JP2014214383A - Fiber product treatment liquid and method of treating fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber product treatment liquid and a method of treating a fiber product which can remove fuzz of a fiber product better.SOLUTION: A fiber product treatment liquid comprises (A) ingredient of an endoglucanase, (B) ingredient of 20-100 mass ppm of one or more selected from calcium ion and magnesium ion and preferably (C1) ingredient of one or more selected from surfactants and silicones. A method of treating a fiber product includes an enzyme treatment step of bringing the fiber product treatment liquid into contact with the fiber product.

Description

  The present invention relates to a textile processing liquid and a textile processing method.

  When a textile product such as clothing is washed, the textile product may become fluffy due to rubbing between textile products that are washing objects. When the fiber product becomes fluffy, the original texture of the fiber product is impaired. For example, when a colored textile product is washed, if the colored textile product becomes fluffy, it tends to appear as faded. In addition, when washing both colored textile products and white textile products, if the white textile products become fluffy and fluffy fibers are missing and adhere to the colored textile products, the appearance of the colored textile products May be damaged.

In order to solve such a problem, a product containing cellulase such as endoglucanase is known as a cleaning agent for removing the fluff generated in the fiber product while washing the fiber product. Cellulase can cut fluff produced in cellulose-containing fibers (for example, cotton, hemp, rayon, or a blended fiber of these with other fibers) to prevent deterioration of the appearance of the fiber product.
As a preparation to remove fluff produced in textile products, a cellulase preparation containing a specific terephthalic acid-alkylene glycol polymer or terephthalic acid-oligoalkylene glycol alone or in combination with an endoglucanase having a cellulose binding domain is proposed. (Patent Document 1). The invention of Patent Document 1 aims to improve the texture of cellulose-containing fibers by increasing endoglucanase activity.

JP 2002-142760 A

However, there is a need for a preparation that can better remove the fluff produced in the textile product (ie, has a high fuzz removal effect).
Then, this invention aims at the textiles processing liquid which can remove the fluff of textiles more favorably.

  As a result of intensive studies, the present inventors have obtained knowledge that fluff produced in a textile product can be better removed by using endoglucanase in water containing a specific metal ion at a specific concentration, The present invention has been reached.

That is, the textile treatment liquid of the present invention contains (A) component: endoglucanase, and (B) component: one or more selected from calcium ions and magnesium ions, 20 to 100 ppm by mass. To do.
Furthermore, it is preferable to contain 1 or more types selected from (C1) component: surfactant and silicone.

The textile product processing method of the present invention is characterized by comprising an enzyme treatment step for bringing the textile product treatment liquid of the present invention into contact with a textile product.
After the enzyme treatment step, the fiber product treated in the enzyme treatment step is added to a treatment liquid that does not contain the component (A) and contains at least one selected from the component (C2): surfactant and silicone. It is preferable to include a dipping step.

  According to the textile treatment liquid of the present invention, the fluff of the textile can be removed better.

(Textile treatment liquid)
The textile treatment liquid of the present invention contains (A) component: endoglucanase and (B) component: one or more selected from calcium ions and magnesium ions.

<(A) component: endoglucanase>
The component (A) is endoglucanase. Endoglucanase is endo-1,4-β-glucanase EC 3.2.1.4, which is a cellulase having an action of hydrolyzing β-1,4-glucopyranosyl bond of β-1,4-glucan. . Component (A) is cellulose, cellulose derivatives (for example, carboxymethylcellulose, hydroxyethylcellulose), lichenin, β-1,4 bond in β-1,3 glucan mixture such as cereal β-D-glucan or xyloglucan And catalyze the internal hydrolysis of other plant materials containing cellulose moieties.

Examples of commercially available products of component (A) include Carezyme 4500L (trade name, manufactured by Novozymes), Carezyme Premium 4500L (trade name, manufactured by Novozymes), Endrase (trade name, manufactured by Novozymes), Cell Clean (product) Name, Novozymes, Inc.), among others, Carezyme 4500L (product name) and Carezyme Premium 4500L (product name) are preferable, and Carezyme Premium 4500L (product name) is more preferable.
(A) A component may be used individually by 1 type and may be used in combination of 2 or more type.

(A) As a component, what has high enzyme activity (vs. non-crystalline activity) with respect to an amorphous cellulose is preferable. It is considered that the fluff produced by friction between fibers has many non-crystalline sites. For this reason, the higher the non-crystalline activity is, the more the fuzz removal effect can be improved.
The non-crystalline activity of the component (A) is preferably 3000 to 9000 units / mL, and more preferably 6000 to 9000 units / mL.
The non-crystalline activity was measured by measuring the Glu-like reducing end produced by the decomposition reaction of phosphoric acid-swelling cellulose, which is an amorphous cellulose, based on the p-hydroxybenzoic acid hydrazine (PAHBAH) method. It is a value calculated from the reducing end amount.

In addition, the ratio ([crystal] / [non-crystal] activity ratio) represented by [enzyme activity for crystalline cellulose (vs. crystal activity)] / [vs. 0.3 is preferable, and 0.05 to 0.1 is more preferable. Removal of fluff requires a certain degree of crystalline decomposition as well as non-crystalline decomposition. When the [crystal] / [non-crystal] activity ratio exceeds the above upper limit value, it is easier to promote the degradation of the fiber product than the fuzz removal effect. If it is less than the lower limit, decomposition of only the non-crystalline fluff is promoted, and the fluff crystalline remains. For this reason, the strength of the fluff is maintained, and the effect of removing the fluff tends to decrease. By setting the [crystal] / [non-crystal] activity ratio within the above range, it is possible to better prevent the fiber product from deteriorating while exhibiting a better fuzz removal effect.
Examples of the component (A) having a [crystal] / [non-crystal] activity ratio of 0.05 to 0.1 include Carezyme 4500L, Carezyme Premium 4500L, and the like.

  The anti-crystal activity was calculated from the measured amount of Glu-like reducing terminal by measuring the Glu-like reducing terminal produced by the decomposition reaction of crystalline cellulose based on the p-hydroxybenzoic acid hydrazine (PAHBAH) method. Value.

The content of the component (A) in the textile treatment liquid is determined, for example, according to the amount of the textile product to be treated. For example, 130,000 to 1,400,000 units per 1 kg of the treatment target. Preferably, 200,000 to 1,100,000 units are more preferable, and 275,000 to 550,000 units are more preferable. If the amount is less than the lower limit, the fluff removing effect may be reduced, and even if the amount exceeds the upper limit, improvement in the fluff removing effect commensurate with it may not be seen, and the textile product may be deteriorated, which is economically disadvantageous. Become.
For example, in a domestic drum-type washing machine (capacity 7 kg), the amount of textile products to be treated is 1 to 3 kg, and the necessary textile product treatment liquid is 8 to 12 L. In a vertical washing machine for home use (capacity 7 kg), the amount of the textile product to be treated is 1 to 3 kg, and the necessary textile product treatment liquid is 15 to 45 L. In a commercial drum-type washing machine (capacity 27 kg), the amount of the textile product to be treated is 15 kg, and the necessary textile treatment liquid is 60 to 90 L.
Therefore, the concentration of the component (A) in the textile treatment liquid is preferably 15,000 to 350,000 units / L, more preferably 22,000 to 300,000 units / L, and 35,000 to 150,000 units / L. Is more preferable.
The unit “unit” of the component (A) content and concentration is non-crystalline activity.

<(B) component: 1 or more types selected from calcium ion and magnesium ion>
The component (B) is at least one selected from calcium ions and magnesium ions. (B) component raises the activity of (A) component and can raise the fluff removal effect of a textiles processing liquid more.
Examples of the supply source of calcium ions include water-soluble calcium compounds containing calcium such as calcium chloride, calcium sulfate, calcium acetate, and calcium oxalate, and water containing calcium ions at a high concentration.
Examples of the supply source of magnesium ions include water-soluble magnesium compounds such as magnesium chloride and magnesium sulfate, and water containing magnesium ions at a high concentration.
The supply source of these (B) components may be used individually by 1 type, and 2 or more types may be used in combination.

The lower limit of the concentration of the component (B) in the textile treatment liquid is 20 ppm by mass or more, preferably 30 ppm by mass or more, more preferably 40 ppm by mass or more, and further preferably 50 ppm by mass or more. If the amount is less than the above lower limit, the fluff removal effect cannot be improved.
The upper limit of the concentration of the component (B) in the textile treatment liquid is 100 ppm by mass or less, preferably 90 ppm by mass or less, more preferably 80 ppm by mass or less, and further preferably 70 ppm by mass or less. Above the upper limit, the effect of removing fuzz may be reduced due to inhibition of binding of the component (A) to the fiber, a decrease in reaction rate due to a decrease in the flexibility of the enzyme molecule, aggregation of the component (A), and the like.

  In the textile treatment liquid, the ratio represented by [(B) component concentration (mass ppm)] / [(A) component concentration (unit / L)] (hereinafter sometimes referred to as B / A ratio) is 0.0002 to 0.0019 is preferred, 0.0006 to 0.0017 is more preferred, and 0.0008 to 0.0014 is even more preferred. If the amount is less than the lower limit, the fluff removal effect cannot be improved, and even if the upper limit is exceeded, the fluff removal effect cannot be further improved, which is economically undesirable.

The concentration of calcium ions in the textile treatment liquid is measured, for example, by the following method. A standard curve is prepared by measuring a potential of a calcium ion standard solution having a predetermined concentration using a calcium electrode (Orion 9720BNWP). The potential of the textile treatment liquid is measured using a calcium electrode, and calculated from the obtained value and the calibration curve.
In addition, when the fiber product treatment liquid contains an ion scavenger such as a chelating agent, the calcium ion concentration of the fiber product treatment liquid containing the ion scavenger is measured.

  The concentration of magnesium ions in the textile treatment liquid is calculated from, for example, a potential measured using a magnesium electrode (DX224-Mg of METLER TOLEDO) and a calibration curve prepared in advance using a magnesium ion standard solution. The

<(C1) component: one or more selected from surfactant and silicone>
The textile treatment liquid may contain one or more selected from (C1) component: surfactant and silicone. By containing the component (C1), it becomes easy for the fiber product treatment liquid to penetrate into the inside of the cellulose-containing fiber (permeation promoting effect), and the fluff cut by the component (A) is quickly put into the fiber product treatment solution. It is possible to suppress dispersion and distribution of the dispersed fluff on the textile product (fuzz adhesion suppression effect).

≪Surfactant≫
As the component (C1) surfactant, any surfactant may be used as long as it has been conventionally used for detergents for textile products. For example, nonionic surfactants, anionic surfactants, and cationic interfaces. Examples of the surfactant include amphoteric surfactants and amphoteric surfactants. Among them, nonionic surfactants are preferable. By using a nonionic surfactant, the penetration promoting effect can be further enhanced and the fuzz removal effect can be further improved.

  The nonionic surfactant is not particularly limited, and for example, a polyoxyalkylene type nonionic surfactant represented by the following general formula (1) is preferably used.

^{_{R 1 -X- (EO) n (}} PO) m -R 2 ··· (1)

(1) In the formula, R ¹ is a hydrocarbon group.
R ¹ has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. When the carbon number is within the above range, the fuzz removal effect and the fuzz adhesion suppression effect can be further enhanced.
R ¹ may or may not have an unsaturated bond.
R ¹ is preferably an alkyl group or an alkenyl group.
R ¹ may be linear or branched, and is preferably branched.
Examples of R ¹ include hydrocarbon groups derived from primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.

R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.
When R ² is an alkyl group, the carbon number of ^{R 2} is from 1 to 3 are preferred.
When R ² is an alkenyl group, R ² has preferably 2 to 3 carbon atoms.

X is a functional group such as O, COO, or CONH.
In the formula (1), when X is O, the nonionic surfactant represented by the formula (1) is an alcohol type nonionic surfactant.
When X is O, R ¹ is a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched carbon number from the viewpoint of further improving the fluff removing effect and the fuzz adhesion inhibiting effect. A 10-20 alkenyl group is preferable, and a linear or branched alkyl group having 10 to 18 carbon atoms or a linear or branched alkenyl group having 10 to 18 carbon atoms is more preferable. When X is O, R ² is preferably a hydrogen atom.

In the formula (1), when X is COO, the nonionic surfactant represented by the formula (1) is a fatty acid ester type nonionic surfactant. When X is COO, R ¹ is a linear or branched alkyl group having 9 to 21 carbon atoms, or a linear or branched carbon number from the viewpoint of further improving the fuzz removal effect and the fuzz adhesion suppression effect. A 9-21 alkenyl group is preferable, and a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms is more preferable. When X is COO, R ² is preferably an alkyl group having 1 to 3 carbon atoms.

(1) In the formula, EO represents an oxyethylene group, and PO represents an oxypropylene group.
n is a number of 3 to 20 representing the average number of EO repeats (that is, the average number of moles of ethylene oxide added), and a number of 5 to 18 is preferred. When n exceeds the above upper limit value, the HLB value becomes too high and the fuzz removal effect and the fuzz adhesion suppression effect tend to decrease. If n is less than the above lower limit value, the odor tends to deteriorate.
m is a number from 0 to 6 representing the average number of repeating POs (that is, the average number of moles of propylene oxide added), and a number from 0 to 3 is preferred.
EO and PO may be mixed and arranged, and EO and PO may be added randomly or may be added in blocks.

In the nonionic surfactant represented by the formula (1), the distribution of the number of repetitions of EO or PO is not particularly limited and is likely to vary depending on the reaction method during production.
The distribution of the number of repetitions of EO or PO is, for example, ethylene oxide or propylene oxide as a raw material (primary or secondary higher alcohol, higher fatty acid, higher fatty acid, using a common alkali catalyst such as sodium hydroxide or potassium hydroxide. When added to a fatty acid amide or the like, the distribution tends to be relatively wide.
The distribution of the number of repetitions of EO or PO is, for example, metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ described in JP-B-615038. When ethylene oxide or propylene oxide is added to the raw material using a specific alkoxylation catalyst such as added magnesium oxide, the distribution tends to be relatively narrow.

  Examples of the nonionic surfactant represented by the formula (1) include, for example, Diadol (trade name, C13 (C represents the number of carbon atoms; the same shall apply hereinafter) manufactured by Mitsubishi Chemical Corporation) and Neodol manufactured by Shell. (Trade name, a mixture of C12 and C13), an alcohol such as Safol 23 (trade name, a mixture of C12 and C13) manufactured by Sasol, or the like, with 12 mol equivalent or 15 mol equivalent ethylene oxide added; C12 obtained by trimerizing butene with 12 mole equivalent or 15 mole equivalent ethylene oxide added to natural alcohol such as CO-1214 or CO-1270 (trade name) manufactured by Procter & Gamble Co. A product obtained by adding 7 moles of ethylene oxide to a C13 alcohol obtained by subjecting an alkene to an oxo process (quotient) Name: Lutensol TO7, manufactured by BASF); 9 mole equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name: Lutensol XP90, manufactured by BASF); What added 7 mol of ethylene oxide to C10 alcohol obtained by subjecting to gerbet reaction (trade name: Lutensol XL70, manufactured by BASF); to C10 alcohol obtained by subjecting pentanol to gerbet reaction, 6 mole equivalent of ethylene oxide added (trade name: Lutensol XA60, manufactured by BASF); 9 mole equivalent, 12 mole equivalent or 15 mole equivalent ethylene oxide added to secondary alcohol having 12 to 14 carbon atoms (Product name : Softanol 90, Softanol 120, Softanol 150, manufactured by Nippon Shokubai Co., Ltd .; 15 mol equivalent of ethylene oxide was added to palm fatty acid methyl (lauric acid / myristic acid = 8/2) using an alkoxylation catalyst. (Polyoxyethylene coconut fatty acid methyl ester (EO 15 mol)) and the like.

Nonionic surfactants other than the above include, for example, alkylene oxide adducts such as alkylphenols and higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylenes thereof. Examples include oxide adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, hydrogenated castor oil alkylene oxide adducts, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, and the like.
These nonionic surfactants may be used singly or in combination of two or more.

The anionic surfactant is not particularly limited. For example, α-sulfo fatty acid ester salt, alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt, higher fatty acid salt, α-olefin sulfonate (AOS), direct Alkyl sulfate ester salt having chain or branched chain, alkane sulfonate having alkyl group, alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkylamide ether carboxylate or alkenylamide ether carboxylate, acylaminocarboxyl Carboxylic acid types such as acid salts, phosphoric acid ester type anions such as alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phenyl phosphoric acid ester salts, glycerin fatty acid ester monophosphoric acid ester salts Surfactants, linear alkylbenzene sulfonic acids or salts thereof, and the like.
These anionic surfactants may be used alone or in a combination of two or more.

  The salt constituting the above-mentioned anionic surfactant is not particularly limited, and examples thereof include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolamine and diethanolamine Etc.

As the α-sulfo fatty acid ester salt, for example, those having 10 to 20 carbon atoms are preferable.
Examples of the alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt include a linear or branched alkyl group having 10 to 20 carbon atoms or a linear or branched alkenyl group having 10 to 20 carbon atoms, and an average What added 1 mol-10 mol ethylene oxide (namely, polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferable.
Examples of higher fatty acid salts include salts of single fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid and oleic acid, and mixed fatty acid salts such as coconut oil fatty acid and bovine fatty acid. Can be mentioned. Examples of the salt constituting the higher fatty acid salt include alkali metal salts such as sodium and potassium, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, 2-amino-2-methylpropanol and 2-amino-2- Examples include alkanolamine salts such as methylpropanediol; basic amino acid salts such as lysine and arginine. The higher fatty acid salt is not necessarily added as a salt to the fiber product treatment liquid, and the higher fatty acid and the base may be added separately to form a fatty acid salt in the fiber product treatment liquid.
As an alpha olefin sulfonate, a C10-C20 thing is preferable, for example.
As an alkyl sulfate ester salt, a C10-C20 thing is preferable, for example.
As the alkane sulfonate, for example, a secondary alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms is preferable.
As a linear alkylbenzenesulfonic acid or its salt, a C8-C16 thing is preferable, for example, and a C10-C14 thing is more preferable.
Among the anionic surfactants described above, α-sulfo fatty acid ester salts, α-olefin sulfonic acid salts and alkyl ether sulfate ester salts are preferable, and α-sulfo fatty acid ester salts are more preferable.

The cationic surfactant is not particularly limited, and examples thereof include aliphatic amines or quaternary ammonium salts thereof, fatty acid amidoamine salts, alkyltrialkylene glycol ammonium salts, acylguanidine derivatives, and mono-N-long chain acyl basicity. Examples include amino acid-based cationic surfactants such as amino acid lower alkyl ester salts, alkylbenzalkonium salts, alkylpyridinium salts, imidazolinium salts, and the like.
These cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of amphoteric surfactants are not particularly limited, for example, alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, or Examples include amphoteric surfactants such as phosphoric acid type.
These amphoteric surfactants may be used alone or in combination of two or more.

≪Silicone≫
The silicone as the component (C1) is not particularly limited as long as it is conventionally used as a detergent for textile products, and examples thereof include amino-modified silicone, polyether-modified silicone, and carboxy-modified silicone. .
The amino-modified silicone is not particularly limited as long as it is a silicone having at least an amino group as a functional group. Commercially available products include SF-8417, BY16-871, BY16-853U, FZ-3705, BY16-849, FZ-3785, BY16-890, BY16-208, manufactured by Toray Dow Corning Co., Ltd. BY16-893, FZ-3789, BY16-878, BY16-891 (all are trade names) and the like.
The polyether-modified silicone is not particularly limited as long as it has at least a polyether group (such as a polyoxyethylene group or a polyoxypropylene group) as a functional group. Commercially available products include SH3775M, SH3772M, SH3749, SF8410, SH8700, BY22-008, SF8421, SILWET L-7601, SILWET L-7002, SILWET L-7602, SILWET manufactured by Toray Dow Corning Co., Ltd. L-7604, SILWET FZ-2104, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-009S09, ABN -F1-009-54, ABN SILWET FZ-2222 (all are trade names); KF352A, KF6008, KF615A, K manufactured by Shin-Etsu Chemical Co., Ltd. 6016KF6017 (trade names); GE Toshiba Silicones Co., Ltd. TSF4450, TSF4452 (trade names), and the like.
The carboxy-modified silicone is not particularly limited as long as it is a silicone having at least a carboxy group as a functional group. Examples of commercially available products include BY16-880 (trade name) manufactured by Toray Dow Corning Co., Ltd.
These silicones may be used alone or in combination of two or more.

  The concentration of the component (C1) in the textile treatment liquid is determined in consideration of the type of the component (C1) and the like. For example, the concentration is preferably 20 mass ppm or more, more preferably 20 to 1000 mass ppm, and more preferably 50 to 500 mass. More preferred is ppm. If it is above the above lower limit value, the effect of promoting the penetration of the textile treatment liquid into the textile can be further enhanced, and the fluff cut by the component (A) can be well dispersed in the textile treatment liquid. It is possible to satisfactorily prevent the fluff from adhering to the textile product. Even if it exceeds the above upper limit value, the improvement of the fuzz removal effect and the fuzz adhesion suppression effect corresponding to it is not seen, which is disadvantageous economically. In addition, when a washing machine is used in the enzyme treatment step described later, if the amount exceeds the upper limit, foaming of the fiber product treatment liquid increases, the shearing force to the treatment target is reduced, and the fuzz removal effect may be reduced. .

  When the textile treatment liquid contains the component (C1), the mass ratio represented by the component (C1) / component (B) (hereinafter sometimes referred to as C1 / B ratio) is preferably 0.4 to 16. 1.5 to 15 is more preferable, and 2 to 5 is more preferable. When the C1 / B ratio exceeds the above upper limit, the content of the component (C1) becomes too large, and the component (A) becomes difficult to bind to the treatment target, or the component (A) is processed from the fiber product to the fiber product. There is a possibility that the fluff removal effect is lowered due to easy detachment into the liquid. If it is less than the lower limit, the component (C1) becomes too small, and the effect of promoting the penetration of the fiber product treatment liquid into the fiber product, the effect of dispersing the fluff, and the effect of preventing the reattachment of the fluff may be reduced.

<Optional component>
The textile treatment liquid may contain the following optional components in addition to the component (A), the component (B), and the component (C1).
For example, in order to provide other functions such as flexibility and stability improvement, for example, polymers such as cationized cellulose, monoethanolamine, diethanolamine, triethanolamine, N-methyl-diethanolamine, N, N-dimethylmono Alkali builders such as ethanolamine, etc., pH adjusters, hydrotropes, fluorescent agents, enzymes, dye transfer inhibitors, recontamination inhibitors (eg, polyvinylpyrrolidone, carboxymethylcellulose, etc.), pearl agents, soil release agents, etc. Is mentioned.

Examples of the thickener or solubilizer include monohydric alcohols having 2 to 4 carbon atoms such as ethanol, 1-propanol, 2-propanol, and 1-butanol; carbon such as ethylene glycol, propylene glycol, butylene glycol, and glycerin. Polyhydric alcohols of 2 to 4; glycols such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol, tetraethylene glycol Ether solvents; glycols such as polyethylene glycol having an average molecular weight of about 200 to 5000, p-toluenesulfonic acid, cumenesulfonic acid , (There is also an effect as antiseptics) benzoate, urea and the like.
The content of the viscosity reducing agent or soluble additive in the textile processing liquid is, for example, 0.01 to 15% by mass.

Examples of the metal scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like.
The content of the metal scavenger in the textile treatment liquid is, for example, 0.1 to 20% by mass.

  Examples of the antioxidant include butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogen sulfite. The content of the antioxidant in the textile treatment liquid is, for example, 0.01 to 2% by mass.

  Examples of antiseptics include Caisson CG (trade name) manufactured by Rohm and Haas. Content of the antiseptic | preservative in a textiles processing liquid shall be 0.001-1 mass%, for example.

The textile treatment liquid can contain an enzyme (arbitrary enzyme) other than the component (A). Examples of the optional enzyme include protease, amylase, lipase, mannanase and the like.
As proteases, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type 2.5, Eraase Ultra 16L, Esperase 2.5L, Esperase 2.5L, Esperase 2.5L, Esperase L , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, trade names available from Genencor, Inc., Purefect L, Purefect OX, Properase L, and the like.
As amylases, trade names such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, trade names available from Genencore Co., Ltd. And trade name DB-250 available from Seikagaku Corporation.
Examples of the lipase include trade names Lipex 100L and Lipolase 100L, which are available from Novozymes as lipase preparations.
Examples of mannanases include Mannaway 4L, which is a mannanase preparation available from Novozymes.
Arbitrary enzymes may be used individually by 1 type, and 2 or more types may be used in combination.

Examples of the flavoring agent include fragrance compositions described in JP-A No. 2002-146399 and JP-A No. 2009-108248.
A flavoring agent may be used individually by 1 type, and 2 or more types may be used in combination.
Content of the flavoring agent in a textiles processing liquid shall be 0.1-3 mass%, for example.

General-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR (all trade names) Is mentioned.
A colorant may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Examples of such emulsions include polystyrene emulsions (trade name: Cybinol RPX-196 PE-3, solid content 40% by mass, manufactured by Syden Chemical Co., Ltd.).
One type of emulsion may be used alone, or two or more types may be used in combination.

Extracts include Inuenju, waurushi, echinacea, koganebana, yellowfin, yellow spider, allspice, oregano, enju, chamomile, honeysuckle, clara, keigai, kei, bay geese, honoki, burdock, comfrey, ginger, firewood, ginger, ginger, Black-tailed millet, elderberry, sage, mistletoe, white-faced quake, thyme, flowering dragonfly, clove, shrimp mandarin, tea tree, barberry, wolfberry, nanten, niyu-ko, yorogisa, shirogaya, bow-fuu, dutch sunbill, hop, honshitan, mountain grape, sunflower Wild mint, cedar, yamakiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsam, haxen Kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, plant extracts such as St. John's Wort.
An extract may be used individually by 1 type, and 2 or more types may be used in combination.

  The fiber product treatment liquid preferably has a pH (25 ° C.) of 4 to 9, and more preferably a pH of 5 to 8. When the pH is 4 to 9, the activity of the component (A) can be increased, and the effect on the fiber product can be reduced as much as possible while further improving the fuzz removal effect.

The pH of the textile treatment liquid can be adjusted with a pH adjuster. Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide, alkanolamine and ammonia. Of these, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid and sodium hydroxide are preferable.
A pH adjuster may be used individually by 1 type, and 2 or more types may be used in combination. For example, after adjusting the pH by adding a certain amount of sulfuric acid, sodium hydroxide or the like, an inorganic acid (preferably hydrochloric acid, sulfuric acid) or potassium hydroxide may be further added for fine adjustment of the pH. .
In the present specification, the pH indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.), etc., with the measurement target being 25 ° C.

<Manufacturing method of textile processing liquid>
The textile treatment liquid is produced according to a conventionally known method for producing a liquid detergent or the like. Examples of the method for producing the textile treatment liquid include a method in which the components (A) to (B) and other components as necessary are dispersed in water so that each has an arbitrary concentration.
Alternatively, the components (A) to (B) and other components as necessary are dispersed in water to prepare a concentrated solution containing each component at a high concentration. The method of diluting with water is mentioned so that it may become -100 mass ppm.

(Processing method for textile products)
The textile product processing method of the present invention includes an enzyme treatment step of bringing the textile product treatment liquid of the present invention into contact with the textile product.

  The enzyme treatment step is a step of bringing the fiber product treatment liquid into contact with the fiber product to be treated. By bringing the fiber product treatment liquid into contact with the fiber product, the component (A) cuts the fluff produced in the fiber product and removes the fluff.

  The type of the fiber product is not particularly limited, but includes, for example, a fiber product made of cellulose or a mixed fiber thereof (sometimes referred to as a cellulose-containing fiber), cellulose-containing fiber, and cellulose. A fiber product or the like containing no fibers is preferred. That is, the present invention is suitable for fiber products containing cellulose-containing fibers.

  Examples of the method of bringing the fiber product treatment liquid into contact with the fiber product include a method of immersing the fiber product in the fiber product treatment liquid (immersion method), a method of applying the fiber product treatment liquid to the fiber product (application method), and the like. Of these, the dipping method is preferred. With the dipping method, the fluff can be removed in a shorter time and better.

In the dipping method, it is preferable to stir the fiber product treatment liquid in which the fiber product is dipped (immersion stirring method). By stirring the fiber product treatment liquid, shearing force can be applied to the fluff and the fluff can be more easily cut.
Examples of the immersion stirring method include a method of stirring a textile treatment liquid in which a treatment target is immersed using a washing machine.
The washing machine used for the immersion stirring method may be either a drum washing machine or a vertical washing machine, and a drum washing machine is preferred. If it is a drum type washing machine, during an enzyme treatment process, it can prevent that a new fluff arises in a candidate for processing, and a shear force suitable for cutting a fluff is given.

In the dipping method, the mass ratio (enzyme treatment bath ratio) represented by the fiber product treatment liquid / fiber product is determined in consideration of the content of the component (A) in the fiber product treatment liquid and the equipment used, For example, 2-40 are preferable.
For example, when a drum type washing machine is used, an enzyme treatment bath ratio of 2 to 20 is preferable, and an enzyme treatment bath ratio of 2.5 to 7.5 is more preferable. If it is more than the said lower limit, a textiles processing liquid will spread over the whole process target, and it will be easier to improve a fluff removal effect. If it is below the above upper limit value, the shearing force to the fluff is good, and the effect of removing the fluff is easier to enhance.
In addition, for example, when a vertical washing machine is used, an enzyme treatment bath ratio of 10 to 40 is preferable, and an enzyme treatment bath ratio of 15 to 30 is more preferable. If it is more than the said lower limit, the shear force to a fluff is favorable and it is easy to raise a fluff removal effect more. Even if it exceeds the upper limit, it is difficult to further improve the shearing force on the fluff.

  The temperature of the textile treatment liquid in the dipping method is determined in consideration of the type of the component (A) and the like, for example, preferably 10 to 60 ° C, more preferably 30 to 50 ° C. If it is less than the said lower limit, there exists a possibility that the activity of (A) component may fall and the fuzz removal effect may fall. If it exceeds the above upper limit, the component (A) tends to be deactivated, and the fuzz removal effect may be reduced.

  The time of the enzyme treatment step is determined in consideration of the type of component (A), the contact method, and the like, and is preferably 5 to 120 minutes, and more preferably 10 to 60 minutes, for example.

The enzyme treatment step may be repeated twice or more by replacing the textile treatment liquid.
In the enzyme treatment step, the components (A) and (B) are dispersed in water, the fiber product is immersed in the solution for an arbitrary time, and then the component (C1) is dispersed in the fiber product treatment liquid, It may be immersed.

After the enzyme treatment step, the step of immersing the fiber product in a treatment liquid (secondary treatment liquid) that does not contain the component (A) and contains at least one selected from the component (C2): surfactant and silicone. (Secondary treatment step) may be provided. By providing the secondary treatment process, the fluff cut from the fiber product is dispersed in the secondary treatment liquid, the fluff adhering to the fiber product is removed, and the fluff adheres to the fiber product is better. Can be prevented.
When the secondary treatment step is provided, the textile treatment liquid used in the enzyme treatment step may or may not contain the component (C1).
In the enzyme treatment step, when a fiber product treatment liquid not containing the component (C1) is used, or when a coating method is used, a secondary treatment step is preferably provided.
When the textile treatment liquid containing the component (C1) is used in the enzyme treatment step and the dipping method is used, the secondary treatment step may not be provided. However, in order to better remove the fluff adhering to the textile product, it is preferable to include a secondary treatment step.

As the secondary treatment step, the immersion stirring method is preferable as in the enzyme treatment step.
In the secondary treatment step, the mass ratio (secondary treatment bath ratio) represented by the secondary treatment liquid / fiber product is preferably, for example, 3 to 50, and more preferably 5 to 30. If the secondary treatment bath ratio is less than the above lower limit value, the fluff removal effect and the fluff adhesion suppression effect may be reduced, and even if the upper limit value is exceeded, the fluff removal effect and the fluff adhesion suppression effect may not be further improved. .

The component (C2) is the same as the component (C1). The component (C2) may be the same as or different from the component (C1).
As the component (C2), an anionic surfactant is preferable. By using an anionic surfactant as the component (C2), the fluff that has been cleaved in the enzyme treatment step and then adhered to the treatment target can be favorably dispersed in the secondary treatment liquid, so that the fuzz removal effect can be further improved. .
The concentration of the component (C2) in the secondary treatment liquid is the same as the concentration of the component (C1) in the textile treatment liquid.

  The secondary treatment solution may or may not contain the component (B). However, if a large amount of the component (B) is attached to the fiber product, the flexibility of the fiber product is impaired. For this reason, the concentration of the component (B) in the secondary treatment liquid is preferably 20 ppm by mass or less, more preferably 10 ppm by mass or less, and the secondary treatment liquid may contain substantially no component (B). Further preferred.

The secondary treatment liquid may contain an optional component other than the component (C2).
The optional component in the secondary treatment liquid is the same as the optional component in the textile treatment liquid.

  The secondary treatment step may be repeated twice or more by replacing the secondary treatment liquid.

  A rinsing step of rinsing the fiber product with water may be provided after or both of the enzyme treatment step and the secondary treatment step. By providing the rinsing step, the fiber product treatment liquid adhering to the fiber product can be removed.

  The fiber product processed by the fiber product processing method of the present embodiment may be processed in another processing step (for example, a step of processing with a softening agent) or may be dried.

  As above-mentioned, since the textiles processing liquid of this invention contains (A) component and (B) component of a specific density | concentration, the fluff produced in the textiles can be removed more favorably.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
<(A) component>
A-1: Carezyme Premium 4500L (trade name, versus non-crystalline activity = 88800 units / mL, [crystal] / [non-crystal] activity ratio: 0.072, manufactured by Novozymes).
A-2: Carezyme 4500L (trade name, vs. non-crystal activity = 73200 units / mL, [crystal] / [non-crystal] activity ratio: 0.074, manufactured by Novozymes).
A-3: Endolase (trade name, versus non-crystal activity = 54100 units / mL, [crystal] / [non-crystal] activity ratio: 0.175, manufactured by Novozymes).
A-4: Cell Clean (trade name, versus non-crystalline activity = 34900 units / mL, [crystal] / [non-crystal] activity ratio: 0.219, manufactured by Novozymes).

<(B) component>
B-1: Calcium chloride (anhydrous) (manufactured by Junsei Chemical Co., Ltd.).
B-2: Magnesium chloride (hexahydrate) (manufactured by Junsei Co., Ltd.).
B-3: Iron chloride (II) (tetrahydrate) (manufactured by Junsei Chemical Co., Ltd.) ... Comparative product of component (B).

<(C1) component and (C2) component>
C-1: LMAO (POEAE (EO 15 mol)). An average of 15 moles of ethylene oxide added to natural alcohol CO-1270 manufactured by Procter & Gamble. Synthesized by the following synthesis method.

<Method for synthesizing C-1>
224.4 g of natural alcohol CO-1270 and 2.0 g of 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. After dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the reaction solution, 760.4 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, the addition rate was adjusted using a blowing tube so that the reaction temperature did not exceed 180 ° C.
After completion of the addition of ethylene oxide, after aging at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes to obtain C-1. It was.

  C-2: LMAL (POEAE (EO 12 mol)). An average of 12 moles of ethylene oxide added to natural alcohol CO-1270 manufactured by Procter & Gamble. Synthesized by the following synthesis method.

≪Synthesis method of C-2≫
C-2 was obtained in the same manner as C-1, except that ethylene oxide was changed to 610.2 g.

C-3: MEE. A mixture of 8 parts by weight of C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) _m OCH ₃ and 2 parts by weight of C ₁₃ H ₂₇ CO (OCH ₂ CH ₂ ) _m OCH ₃ . m = average 15, narrow ratio 33% by mass. Synthesized by the following synthesis method.

<< Synthesis Method of C-3 >>
A synthetic product produced according to Production Example 1 in the examples described in JP-A No. 2000-144179 was used.
Alumina / magnesium hydroxide (commercial name: Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO.Al ₂ O ₃ · wH ₂ O was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere. The obtained calcined alumina / magnesium hydroxide (unmodified) catalyst was obtained. A 4 L autoclave was charged with 2.2 g of calcined alumina hydroxide / magnesium catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, and the catalyst was modified in the autoclave. Done quality. Next, after the inside of the autoclave was replaced with nitrogen, 1052 g of ethylene oxide was introduced while the temperature was maintained at 180 ° C. and the pressure was maintained at 3 atm (0.3 MPa), and the reaction was performed while stirring.
The obtained reaction liquid was cooled to 80 ° C., and after adding 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids, the catalyst and filter aid were filtered off to obtain C-3. The narrow rate of C-3 was 33% by mass.
The narrow rate indicates the proportion of the distribution of the alkylene oxide adduct, and is a value obtained by the method described in JP 2011-137112 A.

C-4: TAG. An average of 7 moles of ethylene oxide adduct of isotridecyl alcohol (C ₁₁ H ₂₃ O (CH ₂ CH ₂ O) ₇ H). Product name: Lutensol TO-7 (manufactured by BASF).

  C-5: POE. Polyoxyethylene alkyl ether (C12-14 secondary alcohol), a branched secondary alcohol having 10 to 14 carbon atoms added with an average of 12 moles of ethylene oxide. Softanol 120 (trade name, manufactured by Nippon Shokubai Co., Ltd.).

  C-6: LAS-Na. Linear alkyl (C10-14) sodium benzenesulfonate. Raipon LS-250 (trade name, pure 50% by mass, pH (1% by mass aq) 7-8, manufactured by Lion Corporation).

C-7: MES. A mixture of 8 parts by weight of C ₁₄ H ₂₉ —CH (SO ₃ Na) —COOCH ₃ and 2 parts by weight of C ₁₆ H ₃₃ —CH (SO ₃ Na) —COOCH ₃ . Synthesized by the following synthesis method.

<< Synthesis Method of C-7 >>
(1) Synthesis of C ₁₄ H ₂₉ —CH (SO ₃ Na) —COOCH ₃ (α-sulfopalmitic acid methyl ester sodium salt) 1 L of 4 equipped with a thermometer, stirrer, dropping funnel and calcium chloride tube for drying In a neck flask, 68 g of palmitic acid methyl ester (product name: Pastel M-16, manufactured by Lion Corporation) and 540 g of carbon tetrachloride were charged. 24 g of sulfuric anhydride (manufactured by Nisso Metal Chemical Co., Ltd., trade name Nisso Sulfan) was added dropwise while maintaining the reaction temperature at 10 to 15 ° C.
After the sulfuric anhydride was added dropwise, the mixture was stirred at reflux for 3 hours.
Next, after distilling off the reaction solvent (carbon tetrachloride) at 50 ° C. in a water bath using an evaporator, 500 mL of methanol (manufactured by Kanto Chemical Co., Inc.) was added and stirred at reflux for 20 minutes. Then, the reaction liquid was adjusted to pH 7 using 20 mass% sodium hydroxide aqueous solution. The reaction solvent (methanol) was distilled off under reduced pressure. At this time, isopropanol was added, and water was also distilled off azeotropically.
The residue (crude product) was added to a mixed solution of ethanol and water (ethanol / water = 9/1 (volume ratio)) and dissolved by heating to 50 to 60 ° C. to remove insoluble matters. The filtrate was cooled to 5 ° C. and recrystallized, and then the precipitate was separated by filtration and vacuum dried to obtain α-sulfopalmitic acid methyl ester sodium salt (C16MES).

(2) Synthesis of C ₁₆ H ₃₃ —CH (SO ₃ Na) —COOCH ₃ (α-sulfostearic acid methyl ester sodium salt) Palmitic acid methyl ester (product name: Pastel M-16, manufactured by Lion Corporation) was changed to 68 g. The methyl α-sulfostearate was synthesized by the same synthesis method as that of the above-mentioned α-sulfopalmitic acid methyl ester sodium salt, except that 75 g of stearic acid methyl ester (product name: Pastel M-18, manufactured by Lion Corporation) was used. An ester sodium salt (C18MES) was obtained.

  (3) C16MES and C18MES obtained by the above synthesis method were mixed at a mass ratio of 8: 2 to obtain C-7.

  C-8: AES. Sodium polyoxyethylene alkyl ether sulfate having 12 to 13 carbon atoms (average added mole number of ethylene oxide: 2). Synthesized by the following synthesis method.

<< Synthesis Method of C-8 >>
In a 4 L autoclave, Neodol 23 (trade name, manufactured by Shell Chemicals Co., Ltd., C12, 13 alcohol (mixture having a mass ratio of 1/1 carbon to 13 carbon), branching rate of 20 mass. %) 400 g and potassium hydroxide catalyst 0.8 g were charged, the inside of the autoclave was purged with nitrogen, and the temperature was increased while stirring. Thereafter, 272 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure of 0.3 MPa to obtain a reaction product (alcohol ethoxylate) having an average addition mole number of ethylene oxide of 2.
280 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 67 g of liquid sulfuric anhydride (sulfane) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After the dropwise addition of liquid sulfuric anhydride, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. This was neutralized with an aqueous sodium hydroxide solution to obtain C-8. In the total ethylene oxide adduct constituting C-8, the total proportion of ethylene oxide adducts having 1 to 3 mol of ethylene oxide added was 35% by mass.

C-9: C12 cation ^{_{(C z H 2z + 1 N}} + (CH 3) 3 Cl - (z = 12)). Arcard 12-37w (trade name, manufactured by Lion Akzo Corporation).

  C-10: Amino-modified silicone. SF8417 (trade name, manufactured by Toray Dow Corning Co., Ltd.).

  C-11: Polyether-modified silicone. SH3775M (trade name, manufactured by Toray Dow Corning Co., Ltd.).

(Examples 1-1 to 1-33, Comparative Examples 1-1 to 1-5)
Each component of the compounding amounts shown in Tables 1 to 5 was dispersed in water, adjusted to pH 7.0 with hydrochloric acid and / or sodium hydroxide, and fiber product treatment liquids having the compositions shown in Tables 6 to 10 were obtained.
About the obtained textile treatment liquid, the fluff removal effect was evaluated, and the results are shown in the table.
In addition, the concentration of the component (A) in Tables 6 to 10 is obtained by converting the anti-crystalline activity measured by the method described in “<Enzyme activity>” below into the number of units per 1 kg of the treatment target. is there.

<Enzyme activity>
<< Preparation of 0.1M phosphate buffer >>
17.6 g of NaH ₂ PO ₄ .2H ₂ O (manufactured by Junsei Chemical Co., Ltd.) and 1.0 g of Belol 537 (nonionic surfactant, manufactured by Akzo Nobel) were dissolved in 900 mL of ion-exchanged water. This was adjusted to pH 7.3 with 0.1 M aqueous sodium hydroxide solution, and then made up to 1000 mL with ion-exchanged water.
≪Preparation of enzyme solution≫
The component (A) was dispersed in 0.1 M phosphate buffer to obtain an enzyme solution having a concentration of component (A) of 30 ppm by volume.
≪Preparation of phosphate swelling cellulose substrate solution≫
Ion-exchanged water (5 mL) was added dropwise to 5 g of powdered cellulose (cotton linter, manufactured by Sigma) to wet the powdered cellulose, and then 150 mL of 85% by mass phosphoric acid solution was added thereto, followed by stirring with a stirrer for 10 minutes while cooling with ice. The powdered cellulose was swollen. Acetone 100 mL was added to the swollen powdered cellulose to precipitate phosphoric acid swollen cellulose. The precipitated phosphate-swelling cellulose was filtered through a 200 mesh sieve and washed with ion exchange water. The washed phosphate-swelled cellulose was dispersed in 500 mL of ion exchange water to obtain a substrate solution.
≪Preparation of powdered cellulose substrate liquid≫
5 g of powdered cellulose (cotton linter, manufactured by Sigma) was dispersed in 500 mL of ion-exchanged water to obtain a powdered cellulose substrate solution. When the powdered cellulose substrate solution was allowed to stand, a precipitate was formed. Therefore, a predetermined amount was collected while stirring with a stirrer and dispersing the powdered cellulose during measurement.
≪Preparation of PAHBAH solution (coloring reagent) ≫
1.50 g of PAHBAH (p-Hydroxybenzoeacidhydrazid, Sigma H-9882), 5.0 g of (+)-potassium sodium tartrate tetrahydrate (Merck808), 0.193 g of Bismuth (III) acetate (Alfa AESAR017574) It melt | dissolved in 2 mass% NaOH aqueous solution, and obtained 100 mL PAHBAH liquid.

≪Measurement method for non-crystalline activity≫
2 mL of enzyme solution and 2 mL of 0.1 M phosphate buffer solution were put in a test tube, and these were stirred and mixed. Next, 2 mL of phosphoric acid-swelled cellulose substrate solution was placed in a test tube, and an enzyme reaction was performed for 60 minutes in a 40 ° C. water bath (reaction operation). Then, 1 mL of 2% by weight NaOH aqueous solution was added to the test tube, and the reaction was performed. Stopped. After stopping the reaction, the sample in the test tube was centrifuged (25 ° C., 4000 rpm, 10 minutes) with a centrifuge (manufactured by Hitachi, Ltd., himac CF7D2) (centrifuge operation). After centrifugation, 4 mL of the supernatant was collected, 2 mL of PAHBAH solution was added to the supernatant, and the mixture was reacted for 10 minutes in boiling water. Thereafter, the supernatant was cooled with water, and the absorbance at 410 nm was measured (absorbance α) using water as a control using an absorptiometer (manufactured by Hitachi, Ltd., U-3010).
Add 2 mL of enzyme solution and 2 mL of 0.1 M phosphate buffer to a test tube, stir, mix, and simultaneously add 2 mL of substrate solution and 1 mL of 2 mass% NaOH aqueous solution. A separation operation was performed, and 2 mL of PAHBAH solution was added to the obtained supernatant to obtain a blank. For water, the absorbance of the blank at 410 nm was measured (absorbance β).
The absorbance β was subtracted from the absorbance α, and this was used as the measured value of each enzyme. Separately, a calibration curve was prepared using glucose at a known concentration, and a reducing sugar production amount (μM) was calculated from the measured values of the respective enzymes based on the calibration curve, and this was used as a reducing sugar production amount.
In this enzyme activity measurement method, the amount of enzyme that produces a reducing sugar corresponding to 1 μM glucose per minute was defined as 1 unit.

≪Measurement method for crystal activity≫
The anti-crystal activity was measured in the same manner as the anti-crystal activity except that a powdered cellulose substrate solution was used instead of the phosphate-swelled cellulose substrate solution.

<Evaluation of fuzz removal effect>
≪Preparation of fluff for judgment≫
A commercially available 100% cotton T-shirt (trade name: border knit (AN146906-11, black x gray) is cut to 10 x 10 cm, and 10 pieces of the cut pieces of fabric are lanes of the Terg-O-meter cleaning tester. A piece of cloth was stirred at 120 ° C. for 10 minutes at 120 ° C., and the cloth piece subjected to the stirring treatment was dried at room temperature and dried. Among the pieces, one cloth having a fluff located in the middle was selected, and this was subjected to a stirring process for 10 minutes to obtain a judgment cloth.
Similarly, the time of the stirring process was changed at intervals of 10 minutes between 20 and 150 minutes, and the determination cloth of each process time was obtained.

≪Preparation of fluff evaluation cloth≫
A commercially available 100% cotton T-shirt (trade name: border knit (AN146906-11, black x gray)) was cut into 10 x 10 cm, and 10 pieces of cut cloth pieces were subjected to a Terg-O-meter cleaning tester. Put it in the lane. At 15 ° C., 900 mL of water was placed in the lane, and the cloth piece was stirred at 120 rpm for 120 minutes. The cloth piece subjected to the stirring treatment was rinsed with 900 mL of water, dehydrated in a washing machine, dried at room temperature and dried. Among the ten pieces of cloth, five pieces having the same degree of fluffing were selected and sewn on a white T-shirt (100% cotton, made by UNIQLO) to obtain a fluffing evaluation cloth.

≪Fuzz removal effect≫
Drum-type laundry with one piece of fluff evaluation cloth and another T-shirt (white, 100% cotton, made by UNIQLO) so as to have the mass of “treatment target (kg)” shown in Tables 6 to 10 (Product name: TW-4000VFL, manufactured by Toshiba Corporation). The amount of the fiber product treatment liquid (40 ° C.) shown in Tables 6 to 10 was put in a drum-type washing machine and washed once in an automatic course (washing process 15 minutes, rinsing process 2 times, dehydration process 4 minutes). The washed fluff evaluation cloth was hung and dried at room temperature. Five pieces of cloth were removed from the dried fluff evaluation cloth. Each cloth was visually compared with the fluffing cloth for judgment, and the fluffing cloth for judgment having the same fluffing condition was selected. The stirring time for the selected fluffing cloth for determination was reduced from 120 minutes, and the average value was taken as the fluff removal effect (Δ minutes). The fuzz removal effect (Δ minute) is 120 at the maximum and -30 at the minimum, and the greater the fuzz removal effect (Δ minute), the better the fuzz removal effect.
In this test, the “washing process 15 minutes” in the automatic course is the enzyme treatment process.

As shown in Tables 6 to 10, Examples 1-1 to 1-33 to which the present invention was applied had a fuzz removal effect (Δ minutes) of 50 or more.
On the other hand, Comparative Examples 1-1 to 1-2 not containing the component (A), and Comparative Examples 1-3 to 1-4 and B-3 components in which the concentration of the component (B) is outside the scope of the present invention are contained. In each of Comparative Examples 1-5, the fluff removing effect (Δ minute) was less than 50.

(Examples 2-1 to 2-13)
According to the composition of the secondary treatment liquid shown in Table 11, secondary treatment liquids for each example were prepared.
A drum-type washing machine (white, 100% cotton, made by UNIQLO) is used to separate one fluff-evaluating fabric and a T-shirt (white, 100% cotton, made by Uniqlo) so as to have the mass of “target (kg)” shown in Table 11. Product name: TW-4000VFL, manufactured by Toshiba Corporation). The textile treatment liquid 10L (40 ° C.) of Example 1-1 was put in a drum-type washing machine, and the textile treatment liquid was drained after 15 minutes of washing process (enzyme treatment process). Next, 10 L of the secondary treatment liquid of each example was put into a drum type washing machine and washed once in an automatic course (15 minutes of washing process, 2 times of rinsing process, 4 minutes of dehydration process). The washed fluff evaluation cloth was hung and dried at room temperature. Five pieces of cloth were removed from the dried fluff evaluation cloth. Each cloth was visually compared with the fluffing cloth for judgment, and the fluffing cloth for judgment having the same fluffing condition was selected. The stirring time for the selected fluffing cloth for determination was reduced from 120 minutes, and the average value was taken as the fluff removal effect (Δ minutes). The fuzz removal effect (Δ minute) is 120 at the maximum and -30 at the minimum, and the greater the fuzz removal effect (Δ minute), the better the fuzz removal effect.
In this test, “washing process 15 minutes” in the automatic course is the secondary treatment process.

  As shown in Table 11, Examples 2-1 to 2-13 to which the present invention is applied have a fuzz removal effect (Δ minutes) of 78 or more, and the fuzz removal effect (Δ minutes) compared to Example 1-1. ) Was growing.

Claims (4)

  (A) Component: Endoglucanase, and (B) component: One or more selected from calcium ions and magnesium ions, 20 to 100 ppm by mass.   Furthermore, (C1) component: The textiles processing liquid of Claim 1 containing 1 or more types selected from surfactant and silicone.   The processing method of a textile product provided with the enzyme treatment process which makes the textiles contact the textiles processing liquid of Claim 1 or 2.   After the enzyme treatment step, the fiber product treated in the enzyme treatment step is added to a treatment liquid that does not contain the component (A) and contains at least one selected from the component (C2): surfactant and silicone. The processing method of the textiles of Claim 3 provided with the process to immerse.