester fraction are mixed at a mass ratio of 8: 2, and the flow-down type thin film reactor is mixed. Then, sulfonation was performed with SO ₃ gas diluted with nitrogen gas at a reaction molar ratio (SO ₃ / fatty acid ester) = 1.2 and a reaction temperature of 80 ° C. Subsequently, after introducing 30 parts by mass of methanol with respect to 100 parts by mass of α-sulfo fatty acid methyl ester, 8.6 parts by mass of 35% by mass hydrogen peroxide was introduced, and bleaching was performed at 80 ° C. for 60 minutes. The bleached α-sulfo fatty acid methyl ester was neutralized with an aqueous sodium hydroxide solution at a neutralization temperature of 40 to 70 ° C. so that pH = 7. Excess methanol was then removed under reduced pressure to give an aqueous slurry of MES-Na. The aqueous slurry had a MES-Na content of 66% by mass and a water content of 27% by mass. The residue contained a small amount of by-product α-sulfo fatty acid disodium salt, unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide and the like. In addition, the compounding quantity of (alpha) -sulfo fatty-acid alkylester salt of Tables 1-5 was shown with the quantity as the said aqueous slurry.

·Soap:
Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C., fatty acid composition: carbon number 12; 11.7%, carbon number 14; 0.4%, carbon Number 16; 29.2%, carbon number 18F0 ^* (stearic acid); 0.7%, C18F1 ^* (oleic acid); 56.8%, carbon number 18F2 ^* (linoleic acid); 1.2%, molecular weight: 289, the blending amounts of soaps shown in Tables 1 to 5 are shown as pure amounts). ^* F0, F1, and F2 represent the number of double bonds in the fatty acid.

Alkyl or alkenyl ether sulfate (AES):
An ethylene oxide average 3 mol adduct (AES EO3) prepared by the method described in Japanese Patent Application No. 2005-325807 (P2005-325807).

Hydroxypropyl methylcellulose (HPMC):
Metroze 60SH10000 (manufactured by Shin-Etsu Chemical Co., Ltd., hydroxypropyl having a weight average molecular weight of about 380,000, a methoxyl group substitution degree of 1.9, a methoxyl group mass% of 28-30%, and a hydroxypropoxyl group mass% of 7-12 Methylcellulose).

Other components-Nonionic surfactant (POE alkyl ether): An average of 15 moles of ethylene oxide adduct (90% pure) of ECOROL26 (alcohol having an alkyl group having 12 to 16 carbon atoms manufactured by ECOGREEN). The compounding amount of the nonionic surfactant described in Tables 1 to 5 is shown as a total amount including impurities other than pure components.
LAS-Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid [manufactured by Lion Co., Ltd., Rypon LH-200 (LAS-H pure content 96% by mass)] with 48% by mass sodium hydroxide aqueous solution A mixture of a neutralized compound and a compound neutralized with a 48% by mass aqueous potassium hydroxide solution in a mass ratio of 2: 1 instead of neutralizing with sodium hydroxide. The compounding quantity of LAS-Na of Tables 1-5 was shown in the quantity as these mixtures.
A-type zeolite: A-type zeolite (trade name: Shilton B, manufactured by Mizusawa Chemical Co., Ltd .; pure content: 80% by mass). The compounding amounts of the A-type zeolites shown in Tables 1 to 5 are shown as the total amount including impurities other than pure components.
MA agent: acrylic acid / maleic anhydride copolymer sodium salt (trade name: Aqualic TL-400, manufactured by Nippon Shokubai Co., Ltd .; pure 40% by mass aqueous solution). The blending amount of the MA agent described in Tables 1 to 5 is shown as a total amount including impurities other than pure components.
-Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).
Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.)
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd., average particle size 490 μm, bulk density 1.30 g / cm ³ ).
Sodium carbonate: granular ash (Asahi Glass Co., Ltd., average particle size 320 μm, bulk density 1.07 g / cm ³ ).
Fluorescent brightener: Chinopearl CBS-X (trade name, manufactured by Ciba Specialty Chemicals) / Chinopearl AMS-GX (trade name, manufactured by Ciba Specialty Chemicals) = 3/1 (mass ratio).
Enzyme: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12T (Novozymes) = 5/4 (mass ratio).

-Coated sodium carbonate particles: 85% by mass of sodium carbonate, 3% by mass of sodium salt of acrylic acid / maleic anhydride copolymer, 7% by mass of lauric acid, water and other balances prepared in the first to third steps shown below Surface-treated inorganic particles consisting of
(First step)
Sodium carbonate was charged into a plow shear mixer (Daihei Kiko Co., Ltd.) equipped with a blade-shaped shovel and a clearance between the shovel and the wall surface of 5 mm (filling rate: 30% by volume), and stirring was started at a main shaft of 150 rpm ( Chopper rotation speed: 1015 rpm, blade tip speed (peripheral speed): 6.9 m / s). Ten seconds after the start of stirring, an aqueous solution of sodium salt of acrylic acid / maleic anhydride copolymer was sprayed for 180 seconds with a pressure nozzle (flat nozzle) having a spray angle of 115 degrees to perform granulation / coating operation. In addition, in the particle | grains prepared at the 1st process, when the moisture content with respect to this particle | grain whole quantity exceeds 10 mass%, hot air is introduce | transduced into the said apparatus and it dries, and the moisture content is adjusted to 10 mass% or less. did.
(Second step)
Subsequently, lauric acid was sprayed and added for 180 seconds with a pressure nozzle (full cone nozzle) having a spray angle of 60 degrees, while continuing the stirring of the Proshear mixer. Subsequently, stirring was continued for 30 seconds to obtain particles.
(Third step)
Next, the obtained particles are packed into a fluidized bed (product name: Glatt-POWREX, model number FD-WRT-20, manufactured by Paulex Co., Ltd.), and after filling, 15 ° C. wind (air) is placed in the fluidized bed. The particles were cooled to 20 ° C., and particles were cooled.
The air velocity in the fluidized bed was adjusted in the range of 0.2 to 10.0 m / s while confirming the fluidized state.
The obtained particles were classified using a sieve having an opening of 2000 μm to obtain surface-treated inorganic particles (coated sodium carbonate particles) passing through a sieve having an opening of 2000 μm.

Low-substituted cellulose acetate (WSCA): Low-substituted cellulose acetate shown in Table 7 prepared in Synthesis Examples 1 to 12 below.

(WSCA synthesis example 1)
5.1 parts by weight of acetic acid and 2.0 parts by weight with respect to 1 part by weight of cellulose acetate (manufactured by Daicel, trade name “L-50”, acetyl group total substitution degree 2.43, 6% viscosity: 110 mPa · s) A part by weight of water was added and stirred at 40 ° C. for 5 hours to obtain a solution having a uniform appearance. 0.13 parts by weight of sulfuric acid was added to this solution, and the resulting solution was kept at 70 ° C. to carry out hydrolysis (partial deacetylation reaction; aging). In this aging process, water was added to the system twice in the middle. That is, 0.67 parts by weight of water was added 1 hour after the reaction was started, and 1.67 parts by weight of water was added after another 2 hours, and the reaction was further continued for 3 hours. The total hydrolysis time is 6 hours. The first aging from the start of the reaction to the first water addition, the second aging from the first water addition to the second water addition, the reaction from the second water addition to the end of the reaction (ripening completed) This is called the third aging.
After carrying out the hydrolysis, the temperature of the system is cooled to room temperature (about 25 ° C.), and 15 parts by weight of acetone / methanol = 1/2 (weight ratio) mixed solvent (precipitating agent) is added to the reaction mixture to cause precipitation. Was generated.
The precipitate was recovered as a wet cake having a solid content of 15% by weight, and washed by adding 8 parts by weight of methanol and draining to a solid content of 15% by weight. This was repeated three times. The washed precipitate was further washed twice with 8 parts by weight of methanol containing 0.004% by weight of potassium acetate, neutralized and dried to obtain cellulose acetate (low-substituted cellulose acetate; WSCA-70-1. 2) was obtained.

(WSCA Synthesis Examples 2 to 12)
Cellulose acetate (low-substituted cellulose acetate) in the same manner as in Synthesis Example 1 except that the reaction temperature, first aging time, second aging time, third aging time, and precipitating agent were changed as shown in Table 7. Got.

  Acetyl group total substitution degree (DS), weight average polymerization degree (DPw), polydispersity (dispersion degree) (Mw / Mn), and composition distribution index (CDI) of low substituted cellulose acetate obtained in each synthesis example Was measured by the following method. Table 7 shows production conditions and measurement results (analytical values) of physical properties of the obtained low-substituted cellulose acetate. “Sample number” in Table 7 means the sample number of the obtained low-substituted cellulose acetate.

(Measurement of substitution degree (DS))
According to the method of Tezuka (Carbohydr. Res. 273, 83 (1995)), the unsubstituted hydroxyl group of the low-substituted cellulose acetate sample was propionylated. The total substitution degree of acetyl group of propionylated cellulose acetate was determined from 169 to 171 ppm acetylcarbonyl signal and 172 to 174 ppm propionylcarbonyl signal in ¹³ C-NMR according to the method of Tezuka (same).

(Measurement of weight average degree of polymerization (DPw), degree of dispersion (Mw / Mn))
The weight average polymerization degree and dispersion degree of low substituted cellulose acetate were determined by conducting GPC-light scattering measurement under the following conditions after being led to propionylated low substituted cellulose acetate.
Equipment: GPC “SYSTEM-21H” manufactured by Shodex
Solvent: Acetone Column: 2 GMHxl (Tosoh), same guard column Flow rate: 0.8 ml / min
Temperature: 29 ° C
Sample concentration: 0.25% (wt / vol)
Injection volume: 100 μl
Detection: MALLS (multi-angle light scattering detector) (manufactured by Wyatt, “DAWN-EOS”)
MALLS correction standard substance: PMMA (molecular weight 27600)

(Measurement of composition distribution index (CDI))
The CDI of low substituted cellulose acetate was determined by conducting HPLC analysis under the following conditions after leading to propionylated low substituted cellulose acetate.
Equipment: Agilent 1100 Series
Column: Waters Nova-Pak phenyl 60Å 4 μm (150 mm × 3.9 mmΦ) + guard column Column temperature: 30 ° C.
Detection: Varian 380-LC
Injection volume: 5.0 μL (sample concentration: 0.1% (wt / vol))
Eluent: Liquid A: MeOH / H ₂ O = 8/1 (v / v), Liquid B: CHCl ₃ / MeOH = 8/1 (v / v)
Gradient: A / B = 80/20 → 0/100 (28 min); Flow rate: 0.7 mL / min
First, a calibration curve of elution time versus DS was created by HPLC analysis of a sample with known DS in the range of 0 to 3 acetyl DS (acetyl group total substitution degree). Based on the calibration curve, the elution curve (time vs. detected intensity curve) of the unknown sample is converted to the DS vs. detected intensity curve (composition distribution curve), and the uncorrected half-value width X of this composition distribution curve is determined. The corrected half width Z of the distribution was determined.
Z = (X ² −Y ² ) ^1/2
Y is a device constant defined by the following equation.
Y = (a−b) x / 3 + b
a: X value of a sample with acetyl DS = 3 b: X value of a sample with acetyl DS = 0 x: Acetyl DS of unknown sample
From the corrected half width Z, the composition distribution index (CDI) was determined by the following formula.
CDI = Z / Z ₀
Here, Z ₀ is the composition distribution generated when acetylation and partial deacetylation in the preparation of all partially substituted cellulose acetates occur with equal probability for all hydroxyl groups (or acetyl groups) of all molecules. Yes, defined by

[Recontamination evaluation method]
The recontamination property was evaluated by the method described in the examples of JP2009-155560A. That is, in this re-contamination evaluation method, a contamination liquid in which dirt is dispersed in a cleaning liquid is prepared in advance, and the adhesion of the dirt to the evaluation cloth is observed. This ability to suppress the adhesion of dirt to the white cloth (evaluation cloth) is referred to as “recontamination preventing ability”.

(1) Preparation of sebum soil Triolein (Kanto Chemical Co., Ltd.) 49.8 parts by mass, oleic acid (Kanto Chemical Co., Ltd.) 49.7 parts by mass, and carbon 0.5 parts by mass (Asahi Carbon ( Co., Ltd.) was mixed and mixed with an ultrasonic device (UTARP-205, SHARP Co., Ltd.) for 2 minutes, and the resulting mixture was used as a sebum soil component (sebum soil model).

(2) Preparation of evaluation cloth (recontaminated cloth) (i) Cotton (attachment treatment of model accumulated sebum)
Unused cotton cloth is difficult to recontaminate, and the sebum accumulates when worn, increasing the recontamination property. Therefore, when evaluating the re-contamination of the cotton cloth, a wearing cloth was assumed, and a cotton cloth in which sebum was attached to the same level as the wearing cloth was used as an evaluation cloth. That is, a mixture of triolein: tripalmitin: oleic acid: palmitic acid: squalene in a ratio of 30: 30: 15: 15: 10 as a model accumulated sebum soil at a mass ratio of 2.5% with respect to cotton. The adhered material was used as an evaluation cloth.
(Ii) Polyester jersey (polyester)
The unused polyester jersey (manufactured by Tanigami Shoten Co., Ltd.) was used. As pretreatment, commercially available detergent top (made by Lion), fully automatic washing machine (made by Matsushita Electric Industrial Co., Ltd., NA-F70SD1), tap water with a temperature of about 50 ° C. and a hardness of about 3 ° DH Then, a cloth having an amount of 20 times the bath ratio was added, washing was carried out twice on the Omakase Course, and the third time was washed with only tap water without using a detergent, and naturally dried was used as the evaluation cloth.

(3) Recontamination prevention evaluation method (Recontamination evaluation method)
(I) Cotton S. Using a Teg-O-Tometer from Testing, the detergent compositions obtained in the examples and comparative examples were prepared to 667 ppm, and the temperature was 25 ° C. and the hardness was 3 ° DH (calcium chloride was dissolved in ion-exchanged water. Prepared), and after stirring to 900 mL of water, the mixture was stirred at 120 rpm for 1 minute. Immediately after, 63 μL of the sebum soil component prepared in the above (1) was added and stirred at 120 rpm for 1 minute to prepare a detergent composition solution containing the sebum soil component.
To the detergent composition solution, three cotton recontaminated cloths (5 cm × 5 cm) and a cotton charge cloth for increasing the bath ratio of the detergent composition solution to the wash object by 20 times are added, and 120 rpm For 10 minutes. After washing, rinsing was performed for 3 minutes, dehydration was performed for 1 minute, and iron drying was performed.
The whiteness (WB value) of the recontaminated cloth is measured using a color meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the amount of change in whiteness before and after washing is determined by the following formula. This evaluated the recontamination prevention power. The smaller the amount of change in whiteness (ΔWB), the better the recontamination prevention power.
Change amount of whiteness before and after washing (ΔWB) = whiteness of recontaminated cloth before washing (WB) −whiteness of recontaminated cloth after washing (WB)
The evaluation of the recontamination preventive power was performed based on the average value of ΔWB for the three recontaminated cloths. Regarding cotton ΔWB, a value less than 2 is markedly excellent, 2 or more and less than 3 is an excellent result, 3 or more and less than 4 are mediocre results, and 4 or more are judged to be poor results. did.

(Ii) Polyester jersey S. Using a Teg-O-Tometer from Testing, the detergent compositions obtained in the examples and comparative examples were prepared to 667 ppm, and the temperature was 25 ° C. and the hardness was 3 ° DH (calcium chloride was dissolved in ion-exchanged water. Prepared), and after stirring to 900 mL of water, the mixture was stirred at 120 rpm for 1 minute. Immediately after, 63 μL of the sebum soil component prepared in the above (1) was added and stirred at 120 rpm for 1 minute to prepare a detergent composition solution containing the sebum soil component.
To the detergent composition solution, three polyester jersey recontaminated cloths (5 cm × 5 cm) and a cotton charge cloth for increasing the bath ratio of the detergent composition solution and the washing object by 20 times are added, Washed for 10 minutes at 120 rpm. After washing, rinsing was performed for 3 minutes, dehydration was performed for 1 minute, and iron drying was performed.
The whiteness (WB value) of the recontaminated cloth is measured using a color meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the amount of change in whiteness before and after washing is determined by the following formula. This evaluated the recontamination prevention power. The smaller the amount of change in whiteness (ΔWB), the better the recontamination prevention power.
Change amount of whiteness before and after washing (ΔWB) = whiteness of recontaminated cloth before washing (WB) −whiteness of recontaminated cloth after washing (WB)
The evaluation of the recontamination preventive power was performed based on the average value of ΔWB for the three recontaminated cloths. Regarding ΔWB of polyester jersey, 10 or less is a remarkably excellent result, 11 to 15 or less is an excellent result, 16 to 25 or less is a mediocre result, and 26 or more is an inferior result. It was judged.

Table 6 shows the blending amounts of cellulose derivatives (WSCA, HPMC) and AES in the detergent compositions obtained in Examples and Comparative Examples and the results of recontamination evaluation. First, Example 4 (detergent composition containing WSCA-70-0.9) will be described as a representative example of the present invention. In comparison with Comparative Example 2, recontamination to cotton is remarkably suppressed. . The effect of preventing recontamination of the detergent composition of Example 4 is equal to or higher than that when AES is used (Comparative Example 1).
Even when AES is used, if HPMC is not used together, re-contamination of the polyester jersey is significant (Comparative Example 3). On the other hand, when WSCA was used instead of AES (Example 13), it was confirmed that in addition to the effect of preventing recontamination of cotton, the effect of preventing recontamination of polyester jersey was sufficiently obtained.
In addition, from Examples 1-12, it turns out that it is especially preferable from the viewpoint of recontamination prevention property that the acetyl group total substitution degree of WSCA shall be 0.5-1.1. It can be seen that the CDI of WSCA is particularly preferably 2 or less from the viewpoint of recontamination prevention.

  The detergent composition of the present invention includes, for example, a detergent for textile products (for example, a detergent for clothing), a household detergent, an industrial detergent (for example, an industrial detergent used in the textile industry), a hard surface detergent, It can be used in various applications such as detergents used for specific applications such as bleaching detergents and partial washing detergents that enhance one of the components.

Claims (2)

  A detergent composition comprising 0.05 to 20% by mass of cellulose acetate having a total acetyl group substitution degree of 0.4 to 1.2, based on the total amount (100% by mass) of the detergent composition. A detergent composition.   Furthermore, the detergent composition of Claim 1 containing 5-20 mass% of alpha-sulfo fatty-acid alkylester salt and 3-10 mass% of soap on the basis of the whole quantity (100 mass%) of a detergent composition.