JP2015221950A - Fiber product treatment liquid and treatment method of fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber product treatment liquid which removes fuzz of a fiber product well and suppresses deterioration of the strength of a fiber product.SOLUTION: A fiber product treatment liquid uses together ingredient (A) 15,000-350,000 unit/L of an endoglucanase and ingredient (B) 1-100 g/L of at least one cationic surfactant selected from tertiary amines and quaternary ammonium salts, and the ratio of [ingredient (B)(mg/L)/ingredient (A)(unit/L)] is preferably 0.02-2.

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 these problems, a preparation containing cellulase such as endoglucanase is known as a preparation for removing fluff produced in a textile product. Cellulase can cut fluff produced in cellulose-containing fibers (for example, cotton, hemp, rayon, or a blended fiber of these with other fibers), and can suppress a decrease in the appearance of the fiber product.
Preparations for removing fluff produced in textile products include (a) one or more cationic fabric softeners, nonionic fabric softeners, or mixtures thereof, (b) cellulase, (c) free radical scavenging There has been proposed a fabric preparation composition comprising a substance selected from the group consisting of an antioxidant, a chelating agent and a mixture thereof (Patent Document 1). The invention of Patent Document 1 aims at effectiveness after long-term storage and fabric safety in a fabric preparation composition used at the time of rinsing.

Japanese National Patent Publication No. 10-500466

In general, enzymes are difficult to act at low temperatures. For this reason, in order to increase the fluff removal effect of cellulase, the temperature of the fiber product treatment liquid is increased to the optimum temperature of the cellulase, the cellulase concentration in the fiber product treatment liquid is increased, and the time for immersion in the fiber product treatment liquid ( It is necessary to take measures such as increasing the immersion time.
However, new equipment is required to raise and maintain the temperature of the textile treatment liquid. Further, if the cellulase concentration in the textile treatment liquid is simply increased or the immersion time is simply increased, the strength of the textile to be treated may be reduced (strength deterioration).
Then, this invention aims at the textiles processing liquid which can remove the fluff of textiles satisfactorily, and can control strength degradation of textiles.

  As a result of intensive studies, the inventors of the present invention have found that when a fiber product is immersed in a fiber product treatment solution having cellulase and a tertiary amine or quaternary ammonium salt in a specific amount, even if a long time has passed, it is excessive. It was found that fiber decomposition does not proceed. This is because the tertiary amine or quaternary ammonium salt is gradually adsorbed to the fiber product, so that the activity of cellulase is not inhibited in the initial stage of immersion, and the amount of tertiary amine or quaternary ammonium adsorbed. This is considered to be because the effect of inhibiting the activity of cellulase increases with each increase.

  The textile product treatment liquid of the present invention comprises (A) component: endoglucanase 15,000-350,000 units / L and (B) component: at least one positive amine selected from tertiary amines and quaternary ammonium salts. It is characterized by having both ionic surfactant 1-100g / L. The ratio represented by [(B) component (mg / L) / (A) component (unit / L)] is preferably 0.02 to 2.

  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.

  According to the textile treatment liquid of the present invention, the fluff of the textile can be removed satisfactorily and the strength deterioration of the textile can be suppressed.

(Textile treatment liquid)
The textile product treatment liquid of the present invention has (A) component: endoglucanase and (B) component: at least one cationic surfactant selected from tertiary amines and quaternary ammonium salts. .

<(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 30,000 to 90,000 units / mL, more preferably 60,000 to 90,000 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. Amorphous activity] in the component (A) is 0.05 to 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 suppress the strength deterioration of the fiber product 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 15,000 to 350,000 units / L, more preferably 22,000 to 300,000 units / L, and 35,000 to 150,000 units / L. Further preferred. If the amount is less than the above lower limit value, the effect of removing fluff becomes insufficient, and if the value exceeds the above upper limit value, strength deterioration of the fiber cannot be sufficiently suppressed.
The unit “unit” of the component (A) content and concentration is non-crystalline activity.

<(B) component: at least one cationic surfactant selected from tertiary amines and quaternary ammonium salts>
Component (B) is at least one cationic surfactant selected from tertiary amines and quaternary ammonium salts. (B) By containing a component, the strength deterioration of a textile product can be suppressed.
As the component (B), a quaternary ammonium salt is preferable, and a dialkyl quaternary ammonium salt represented by the following general formula (I) is more preferable. By containing these components (B), the strength deterioration of the fiber product can be suppressed more favorably.

In the above formula (I), R ¹ is a hydrocarbon group having 4 to 20 carbon atoms. If the amount is less than the above lower limit value, the effect of suppressing the strength deterioration of the fiber product may be reduced, and if the value exceeds the upper limit value, the melting point becomes too high and it is difficult to prepare the fiber product treatment liquid.
R ² is a hydrocarbon group having 4 to 20 carbon atoms, a methyl group, an ethyl group, or a hydroxyethyl group. When R ² is a hydrocarbon group having 4 to 20 carbon atoms, if the carbon number is less than the above lower limit, the effect of suppressing the strength deterioration of the fiber product may be reduced, and if it exceeds the upper limit, the melting point becomes high. It is too difficult to prepare a textile treatment liquid.
R ³ and R ⁴ are each independently a methyl group, an ethyl group or a hydroxyethyl group.
X ⁻ is a counter ion. Examples of X ⁻ include halogen ions such as chlorine ions and bromine ions; organic anions such as alkyl sulfate ions having 1 to 3 carbon atoms (for example, CH ₃ SO ₄ ⁻ ) and acetate ions; OH ^{− and the} like. Among these, a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms are preferable, and a chlorine ion and CH ₃ SO ₄ ^— are more preferable.

In the case of the dialkylammonium salt, the carbon number of the hydrocarbon group of R ¹ and R ² is 10 to 20, more preferably 14 to 20, and R ³ and R ⁴ are each independently a methyl group, an ethyl group or a hydroxyethyl group. It is a group.
In the case of a monoalkylammonium salt, the hydrocarbon group of R ¹ has 10 to 20 carbon atoms, more preferably 16 to 20 carbon atoms, and R ² , R ³ and R ⁴ are each independently a methyl group, an ethyl group or a hydroxy group. It is an ethyl group.

Further, as the quaternary ammonium salt, an alkyl quaternary ammonium salt represented by the above general formula (I) may be added with ethylene oxide and / or propylene oxide.
Ethylene oxide and / or propylene oxide are introduced in R ¹ alone or in R ¹ and R ² . The total of the average addition mole number of ethylene oxide and the average addition mole number of propylene oxide is preferably 0 to 10 moles in one hydrocarbon group.

  The quaternary ammonium salt can be obtained by reacting a tertiary amine or a neutralized product thereof described later with a quaternizing agent. The quaternizing agent is a quaternizing agent by introducing a hydrocarbon group such as a methyl group into a tertiary nitrogen atom of a tertiary amine, and examples thereof include methyl chloride and dimethyl sulfate.

Examples of the tertiary amine include one or more selected from the group consisting of an amine compound containing at least one ester group and a neutralized product of the amine compound. As a neutralized material, the neutralized material by organic acids, such as methyl sulfuric acid, or inorganic acids, such as hydrochloric acid and a sulfuric acid, is mentioned.
Examples of the tertiary amine include compounds represented by the following general formulas (II-1) to (II-7). The compounds represented by formulas (II-1) to (II-7) are sometimes referred to as compounds (II-1) to (II-7), respectively.

In formulas (II-1) to (II-7), each R is independently a fatty acid residue having 10 to 24 carbon atoms.
The fatty acid residue is a residue obtained by removing a carboxy group from a fatty acid.
The carbon number of R is preferably 16-20.
R may be saturated or unsaturated.
R may be linear or branched.
R is a saturated or unsaturated type having 16 to 20 carbon atoms and is preferably a linear fatty acid residue.

From the viewpoint of better suppressing the strength deterioration of the textile product, the saturation / unsaturation ratio (mass ratio) of the fatty acid serving as the R is preferably 80/20 to 0/100, more preferably from 60/40 to 0/100. preferable.
When R is an unsaturated fatty acid residue, a cis isomer and a trans isomer exist, but the mass ratio of the cis isomer / trans isomer is preferably 50/50 to 100/0, particularly 70/30 to 90/10. preferable.

The fatty acids that are the source of R include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10-60), partially hydrogenated beef tallow fatty acid ( Iodine value 10-60) etc. are mentioned. Among them, fatty acids prepared by combining two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid at an arbitrary ratio to satisfy the following conditions (a) to (c) It is preferable to use a composition.
(A) The ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 70/30 to 10/90, more preferably 60/40 to 40/60.
(B) The ratio (mass ratio) of cis isomer / trans isomer is 70/30 to 90/10.
(C) The fatty acid having 18 carbon atoms is 60% by mass or more, preferably 80% by mass or more, the fatty acid having 20 carbon atoms is less than 2% by mass, and the fatty acid having 22 carbon atoms is less than 1% by mass.

Compounds (II-1) and (II-2) can be synthesized by a condensation reaction of the fatty acid composition or fatty acid methyl ester composition and methyldiethanolamine. At that time, from the viewpoint of better suppressing the strength deterioration of the textile product, the abundance ratio represented by “compound (II-1) / compound (II-2)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize so that
The fatty acid methyl ester composition is a combination of two or more fatty acid methyl esters in any proportion.
When these are quaternized, it is preferable to use dimethyl sulfate as a quaternizing agent. At that time, from the viewpoint of flexibility, the abundance ratio represented by “a quaternized compound (II-1) / a quaternized compound (II-2)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize.

Compounds (II-3) to (II-5) can be synthesized by a condensation reaction between the fatty acid composition or the fatty acid methyl ester composition and triethanolamine. In that case, the content ratio of each component with respect to the total mass of the compounds (II-3) to (II-5) is such that the compound (II-3) is from 1 to 60% by mass, compound (II-4) is preferably 5 to 98% by mass, compound (II-5) is preferably 0.1 to 40% by mass, compound (II-3) is 30 to 60% by mass, More preferably, the compound (II-4) is 10 to 55% by mass and the compound (II-5) is 5 to 35% by mass.
Moreover, when quaternizing these, it is preferable to use a dimethyl sulfate as a quaternizing agent at the point which makes a quaternization reaction fully advance. The abundance ratio of each quaternized compound (II-3) to (II-5) is a mass ratio from the viewpoint of flexibility, and the quaternized compound (II-3) is 1 to 60% by mass, the compound ( It is preferable that the quaternized product of II-4) is 5 to 98% by mass and the quaternized product of compound (II-5) is 0.1 to 40% by mass, and the quaternized product of compound (II-3) is It is more preferable that 30 to 60% by mass, the quaternized compound (II-4) is 10 to 55% by mass, and the quaternized compound (II-5) is 5 to 35% by mass. In addition, when compounds (II-3) to (II-5) are quaternized, esteramine that has not been quaternized remains after the quaternization reaction. At that time, the ratio of “quaternized product / non-quaternized ester amine” is preferably in the range of a mass ratio of 70/30 to 99/1.

Compounds (II-6) and (II-7) were obtained from the above-mentioned fatty acid composition, an adduct of N-methylethanolamine and acrylonitrile from JOrg. Chem. , 26, 3409 (1960), by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by a known method. In that case, it is preferable to synthesize | combine so that the abundance ratio represented by "compound (II-6) / compound (II-7)" may be 99/1-50/50 by mass ratio.
When quaternizing these, it is preferable to use methyl chloride as a quaternizing agent, which is expressed by “a quaternized compound (II-6) / a quaternized compound (II-7)”. It is preferable to synthesize the abundance ratio such that the mass ratio is 99/1 to 50/50.

  In the present invention, a quaternary ammonium salt which is a quaternized product of the mixture of the above compounds (II-3) to (II-5) is preferable.

  Content of the (B) component in a textiles processing liquid is 1-100 g / L, 2-50 g / L is more preferable, and 5-30 g / L is further more preferable. If it exceeds the upper limit, the inhibitory effect on the activity of the component (A) is too great, and a sufficient fluff removing effect cannot be obtained. If it is less than the said lower limit, the effect which stops the excessive decomposition | disassembly of the fiber by (A) component is weak, and the strength deterioration of a textiles cannot fully be suppressed.

  In the textile treatment liquid, the B / A ratio represented by [(B) component (mg / L) / (A) component (unit / L)] is preferably 0.02 to 2, preferably 0.04 to 1. .5 is more preferable, and 0.1 to 1 is more preferable. If the B / A ratio is less than the above lower limit value, the effect of suppressing the deterioration of the strength of the fiber product may be reduced, and if it exceeds the upper limit value, the fuzz removal effect may be reduced.

<Optional component>
The textile processing liquid of this invention may contain arbitrary components other than (A)-(B) component. Examples of optional components include calcium ions and / or magnesium ions, surfactants (optional surfactants) other than component (B), polymers such as silicone and cationized cellulose, monoethanolamine, diethanolamine, and triethanolamine. , N-methyl-diethanolamine, alkali builders such as alkanolamines such as N, N-dimethylmonoethanolamine, pH adjusters, hydrotropes, fluorescent agents, (A) enzyme other than component (arbitrary enzyme), migration prevention Agents, anti-staining agents (for example, polyvinyl pyrrolidone, carboxymethyl cellulose, etc.), pearl agents, soil release agents, and the like.

≪Calcium ion and / or magnesium ion≫
The textile treatment liquid may contain calcium ions and / or magnesium ions in order to enhance the activity of the component (A) and enhance the fluff removal effect.
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 source of these components may be used alone or in combination of two or more.
The lower limit of the total amount of calcium ions and magnesium ions in the textile treatment liquid is preferably 20 mass ppm or more, more preferably 30 mass ppm or more, further preferably 40 mass ppm or more, and particularly preferably 50 mass ppm or more. If it is more than the said lower limit, it is easy to improve a fuzz removal effect.
The upper limit of the total amount of calcium ions and magnesium ions in the textile treatment liquid is preferably 100 mass ppm or less, more preferably 90 mass ppm or less, still more preferably 80 mass ppm or less, and particularly preferably 70 mass ppm 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.
The ratio represented by [total amount of calcium ions and magnesium ions (mass ppm)] / [concentration of component (A) (unit / L)] in the fiber product treatment solution is 0.0002 to 0.0019. Preferably, 0.0006 to 0.0017 is more preferable, and 0.0008 to 0.0014 is more preferable. If it is less than the lower limit, it is difficult to obtain the effect of blending calcium ions or magnesium ions, and even if it exceeds the upper limit, further improvement of the fluff removal effect cannot be achieved, 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

≪Optional surfactant≫
Examples of the optional surfactant include nonionic surfactants, cationic surfactants other than the component (B), and amphoteric surfactants. By containing an optional surfactant, the fiber product treatment liquid easily penetrates into the cellulose-containing fiber (permeation promoting effect), and the fluff cut by the component (A) is promptly put into the fiber product treatment liquid. It is possible to suppress the dispersed fuzz from adhering to the fiber product (fuzz adhesion prevention effect).

Any arbitrary surfactant may be used as long as it is conventionally used for a detergent for textile products, and among them, a nonionic surfactant is 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 (III) is preferably used.

_{^{R 11 -Y- (EO) n (}} PO) m -R 12 ··· (III)

In the formula (III), R ¹¹ is a hydrocarbon group.
R ¹¹ 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 ¹¹ may or may not have an unsaturated bond.
R ¹¹ is preferably an alkyl group or an alkenyl group.
R ¹¹ may be linear or branched and is preferably branched.
Examples of R ¹¹ include hydrocarbon groups derived from primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.

R ¹² 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 ¹² is an alkyl group, R ¹² preferably has 1 to 3 carbon atoms.
When R ¹² is an alkenyl group, R ¹² preferably has 2 to 3 carbon atoms.

Y is a functional group such as O, COO, and CONH.
In the formula (III), when Y is O, the nonionic surfactant represented by the formula (III) is an alcohol type nonionic surfactant.
When Y is O, R ¹¹ 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 fuzz removal effect and the fuzz adhesion suppressing 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 Y is O, R ¹² is preferably a hydrogen atom.

In the formula (III), when Y is COO, the nonionic surfactant represented by the formula (III) is a fatty acid ester type nonionic surfactant. When Y is COO, R ¹¹ 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 Y is COO, R ¹² is preferably an alkyl group having 1 to 3 carbon atoms.

(III) 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 (III), 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 (III) include, for example, Diadol (trade name, C13 (C represents the number of carbon atoms; the same shall apply hereinafter) manufactured by Mitsubishi Chemical Corporation) manufactured by Shell. A 12 mol equivalent or 15 mol equivalent of ethylene oxide is added to an alcohol such as Neodol (trade name, mixture of C12 and C13), Sasol 23 (trade name, mixture of C12 and C13) manufactured by Sasol. Obtained by adding 12 equivalents or 15 equivalents of ethylene oxide to a natural alcohol such as CO-1214 or CO-1270 (trade name) manufactured by Procter &Gamble; obtained by trimerizing butene 7 mole equivalent of ethylene oxide added to C13 alcohol obtained by subjecting C12 alkene to oxo process Product name: Lutensol TO7, manufactured by BASF); 9 mol equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name: Lutensol XP90, manufactured by BASF); Is obtained by adding 7 mol equivalent of ethylene oxide to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name: Lutensol XL70, manufactured by BASF); to C10 alcohol obtained by subjecting pentanol to garvet reaction , 6 mol equivalent ethylene oxide added (trade name: Lutensol XA60, manufactured by BASF); 9 mol equivalent, 12 mol equivalent or 15 mol equivalent ethylene oxide with respect to secondary alcohol having 12 to 14 carbon atoms Added (quotient Product name: Softanol 90, Softanol 120, Softanol 150, manufactured by Nippon Shokubai Co., Ltd .; Palm fatty acid methyl (lauric acid / myristic acid = 8/2) is added with 15 mole equivalent of ethylene oxide 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 cationic surfactant other than the component (B) is not particularly limited, and examples thereof include aliphatic amines, fatty acid amidoamine salts, alkyltrialkylene glycol ammonium salts, acylguanidine derivatives, and mono-N-long chain acyl basics. 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.

The amphoteric surfactant is not particularly limited, and for example, alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, or phosphoric acid Examples include amphoteric surfactants such as molds.
These amphoteric surfactants may be used alone or in combination of two or more.

The arbitrary surfactant mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the optional surfactant in the textile treatment liquid is, for example, preferably 0.02 g / L or more, more preferably 0.02-1 g / L, and even more preferably 0.05-0.5 g / L.
In addition, it is preferable that a textile treatment liquid does not contain an anionic surfactant as an arbitrary surfactant. This is because the anionic surfactant may reduce the effect of the component (B).

≪Silicone≫
The silicone 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 is a silicone having 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.
For example, the content of silicone in the textile treatment liquid is preferably 0.02 g / L or more, more preferably 0.02 to 1 g / L, and even more preferably 0.05 to 0.5 g / L.

≪Thinning agent or solubilizer≫
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.

≪Metal scavenger≫
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.

≪Preservatives≫
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.

≪Arbitrary enzyme≫
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, Evaluse Ultra 16L, 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.

≪Flavorant≫
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.

≪Colorant≫
Colorants include 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, and 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.

≪Emulsifier≫
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.

≪Extract≫
Extracts include Inuenju, Ouurushi, Echinacea, Koganebana, yellowfin, yellow spider, allspice, oregano, Enju, chamomile, honeysuckle, Clara, Keigai, Kay, 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.

<PH>
The fiber product treatment liquid preferably has a pH (25 ° C.) of 4 to 9, and more preferably a pH of 5 to 8. If it is in the said range, the activity of (A) component can be heightened and the further improvement of a fluff removal effect can be aimed at, making the influence on textiles as low as possible.
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. B) A method of diluting with water so that the component has a predetermined concentration can be mentioned.

<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) and a method of applying the fiber product treatment liquid to the fiber product (application method). The dipping method is preferred. If it is an immersion method, a fluff can be removed more favorably.

  As the dipping method, the textile product treatment liquid in which the textile product is soaked is agitated using a washing machine (stirring soaking method), and the textile product is soaked in the textile treatment liquid contained in a container such as a bucket. Examples of such a method include a method of standing (stationary dipping method).

10-60 degreeC is preferable, as for the temperature of the textile treatment liquid in an enzyme treatment process, 30-50 degreeC is more preferable, and 35-45 degreeC is further more preferable. 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.
In general households, it is difficult to maintain the temperature of the textile treatment liquid. For this reason, when the immersion method is adopted in a general household, a stationary immersion method in which a fiber product treatment liquid adjusted to an arbitrary temperature is placed in a container such as a bucket and the fiber product is immersed therein is preferable.

In the dipping method, the amount of the textile product (processing object) to be immersed is determined according to the content of the component (A) and the content of the component (B) in the textile processing liquid.
The amount of the processing object to be immersed is preferably, for example, an amount such that the component (A) is 130,000 to 1,400,000 units, and 200,000 to 1,100,000 units per 1 kg of the processing target. The amount is more preferable, and an amount that is 275,000 to 550,000 units is 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.
In addition, the amount of the processing object to be immersed is preferably such that the component (B) is 0.001 to 1 kg, more preferably 0.005 to 0.75 kg, with respect to 1 kg of the processing target. An amount of 0.05 to 0.5 kg is more preferable. Even if it exceeds the upper limit, it is difficult to further improve the effect of suppressing the strength deterioration of the fiber product, which is economically undesirable. If it is less than the said lower limit, it is difficult to aim at suppression of the strength deterioration of a textile product.

  The immersion time in the immersion method is preferably, for example, 1 to 10 hours, and more preferably 3 to 6 hours. If the amount is less than the above lower limit value, the fuzz removal effect may be reduced, and if the value exceeds the above upper limit value, the strength of the fiber product tends to deteriorate.

  The enzyme treatment process may be repeated twice or more by replacing the textile treatment liquid.

In the textile treatment method of the present invention, a washing step may be provided before or after the enzyme treatment step. The washing step is preferably provided after the enzyme treatment step. By providing a washing step after the enzyme treatment step, the fluff cut from the fiber product is dispersed in the cleaning liquid, the fluff adhering to the fiber product is removed, and the fluff adheres to the fiber product. It can be suppressed well.
Examples of the washing step include a method in which a textile product is put into a washing liquid in which water or a detergent is dispersed and washed with a washing machine. Alternatively, after the enzyme treatment step, a method of adding a cleaning agent to the textile treatment liquid and washing the textile can be mentioned.

  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).

  As described above, since the textile treatment liquid of the present invention contains the component (A) and the component (B) at a specific concentration, the fluff produced in the textile is more suppressed while suppressing the strength deterioration of the textile. It can be removed well.

  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: endoglucanase>
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: 0.073, manufactured by Novozymes).

<(B) component: Cationic surfactant>
B-1: Dichlorinated beef tallow alkyldimethylammonium (Arcard 2HT-75 (trade name), 75% by mass of active ingredient, manufactured by Lion Akzo Corporation).
B-2: Dialkyl chloride (carbon number 14 to 18) dimethylammonium (Arcard 2HP-75 (trade name), active ingredient 75 mass%, manufactured by Lion Akzo Co., Ltd.).
B-3: Chlorinated tallow ester amide type ammonium. Synthesized by the following synthesis method.

<< B-3: Synthetic Method of Chlorinated Tallow Esteramide Ammonium Salt >>
B-3 was synthesized according to the following procedure in accordance with the method described in JP-A-5-230001.
From an adduct of N-methylethanolamine and acrylonitrile, J. Org. Org. Chem. , 26, 3409 (1960), N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine was synthesized by a known method. 66 g of N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine and 284 g of hardened beef tallow fatty acid were charged into a four-necked flask equipped with a stirrer, a thermometer and a dehydrating tube. The temperature was raised to 180 ° C., and heating was carried out at 180 ° C. for 10 hours while distilling off generated water, thereby obtaining 300 g of a reaction product. As a result of measuring the acid value, saponification value, hydroxyl value, total amine value, tertiary amine value of the obtained reaction product and examining the composition of the reaction product, 86% by mass of the dialkyl product and 10% of the monoalkylamide product were obtained. The mass% and unreacted fatty acid were 4 mass%. Moreover, from the analysis by gas chromatography, 0.1 mass% of unreacted N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine was contained in the reaction product. Finally, 53 g of unmodified ethanol (manufactured by Mitsubishi Chemical Corporation) was added to obtain B-3 as an ethanol solution having a solid content of 85% by mass.

B-4: Methyl bis [ethyl (tallowate)]-2-hydroxyethyl ammonium sulfate (STEPANTEX VK 90: 90% by mass of active ingredient: manufactured by Stepan).
B-5: Alkyl chloride (having 16 to 18 carbon atoms) trimethylammonium (Arcard T-800: 50% by mass of active ingredient: manufactured by Lion Akzo Corporation).
B-6: Didecyldimethylammonium chloride (Arcard 210-80E: active ingredient 80% by mass: Lion Akzo Co., Ltd.).

  Nonionic surfactant: LMAO. An average of 15 moles of ethylene oxide added to natural alcohol CO-1270 manufactured by Procter & Gamble. Synthesized by the following synthesis method.

≪Synthesis method of LMAO≫
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 a reaction product. .
Next, the reaction product was cooled to 100 ° C. or less, and neutralized by adding a 70% by mass toluene-sulfonic acid solution so that the pH of the 1% by mass aqueous solution of the reaction product was 7, to obtain LMAO.

(Examples 1-15, Comparative Examples 1-6)
According to the composition shown in Tables 1-2, each component was dispersed in tap water and adjusted to pH 7.0 with hydrochloric acid and / or sodium hydroxide to obtain a textile treatment liquid.
About the obtained textile treatment liquid, the fuzz removal effect and the fiber strength reduction rate were evaluated. The results are shown in the table.
In addition, the compounding quantity in a table | surface is a pure part conversion value.

(Evaluation method)
<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). 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 fluff removal effect, fiber strength reduction rate>
≪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 in the middle was selected and used as a judgment cloth subjected to a stirring process for 10 minutes.
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) 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 rpm for 120 minutes, rinsed with 900 ml of water, and dehydrated in a washing machine. After drying at room temperature, select 10 pieces of fabric with the same level of fluffing, sew them on a white T-shirt (100% cotton, made by Uniqlo), and evaluate the fluffing It was.

≪Fiber strength evaluation cloth≫
Cotton cloth of the dyeing fastness test cloth Unsilled (Tanigami Shoten) was cut into 1 m x 1 m to obtain a fiber strength evaluation cloth.

≪Enzyme treatment≫
Put 10L of the fiber treatment liquid of each example into a 10L capacity bucket, put in two sheets of fluff evaluation cloth and two sheets of fiber strength evaluation cloth, and at room temperature (25 ° C) for 6 hours or 24 hours. Immersion (enzyme treatment step).

≪Laundry treatment≫
After the enzyme treatment step, the fluff evaluation cloth and the fiber strength evaluation cloth are taken out, and the clothes with another T-shirt (white, 100% cotton, made by UNIQLO) are added to the vertical washing machine washing machine (product name: AW- Put in 800 form, manufactured by Toshiba Corporation, add 20 mL of commercially available liquid detergent (Acron), tap water (15 ° C) in an automatic course (12 minutes washing process, 2 rinsing processes, 6 minutes dehydration process) Washed once (washing process). The washed fluff evaluation cloth was hung and dried at room temperature.

≪Fuzz removal effect≫
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. At 50 hours or more after 6 hours of immersion.

≪Fiber strength≫
The fiber strength test cloth subjected to the washing treatment and the fiber strength test cloth subjected to only the washing treatment without being subjected to the enzyme treatment were cut into (width 100 mm), and “JIS L1096: 2010 Fabric and knitted fabric test method 8. The tensile strength was measured according to “14.1 JIS method B method (grab method)”. At this time, the gripping interval was 76 mm, the tensile speed was 300 mm / min, the tensile strength of the five test pieces was measured, and the average value (α) was calculated.
The tensile strength (β) of the fiber strength test cloth not subjected to the enzyme treatment was set to 100, and the relative fiber strength reduction rate (%) was calculated by the following equation (i). Further, the amount of increase in the strength reduction rate was determined by the following equation (ii). The comparison was made in the lateral direction (the direction in which the wefts extend) of the fabric having weak fiber strength.
In the 6-hour immersion product, a fiber strength reduction rate of 20% or less was accepted. In the 24-hour immersion product, the fiber strength reduction rate was 30% or less. An increase in strength decrease rate of 10 or less was considered acceptable.

  Fiber strength reduction rate (%) = (β−α) ÷ β × 100 (i)

  Strength reduction rate increase amount = [Fiber strength reduction rate of 24 hour immersion product (%)] − [Fiber strength reduction rate of 6 hour immersion product (%)] (ii)

As shown in Tables 1-2, in Examples 1 to 15 to which the present invention was applied, all of the fuzz removal effect, the fiber strength reduction rate, and the strength reduction rate increase could be judged as acceptable.
In Comparative Example 1 containing no component (A), no fluff removal effect was observed.
In Comparative Example 2 containing no component (B), the fiber strength decrease rate of the 24-hour immersion product was 35% and the strength decrease rate increase amount was 15.
In Comparative Example 3 in which the content of the component (A) is 400,000 units / L, the fiber strength reduction rate of the 6-hour soaked product was 22%.
In Comparative Example 4 in which the content of the component (A) is 10,000 units / L, the fluff removal effect of the 6-hour immersion product was Δ40 minutes.
In Comparative Example 5 in which the content of the component (B) was 250 g / L, the fluff removal effect of the 6-hour immersion product was Δ45 minutes.
In Comparative Example 6 in which the content of the component (B) was 0.1 g / L, the fiber strength reduction rate of the 24-hour immersion product was 31%, and the strength reduction rate increase amount was 12.
From these results, it was found that by applying the present invention, the fluff of the fiber product can be removed well and the strength deterioration of the fiber product can be suppressed.

Claims (3)

  Component (A): Endoglucanase 15,000-350,000 units / L; Component (B): At least one cationic surfactant selected from tertiary amines and quaternary ammonium salts 1-100 g / L is a fiber product treatment liquid.   The ratio represented by [(B) component (mg / L) / (A) component (unit / L)] is 0.02-2, The textiles processing liquid of Claim 1.   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.