CN102791922A - Process for treating cellulosic fibers or cellulosic fiber products - Google Patents

Abstract

The invention provides a method for treating cellulose fiber or cellulose fiber products, and cellulose fiber or cellulose fiber products, wherein the method can provide the cellulose fiber or cellulose fiber products with the function of almost the same cleaning effect as the case of using detergent even in the case of washing without using detergent, and can realize high softness and washing durability. The method for treating cellulose fibers or cellulose fiber products of the present invention comprises: a step of hydrophilizing cellulose fibers or cellulose fiber products; and a step of crosslinking the hydrophilized cellulose fiber or cellulose fiber product using an ester finishing agent and a carbodiimide crosslinking agent, wherein the ester finishing agent contains: ester compounds produced by esterification of oxidatively or acid-modified polyethylene with ethylene oxide and/or propylene oxide adducts of aliphatic alcohols or aliphatic amines.

Description

Process for treating cellulosic fibers or cellulosic fiber products

technical field

The present invention relates to a method for treating cellulosic fibers or cellulosic fiber products and cellulosic fibers or cellulosic fiber products, which can give cellulosic fibers or cellulosic fiber products cleaning without using a detergent. Even in the case of using detergent, it can obtain almost the same cleaning effect as the case of using detergent, and can realize high softness and washing durability.

Background technique

It is common sense to use detergent to wash soiled fiber products. This is achieved by promoting the detachment of stain components from the fiber surface by the effect of the surfactant, which is the main component of the detergent. However, when a large amount of detergent is discharged into the environment, it is pointed out that there is a possibility of remarkably polluting environments such as oceans and lakes. On the other hand, in recent years, the components in detergents have been re-examined, and detergents mainly contain components that have little impact on the environment, and detergents that can achieve the same cleaning effect as conventional detergents with a small amount. developed and marketed. However, the amount of detergent used and discharged in household use and industrial use is huge, and how to reduce the impact on the environment is still a big issue.

On the other hand, by studying a washing machine and a washing method, a washing method that can obtain the same cleaning effect as when using a detergent is studied without using a detergent. For example, Patent Document 1 discloses a washing method in which clothes are passed through a mixture of water and air at high speed, which has a cleaning effect even without adding a detergent containing hydronium ions or hydroxyl ions. However, there are reports that this method requires a special washing machine and does not sufficiently clean stains caused by oily components such as sebum stains.

On the other hand, the inventors of the present application disclosed in Patent Document 2 a method of imparting a detergent-free cleaning function to fibers or fiber products by subjecting fibers or fiber products to a hydrophilization treatment. The fiber product obtained by this method can obtain almost the same cleaning effect as when using a detergent even if it is washed without using a detergent, but the softness will be reduced by the hydrophilization treatment. In addition, the treated fiber products have disadvantages such as a reduction in softness by washing.

prior art literature

Patent Document 1: Japanese Patent Laid-Open No. 2000-237485

Patent Document 2: International Publication No. WO05/005711 Pamphlet

Contents of the invention

The problem to be solved by the invention

In view of the current situation, the present invention aims to provide a treatment method for cellulose fibers or cellulose fiber products, and a cellulose fiber or cellulose fiber product, which can impart cellulose fibers or cellulose fiber products Even in the case of washing without using a detergent, it can obtain almost the same cleaning effect as when using a detergent, and can realize high softness and washing durability.

method used to solve the problem

The method for treating cellulosic fibers or cellulosic fiber products of the present invention includes: a step of hydrophilizing cellulosic fibers or cellulosic fiber products; Fiber or cellulosic fiber products, the process of using ester finishing agent and carbodiimide crosslinking agent to carry out crosslinking. Esters produced by the esterification of ethylene oxide and/or propylene oxide adducts.

Hereinafter, the present invention will be described in detail.

As a method for improving the softness of cellulosic fibers or cellulosic fiber products subjected to hydrophilic treatment, silicone-based softeners, polyester-based softeners, polyamide-based softeners, and polyurethane-based softeners can be considered. , polyethylene softener and other softening agents, but in the case of using these softeners to treat cellulosic fibers or cellulosic fiber products, the hydrophilicity of cellulosic fibers or cellulosic fiber products exists Significant reduction, or the problem of softness reduction due to washing. In addition, it is also conceivable to use the existing durable water-absorbing softening agent, but the use of these durable water-absorbing softening agents for hydrophilized cellulosic fibers or cellulosic fiber products is different from that of ordinary cellulose. Compared with the case of using fiber-like or cellulose-based fiber products, the washing durability tends to be poor and the softness tends to decrease. In addition, there is also a problem that the durable water-absorbing softener remaining on the surface of the fiber inhibits the washing function without detergent.

On the other hand, the inventors of the present invention conducted intensive studies and found that by using a predetermined ester finishing agent and a carbodiimide crosslinking agent in combination, the cellulose fibers or fibers subjected to the hydrophilic treatment By cross-linking the vegan fiber products, it is possible to obtain cellulosic fibers or cellulose that have excellent detergent-free washing function, are endowed with high softness, and are hard to lose softness even after repeated washing. Fibrous products, thus completing the present invention.

In the method for treating cellulosic fibers or cellulosic fiber products of the present invention, first, the step of subjecting cellulosic fibers or cellulosic fiber products to a hydrophilic treatment is performed.

By performing the above-mentioned hydrophilization treatment, a detergent-free cleaning function can be imparted. This is because the stains that cause problems in cellulose fibers or cellulose fiber products are almost all oily components represented by sebum stains. By hydrophilizing cellulose fibers or cellulose fiber products, stains The binding force between ingredients and fibers is weakened, and stained ingredients can be peeled off by just passing water without using surfactants. In addition, stains other than oily components can be peeled off only by washing with a large amount of water without using surfactants.

The detergent-free washing function in this manual means that even in the case of washing without detergent, the cleaning effect can be obtained approximately the same as that of the case of washing with detergent. To obtain approximately the same cleaning effect means: The cleaning effect of the cellulosic fibers or cellulosic fiber products of the hydrophilization treatment carried out by the treatment method of the cellulosic fibers or cellulosic fiber products of the present invention without using detergent, compared with that of untreated Cellulosic fibers or cellulosic fiber products have the same washing effect when washed with detergent. Specifically, for example, when the target cellulose fiber or cellulose fiber product is white, the hydrophilization by the treatment method of the cellulose fiber or cellulose fiber product of the present invention is carried out. The amount of change in the whiteness of the treated cellulose fibers or cellulose fiber products after they are soiled and washed without detergent and before soiling is the difference between the untreated fibers The change in whiteness of the cellulose fiber or cellulose fiber product after it is soiled and washed with a detergent is within 110% of the change in whiteness of the cellulose fiber or cellulose fiber product before soiling. In addition, when the cellulosic fibers or cellulosic fiber products to be targeted are colored substances including white, for example, after the treatment method of the cellulosic fibers or cellulosic fiber products of the present invention is carried out, the affinity The residual rate (%) of oleic acid after hydration-treated cellulosic fibers or cellulosic fiber products are attached with oleic acid 10% o.w.f., gelatin 2.5% o.w.f., after washing without detergent, is in untreated fiber products 10% o.w.f. of oleic acid and 2.5% o.w.f. of gelatin are attached, and the remaining rate (%) of oleic acid after washing with detergent is within 110% of the remaining rate.

The above-mentioned cellulosic fibers or cellulosic fiber products include monofilaments and products using monofilaments. Examples of products using monofilaments include threads such as cotton threads and blended cotton threads, or products made of threads such as cotton cloth. , sliver (bundle), etc.

In addition, in the processing method of the cellulose-based fiber or a cellulose-based fiber product of this invention, the fiber other than the said cellulose-based fiber can also be used. Examples of fibers other than the above-mentioned cellulose fibers include fibers made of natural fibers such as hemp, silk, and wool; polyethylene terephthalate, rayon, high-humidity modulus viscose fibers, cuprammonium short fibers, Fibers composed of acetate, nylon, vinylon, vinylidene, polyvinyl chloride, acrylic, acrylic, polyethylene, polypropylene, polyurethane and other synthetic fibers; their mixed fibers, etc.

In addition, the fibrous fiber products in this specification refer to clothing such as underwear, tops, socks, gloves, hats, hair bands, etc., and also include handkerchiefs, towels, masks, scarves, sheets, pillowcases, bedding, mats, diapers, rubber All articles using cellulosic fibers such as diapers.

The above-mentioned hydrophilization treatment is not particularly limited, for example, it is preferably selected from the method of introducing a hydrophilic group, the method of introducing a hydrophilic molecule, the method of physically modifying the surface, and the method of using a hydrophilic substance. At least one of the methods for coating the coating agent is carried out.

The method for introducing a hydrophilic group is not particularly limited, for example, it is possible to combine molecules constituting cellulosic fibers or cellulosic fiber products with carboxyl groups, amino groups, sulfone groups, hydroxyl groups, phosphoric acid groups, epoxy groups, ether residues, etc. Polar groups such as radicals or hydrophilic groups such as groups having these groups are directly bonded.

The method for introducing the hydrophilic molecule is not particularly limited, but examples include combining molecules constituting cellulosic fibers or cellulosic fiber products with polar groups such as carboxyl groups, amino groups, and sulfone groups, or groups having these groups. Molecular bonding of hydrophilic groups such as groups, or graft polymerization with methacrylamide, hydroxyethyl acrylate, acrylic acid, methacrylic acid, etc. to combine with highly hydrophilic side chains, etc.

The method for physically modifying the surface is not particularly limited, and examples include plasma treatment and corona treatment on the surface of cellulose fibers or cellulose fiber products; ultraviolet rays, electron beams, radiation, lasers, etc. Ionization active line treatment; flame treatment, ozone treatment, yeast microorganism treatment and other treatment methods.

The method of coating with a coating agent containing a hydrophilic substance is not particularly limited, and examples thereof include acrylic resins, methacrylic resins, polyurethane resins, silicone resins, glyoxal resins, vinyl acetate resins, etc. Adhesive resins such as resin, vinylidene chloride resin, butadiene resin, melamine resin, epoxy resin, acrylic-silicone copolymer resin, ethylene-vinyl acetate copolymer resin, isobutylene-maleic anhydride copolymer resin, etc. A coating agent obtained by dissolving a hydrophilic substance such as a hydrophilic vinyl compound, a polyoxyalkylene compound, or a hydrophilic natural compound in a cellulose-based fiber or a method of coating the surface of a cellulose-based fiber product . In addition, after coating these monomers or oligomers, it is also possible to make them react and perform resinization.

In the method for treating cellulosic fibers or cellulosic fiber products of the present invention, it is preferable to set the moisture absorption rate of the cellulosic fibers to 7.1% or more by hydrophilic treatment. When it is less than 7.1%, the binding force between the oily stain component and cellulose fibers or cellulose fiber products is strong, and it may be difficult to sufficiently remove the stain component only with water. It is more preferably 7.5% or more. The upper limit of the moisture absorption rate is not particularly limited, but usually the upper limit is preferably 20%, more preferably 15%.

In addition, the said moisture absorption rate can be calculated|required by following formula (1).

Moisture absorption rate (%)=([Confirmed weight]÷[Absolute dry weight]-1)×100 (1)

In the above formula (1), the absolute dry weight is calculated by the following operation: for example, put the cellulose fiber or the cellulose fiber product to be measured into a weighing bottle, dry it at 105°C for 2 hours, and then weigh it. , obtained by subtracting the weight of the weighing bottle weighed in advance. In addition, the standard weight is calculated by the following operation: For example, after placing the cellulosic fibers or cellulosic fiber products in a weighing bottle and measuring the absolute dry weight in an atmosphere at a temperature of 20°C and a humidity of 65%RH for 24 hours, It weighs, subtracts the weight of the weighing bottle, and obtains it. In addition, for the measurement of the absolute dry weight and the standard weight, for example, a small piece of gray fabric having a size of about 10×20 cm can be used. For weighing, the measurement is repeated until the weight becomes constant.

The method of the above-mentioned hydrophilization treatment is not particularly limited, but a method of introducing a carboxyl group is suitable from the viewpoint of relatively easily imparting a high moisture absorption rate. In addition, the carboxyl group in the present invention also includes salts such as sodium salts and potassium salts.

One of preferred embodiments of the above-mentioned method for introducing carboxyl groups into cellulosic fibers will be described. Carboxyl groups can be easily introduced into cellulose fibers in the form of carboxymethyl groups, for example, by contacting cellulose fibers with a treatment solution containing monochloroacetic acid or an alkali metal salt (for example, sodium salt, potassium salt) of monochloroacetic acid. middle. Hereinafter, such introduction of a carboxymethyl group is referred to as carboxymethylation.

As the concentration of monochloroacetic acid or an alkali metal salt of monochloroacetic acid in the treatment solution for the above-mentioned carboxymethylation, the conditions for the treatment solution that can obtain the target degree of processing can be appropriately determined, and it is preferably 10 to 500 g/ L, more preferably 50-300 g/L, still more preferably 100-200 g/L.

In the above-mentioned treatment solution for carboxymethylation, it is preferable to mix an alkali metal hydroxide, for example, sodium hydroxide. By adding sodium hydroxide, the degree of carboxymethylation of the obtained treated fibers can be increased. There is a tendency for the reaction degree to increase as the concentration of sodium hydroxide in the treatment liquid increases, and the concentration of sodium hydroxide in the treatment liquid is usually preferably 20 g/L or more. However, if a large amount of sodium hydroxide is added, the texture of the obtained fiber tends to deteriorate, so caution is required.

As a method of bringing the cellulose fiber into contact with the above-mentioned treatment liquid, for example, a flow method in which the fiber is rotated in the treatment liquid; a method in which the fiber is dipped in the treatment liquid and then padding (extrusion), and the like can be mentioned. From the viewpoint of use efficiency, it is more effective to reduce the liquor ratio (the ratio of the treatment liquid used), and from this point of view, the method of rolling after dipping is more effective. In addition, the temperature conditions at the time of bringing the cellulose-based fibers into contact with the treatment liquid are not particularly limited, and can be, for example, within a range of 5 to 50°C.

The time for bringing the cellulose-based fibers into contact with the treatment liquid may be appropriately selected from various conditions such as the intended degree of carboxymethylation, the concentration of monochloroacetic acid during the treatment, and the concentration of sodium hydroxide. It may be brought into contact at room temperature for several hours to several days, or the required time may be shortened by heat treatment.

In the case where the texture of clothing such as underwear is particularly required, it is preferable to adjust the concentration of monochloroacetic acid or alkali metal salt of monochloroacetic acid in the treatment liquid, the concentration of alkali metal hydroxide in the treatment liquid, and the treatment temperature and processing time. Among them, increasing the concentration of alkali metal hydroxide in the treatment liquid tends to cause damage to the cellulose fibers and tend to harden the texture. Therefore, the concentration of the hydroxide of the alkali metal in the treatment liquid is preferably as low as possible, and the treatment temperature is preferably set at a low temperature to suppress the influence of the hydroxide of the alkali metal. On the other hand, in order to obtain a sufficient degree of carboxymethylation even when the concentration of the hydroxide of the alkali metal is suppressed very low, it is necessary to dilute monochloroacetic acid or monochloroacetic acid in the treatment liquid. If the concentration of the alkali metal salt is set higher, the treatment time will be extended. Specifically, in the process of making the cellulose fiber, the concentration of alkali metal hydroxide is 20-100g/L, and the concentration of monochloroacetic acid or alkali metal salt of monochloroacetic acid is 100-400g/L. When the liquid is contacted at 10-40°C for 6-48 hours, sufficient moisture absorption and texture can be achieved.

The preferable lower limit of the said degree of carboxymethylation is 0.1 mol%. When it is less than 0.1 mol%, it becomes difficult to obtain sufficient moisture absorption. More preferably, the lower limit is 1 mol%. The upper limit of the degree of carboxymethylation is not particularly limited, but the upper limit is preferably 10 mol%, more preferably 5 mol%.

In addition, in this specification, the degree of carboxymethylation refers to the ratio (%) of the hydroxyl group of cellulose that has undergone carboxymethylation, that is, the number of COO groups after carboxymethylation relative to the number of untreated fibers The ratio (%) of the number of hydroxyl groups of the prime. In addition, COO in cellulose fibers can be determined by changing all COO groups of cellulose fibers into COOH groups, immersing them in an aqueous sodium hydroxide solution (0.1N), and quantifying the amount of Na used for substitution. number of bases. By titrating with hydrochloric acid (0.1N) the sodium hydroxide aqueous solution after immersing the treated cellulose fiber or cellulose fiber product, the amount of Na used for substitution can be quantified. Specifically, the following measurement methods can be employed.

First, the treated cellulose fibers (for example, small pieces of gray cloth) are immersed in 0.3N hydrochloric acid for 1 hour at a bath ratio of 1:50 and a liquid temperature of 20°C. All COO groups will be converted into COOH groups, and dehydration and drying , remove residual HCl, take about 4g as a sample, and weigh the absolute dry weight (W(g)). Next, the cellulose fibers and the like after weighing the absolute dry weight were immersed in 50 mL (B (mL)) of an accurately weighed 0.1 N sodium hydroxide aqueous solution, and left at a liquid temperature of 20° C. for one night. The COOH group is replaced by COONa. Next, in order to quantify Na used for substitution, the liquid was titrated with 0.1N hydrochloric acid, and the titrated value was expressed as X (mL). Phenolphthalein can be used as an indicator.

From the absolute dry weight (W (g)) of cellulose fibers, etc., the volume of sodium hydroxide aqueous solution (B (mL)), and the volume of hydrochloric acid required for titration (X (mL)), according to the following formula ( 2) Calculate the degree of carboxymethylation.

Degree of carboxymethylation (mol%)

=162.14×(B-X)÷[10000W-59.04×(B-X)]÷3×100 (2)

As the above-mentioned hydrophilization treatment method, a method of graft-polymerizing at least one monomer selected from methacrylamide, hydroxyethyl acrylate, acrylic acid, and methacrylic acid in cellulosic fibers is also preferable.

As a method of the above-mentioned grafting, for example, a method in which the above-mentioned monomer is subjected to a polymerization reaction in a state of being in contact with cellulose-based fibers, etc. can be mentioned. Specifically, for example, by immersing and extruding cellulosic fibers in a liquid containing the above-mentioned monomers and a polymerization initiator (for example, ammonium persulfate, etc.), and then heating, it is possible to obtain cellulose fibers grafted with hydrophilic molecules. Cellulosic fibers.

As the amount of hydrophilic molecules introduced by the above-mentioned grafting, it can be appropriately selected in consideration of the type of hydrophilic molecules, the moisture absorption rate required for cellulose fibers, etc., and the preferred lower limit of the grafting rate is 1%. When the branch rate is less than 1%, sufficient moisture absorption may not be obtained. The lower limit is more preferably 2%, and the upper limit of the grafting ratio is not particularly limited, but the upper limit is preferably 30%, more preferably 25%, and still more preferably 20%.

In addition, in this specification, the absolute dry weight (absolute dry weight before treatment) and the absolute dry weight after grafting (absolute dry weight after treatment) of cellulose fibers before grafting can be calculated according to the following formula ( 3) Calculate the grafting rate.

Grafting rate (%)=([Absolute dry weight after treatment]÷[Absolute dry weight before treatment]-1)×100(3)

In the above formula (3), for example, by putting a small piece of gray cloth with a size of about 10×20 cm into a weighing bottle, drying it at 105°C for 2 hours, then weighing it, and subtracting the weight of the weighing bottle weighed in advance, the The absolute dry weight can be calculated.

In the method for treating cellulosic fibers or cellulosic fiber products of the present invention, the cellulose fibers subjected to the hydrophilization treatment are then subjected to a predetermined ester finishing agent and a carbodiimide crosslinking agent. The process of cross-linking fiber or cellulose fiber products. Hereinafter, this step is also referred to as a crosslinking step.

In the present invention, as a specific example of the above-mentioned cross-linking step, for example, immersing the fibers subjected to the hydrophilic treatment in the cross-linking treatment liquid containing the above-mentioned ester type finishing agent, carbodiimide type cross-linking agent, and catalyst A method in which vegan fibers or cellulose fiber products are then rolled (extruded) and dried; a liquid flow method in which cellulose fibers or cellulose fiber products are rotated in a cross-linking treatment liquid, etc. Among them, the method of rolling after dipping is effective.

The above-mentioned ester finishing agent contains ester compounds produced by the esterification reaction of oxidation-modified or acid-modified polyethylene with ethylene oxide and/or propylene oxide adducts of aliphatic alcohols or aliphatic amines. By using the above-mentioned ester-based finishing agent, it has an excellent detergent-free washing function and has high flexibility. In addition, flexibility can be maintained even after repeated washings by using a carbodiimide crosslinking agent described later in combination.

Hereinafter, the said ester compound is also called A component.

Examples of the above oxidation-modified or acid-modified polyethylene include: modified polyethylene obtained by air oxidation or thermal decomposition of polyethylene to introduce carboxyl groups; polyethylene obtained by copolymerizing vinyl carboxylic acids such as acrylic acid and methacrylic acid. modified polyethylene etc. As commercially available items, for example, AC-639, AC-580, AC-540 (all produced by Honeywell International), Mitsui Hiwax4202E, 1105A (all produced by Mitsui Chemicals), SunwaxE-310 (produced by Sanyo Chemical Industry Co., Ltd.) )wait.

As the ethylene oxide and/or propylene oxide adducts of the above-mentioned aliphatic alcohols or aliphatic amines, ethylene oxide and/or ethylene oxide and/or Ethylene oxide and/or propylene oxide adducts of propylene oxide.

Among these, ethylene oxide and/or propylene oxide adducts of aliphatic alcohols are more preferred from the viewpoint of less reduction in whiteness during processing of cellulose fibers or cellulose fiber products. The HLB of the ethylene oxide and/or propylene oxide adduct is preferably 10-19, more preferably 12-17 in order to express water absorption. Moreover, when HLB exists in the said range, a more stable emulsion can be obtained as an ester type finishing agent, Moreover, HLB in this specification is the value calculated|required by Griffin's formula.

The reaction of the above-mentioned oxidation-modified or acid-modified polyethylene with the above-mentioned ethylene oxide and/or propylene oxide adduct can be carried out by the following operation: for example, adding the above-mentioned oxidation-modified or acid-modified poly The above-mentioned ethylene oxide and/or propylene oxide adducts with equivalent molar equivalents of ethylene oxide are added as a catalyst with p-toluenesulfonic acid, and dehydration reaction is carried out at 180-220° C. for 3-5 hours under nitrogen flow. The reaction rate can be tracked by oxidation measurement with a mixed solvent of xylene/dimethylsulfoxide (2/1 to 9/1). In the present invention, the reaction rate of the reactants is preferably 70 to 95%. More preferably, it is 80 to 90%. When the reaction rate of esterification is less than the above-mentioned lower limit, a stable emulsion may not be obtained, and water absorption may be inhibited when handling cellulosic fibers or cellulosic fiber products. In addition, when the above upper limit is exceeded, the crosslinking reaction between the ester finishing agent and the carbodiimide crosslinking agent cannot proceed sufficiently, and the washing durability may be impaired when cellulosic fibers or cellulosic fiber products are treated.

In the above-mentioned ethylene oxide and/or propylene oxide adducts, the aliphatic alcohol or aliphatic amine may be saturated or unsaturated, preferably saturated. The number of carbon atoms is preferably 4-22, more preferably 8-20. When using an aliphatic alcohol or aliphatic amine with a carbon number less than the above-mentioned lower limit, the softness may be deteriorated when processing cellulose fibers or cellulose fiber products, and when using an aliphatic alcohol or aliphatic amine exceeding the above-mentioned upper limit When handling cellulosic fibers or cellulosic fiber products, the water absorption may be deteriorated.

The above-mentioned ester finishing agent preferably further contains a water-soluble polyester resin represented by the following general formula [1].

Hereinafter, the above-mentioned water-soluble polyester resin is also referred to as B component.

In the general formula [1], R ₁ represents a HO-group or HO(R ₂ O) _a -group, R ₂ represents an alkylene group having 2 to 4 carbon atoms, a represents an integer of 1 to 200, and a is 2 or more In the case of , R ₂ O may be the same or different, and in the case of two or more R ₂ Os, random addition or block addition may be used, b represents an integer from 1 to 100, and R ₄ may be the same It can also be different, respectively represent a hydrogen atom or -SO ₃ X group (X represents a hydrogen atom, an alkali metal or an amine), and R ₃ is a hydrogen atom or a group represented by the following general formula [2].

In general formula [2], R ₄ represents the same group as R ₄ in formula [1].

In the above general formula [1], R ₁ represents a HO-group or a HO(R ₂ O) _a - group, and R ₂ represents an alkylene group having 2 to 4 carbon atoms.

Examples of the above-mentioned alkylene group having 2 to 4 carbon atoms include ethylene group, trimethylene group, propylene group, tetramethylene group, and butylene group, and are particularly preferred from the viewpoint of solubility or dispersibility in water. Ethylene.

The said a represents the integer of 1-200, More preferably, it is 1-150. When the above-mentioned a exceeds the above-mentioned upper limit, the viscosity of the polyester resin becomes too high, making it difficult to use.

When the above-mentioned a is 2 or more, R ₂ O may be the same or different, and when there are 2 or more types of R ₂ O, random addition or block addition may be used.

Moreover, said b represents the integer of 1-100, More preferably, it is 1-50. When the above-mentioned upper limit is exceeded, the viscosity of the polyester resin becomes too high, making it difficult to handle it.

In addition, R ₄ may be the same or different, and each represents a hydrogen atom or a -SO ₃ X group, and among the -SO ₃ X groups, X represents a hydrogen atom, an alkali metal or an amine.

Examples of the above-mentioned alkali metals include lithium, sodium, and potassium. Examples of the above-mentioned amines include primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine, and allylamine; dimethylamine, diethylamine, dipropylamine, Secondary amines such as dibutylamine and diallylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.

In addition, R ₃ represents a hydrogen atom or a group represented by the above general formula [2], and in the above general formula [2], R ₄ represents the same group as R ₄ in formula [1].

The above-mentioned water-soluble polyester resin can be produced from an aromatic dicarboxylic acid or a derivative thereof, and an alkylene glycol and/or polyalkylene glycol according to a known method.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid and thioisophthalic acid. Examples of derivatives thereof include lower alkyl esters such as dimethyl, diethyl, dipropyl, and dibutyl esters of these dicarboxylic acids, chlorides of these dicarboxylic acids, and phthalic anhydride. These aromatic dicarboxylic acids or derivatives thereof may be used alone or in combination of two or more.

The polymerization ratio of the aromatic dicarboxylic acid or derivative thereof is not particularly limited, but when using an aromatic dicarboxylic acid or derivative thereof having a -SO ₃ X group, the polymerization ratio is preferably 50 mol % or less. When the polymerization ratio of the aromatic dicarboxylic acid derivative having -SO ₃ X group exceeds the above-mentioned upper limit, sometimes the polycondensation reaction of the water-soluble polyester resin is difficult to proceed, or the shedding caused by washing is aggravated, and it is difficult to obtain further improvement without detergent. Detergent effect.

The weight average molecular weight of the said water-soluble polyester resin becomes like this. Preferably it is 3000-60000, More preferably, it is 5000-30000.

When the weight-average molecular weight of the water-soluble polyester resin is less than the above-mentioned lower limit, detachment by washing is intensified, and the effect of further improving detergent-free detergency cannot be obtained. On the other hand, when the above upper limit is exceeded, the viscosity of the water-soluble polyester resin becomes too high, making it difficult to use. In addition, the weight-average molecular weight of the water-soluble polyester resin can be determined by gel permeation chromatography using monodisperse polyethylene glycol of known molecular weight as a measurement standard substance.

In this invention, when using said A component and B component together, it is preferable that the mass ratio of A component:B component is 1:0.01-1:1. By being within the above range, a high-quality and stable emulsion can be obtained, and when handling cellulosic fibers or cellulosic fiber products, the detergent-free cleaning performance can be further improved.

In the present invention, the above-mentioned components A and B are used together, and these components can be emulsified in water, but it is also possible to mix glycerides, polyol fatty acid esters, polyamine higher fatty acid amides, paraffin wax, water-soluble acrylic resins, amino acids, etc. Modified silicone, etc., to obtain a more stable and high-quality emulsion.

In the present invention, the treatment amount of the above-mentioned ester finishing agent, preferably the adhesion amount of component A in the fiber product, is 0.1-5% o.w.f. as a non-volatile component, more preferably 0.5-2% o.w.f. When the adhesion amount of the above-mentioned A component is less than the above-mentioned lower limit, the washing durability of the treated cellulose-based fibers or cellulose-based fiber products is insufficient, and when it exceeds the above-mentioned upper limit, the treated cellulose-based fibers or cellulose-based fiber products The improvement of softness beyond the upper limit cannot be obtained in the product, which is uneconomical and may impair the non-detergent washing function. In addition, the non-volatile content refers to the remaining content after drying at 105° C. for 3 hours, and % o.w.f. refers to the ratio to the fiber weight.

In the present invention, a carbodiimide crosslinking agent is used as a crosslinking agent together with the above-mentioned ester finishing agent. The carbodiimide-based crosslinking agent causes a crosslinking reaction to impart washing durability to cellulosic fibers or cellulosic fiber products, thereby preventing a decrease in softness.

The above-mentioned carbodiimide crosslinking agent refers to a crosslinking agent containing a carbodiimide group represented by (-N=C=N-). As the above-mentioned carbodiimide crosslinking agent, it is preferable to contain a plurality of carbodiimide groups in one molecule. Furthermore, a water-soluble carbodiimide-based crosslinking agent is more preferable from the viewpoint of handleability and hygroscopicity.

Examples of the carbodiimide-based crosslinking agent include compounds having at least two carbodiimide groups in the molecule, such as polycarbodiimide compounds obtained by decarbonation condensation reaction of diisocyanate in the presence of a catalyst.

As a commercial item, for example, "Carbodilite SV-02", "Carbodilite V-02", "Carbodilite V-02-L1", "Carbodilite V-04", "Carbodilite E-01", "Carbodilite E-02" ( Both are produced by Nisshinbo Chemical Co., Ltd.) and so on.

Among these, "Carbodilite E-01" and "Carbodilite E-02" are more preferable from the viewpoint of stability in the treatment bath.

The treatment amount of the above-mentioned carbodiimide-based crosslinking agent, preferably the amount attached to cellulosic fibers or cellulosic fiber products, is 0.01 to 0.5% o.w.f. as a non-volatile component. When the adhesion amount of the above-mentioned carbodiimide crosslinking agent is less than the above-mentioned lower limit, the washing durability of the treated cellulose fibers or cellulose fiber products is insufficient, and when it exceeds the above-mentioned upper limit, the treated cellulose fibers Fiber or cellulosic fiber products cannot obtain washing durability above the upper limit, are uneconomical, and may impair softness.

In the above-mentioned crosslinking step, a catalyst may be contained in order to promote the crosslinking reaction.

In addition, the above-mentioned cross-linking treatment liquid may contain additives such as antifungal agents, antioxidants, light stabilizers, antistatic agents, conductive agents, flame retardants, and pigments as necessary.

The immersion time in the cross-linking treatment liquid in the above-mentioned cross-linking step, and the squeeze-out rate of the impregnated cellulose fibers or cellulosic fiber products during extrusion can be appropriately selected according to desired performance.

In addition, in the above-mentioned crosslinking step, the lower limit of the drying temperature is preferably 80°C, and the upper limit is preferably 150°C. When it is less than 80° C., the above-mentioned crosslinking agent cannot be sufficiently crosslinked, and the washing durability may decrease. When the temperature exceeds 150°C, the chemical will be deteriorated.

According to the method for treating cellulosic fibers or cellulosic fiber products of the present invention, it is possible to impart to cellulosic fibers or cellulosic fiber products even in the case of washing without using a detergent. A function of the same effect as in the case of agents. In addition, when washing is performed without using a detergent, the operation of removing the detergent (rinsing operation) can be omitted, and thus washing can be performed in a short time. Such shortening of the washing time can greatly save resources such as water and electricity. Furthermore, the fiber products subjected to the method of treating cellulose fibers or cellulosic fiber products of the present invention are extremely excellent in moisture absorption and desorption properties, and have the secondary effect of being excellent in wearing comfort.

In addition, according to the present invention, by performing a crosslinking step using a predetermined ester-based finishing agent and a carbodiimide-based crosslinking agent in combination, it is possible to obtain a product having excellent detergent-free washing function and having both high softness and washing durability. Cellulosic fibers or cellulosic fiber products.

Cellulosic fibers or cellulosic fiber products obtained by using the method of treating cellulosic fibers or cellulosic fiber products of the present invention are also one of the present invention.

The cellulosic fibers or cellulosic fiber products of the present invention may further contain a deodorant. When a carboxymethyl group is introduced as a hydrophilization treatment, it has a high deodorizing effect, but by blending a deodorant, a higher deodorizing effect can be obtained.

The deodorant is not particularly limited, and conventionally known deodorants such as zinc oxides, titanium oxides, silvers, zeolites, and plant extracts can be used, for example. Among them, zinc oxide-based deodorants are preferably used from the viewpoint of easy processing of fibers.

Invention effect

According to the present invention, it is possible to provide cellulosic fibers or cellulosic fiber products with the function of obtaining almost the same cleaning effect as when using a detergent even when washing without using a detergent, and it is possible to achieve high A method for treating cellulosic fibers or cellulosic fiber products with improved softness and washing durability, and cellulosic fibers or cellulosic fiber products.

Detailed ways

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

(Example 1)

Cotton fabric (100% cotton, 40/1 (40 count single yarn) cylindrical rib fabric) is used as the gray fabric, and treated with sodium monochloroacetate (200g/L) and sodium hydroxide (70g/L) The solution was dipped at a bath ratio of 1:20, squeezed using a padder, and allowed to stand at 25° C. for 24 hours to react. Wash with water to remove unreacted substances, and dry to obtain a hydrophilized cotton fabric.

The carboxymethylation degree of the obtained hydrophilic cotton fabric was measured to be 2.67, and the moisture absorption rate was measured to be 8.9%.

To 187 g of oxidatively modified polyethylene Hiwax1105A (manufactured by Mitsui Chemicals, acid value 60), 168 g of ethylene oxide 15 molar adducts (HLB 14.6) of cetyl alcohol and 0.6 g of p-toluenesulfonic acid were added. The temperature was raised under nitrogen flow, and the dehydration reaction was carried out at 180-220° C. for 4 hours to obtain 342.8 g of product (1) with a reaction rate of 83%.

Add 77.6 g (0.4 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of dimethyl 5-thioisophthalate sodium salt, polyethylene glycol (PEG4000, manufactured by Sanyo Chemical Industry Co., Ltd., trade name , Average molecular weight: about 3100) 279g (0.09 mole), monoethylene glycol 68.2g (1.1 mole), antimony trioxide 0.1g, zinc acetate 0.1g, heat up under nitrogen flow, and slowly heat up to 130-180°C after 2 hours , for transesterification reaction. After slowly raising the temperature to 180-250° C. for 2 hours, stop the nitrogen flow, and carry out the reaction at 250-260° C. under a reduced pressure of about 5 mmHg for 2 hours, and then react at 260° C. and a reduced pressure of about 2 mmHg for 30 minutes. 400 g of the water-soluble polyester resin (II) was obtained. The weight-average molecular weight of this water-soluble polyester resin (II) is about 14000 by gel permeation chromatography [high-efficiency GPC manufactured by Tosoh Corporation in Japan, HLC-8120 type, measurement standard substance: polyethylene glycol] .

Dissolve 100g of product (I) and 20g of water-soluble polyester resin (II) at 85-90°C, add 280g of hot water at 85-90°C for emulsification, and obtain a total of 400g of ester finishing agent. The component A contained in this ester-based finishing agent was 25% by mass as a non-volatile component.

Next, the polycarbodiimide crosslinking agent (Carbodilite E-01, manufactured by Nisshinbo Chemical Co., Ltd., manufactured by Nisshinbo Chemical Co., Ltd. The obtained hydrophilized cotton fabric was dipped in a treatment liquid having a non-volatile content of 39.7% by mass, and squeezed using a padding machine at a squeeze ratio of 100%. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth. Under the above conditions, the adhesion amount of component A (as a non-volatile component) is 3% by mass × 25% by mass × 100% = 0.75% o.w.f., and the adhesion amount of a carbodiimide crosslinking agent (as a non-volatile component) is 0.4 Mass % × 39.7 mass % × 100% = 0.16% o.w.f.

(Example 2)

After the hydrophilized cotton fabric was obtained using the same method as in Example 1, the polycarbodiimide crosslinking agent containing 5% by mass of the ester finishing agent obtained in Example 1 as a carbodiimide crosslinking agent (Carbodilite E-01, manufactured by Nisshinbo Chemical Co., Ltd.) The obtained hydrophilized cotton fabric was dipped in 0.4% by mass of the treatment solution, and then squeezed using a padding machine at a squeeze ratio of 100%. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth. Under the above conditions, the adhesion amount of component A (as a non-volatile component) is 5% by mass × 25% by mass × 100% = 1.25% o.w.f., and the adhesion amount of a carbodiimide crosslinking agent (as a non-volatile component) is 0.4 Mass % × 39.7 mass % × 100% = 0.16% o.w.f.

(Example 3)

After the hydrophilized cotton fabric was obtained by the same method as in Example 1, the polycarbodiimide crosslinking agent containing 7% by mass of the ester finishing agent obtained in Example 1 as a carbodiimide crosslinking agent (Carbodilite E-01, manufactured by Nisshinbo Chemical Co., Ltd.) The obtained hydrophilized cotton fabric was dipped in 0.4% by mass of the treatment solution, and then squeezed using a padding machine at a squeeze rate of 100%. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth. Under the above conditions, the adhesion amount of component A (as a non-volatile component) is 7% by mass × 25% by mass × 100% = 1.75% o.w.f., and the adhesion amount of a carbodiimide crosslinking agent (as a non-volatile component) is 0.4 Mass % × 39.7 mass % × 100% = 0.16% o.w.f.

(comparative example 1)

After using the same method as in Example 1 to obtain the hydrophilized cotton fabric, in the treatment solution containing 3% by mass of the ester finishing agent obtained in Example 1, the obtained hydrophilized cotton fabric was soaked, and then, using a padding machine to Squeeze with 100% extrusion rate. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth. Under the above conditions, the adhesion amount of component A (as a non-volatile component) is 3% by mass x 25% by mass x 100% = 0.75% o.w.f.

(comparative example 2)

After using the same method as in Example 1 to obtain the hydrophilized cotton fabric, in the treatment solution containing 5% by mass of the ester finishing agent obtained in Example 1, the obtained hydrophilized cotton fabric was soaked, and then, using a padding machine to Squeeze with 100% extrusion rate. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth. Under the above conditions, the adhesion amount of component A (as a non-volatile component) is 5% by mass x 25% by mass x 100% = 1.25% o.w.f.

(comparative example 3)

After using the same method as in Example 1 to obtain the hydrophilized cotton fabric, in the treatment solution containing 7% by mass of the ester finishing agent obtained in Example 1, the obtained hydrophilized cotton fabric was soaked, and then, using a padding machine to Squeeze with 100% extrusion rate. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth. Under the above conditions, the adhesion amount of component A (as a non-volatile component) is 7% by mass x 25% by mass x 100% = 1.75% o.w.f.

(comparative example 4)

The hydrophilized cotton fabric obtained by the same method as in Example 1 was used as the treated cloth.

(comparative example 5)

After using the same method as in Example 1 to obtain a hydrophilized cotton fabric, soak the obtained hydrophilized cotton fabric in a treatment solution containing 2% by mass of a silicone softener (SOFTEX A-1500, produced by Hokko Chemicals CO., LTD). Cottonized fabric is then squeezed using a padding machine with a squeeze rate of 100%. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth.

(comparative example 6)

After the hydrophilized cotton fabric was obtained by the same method as in Example 1, 3% by mass of a durable silicone softener (TK Silicon EP-301E, manufactured by Takamatsu Oil Co., Ltd.) as a carbodiimide crosslinking agent was added. The obtained hydrophilized cotton fabric was dipped in 0.4% by mass of a polycarbodiimide-based crosslinking agent (CarbodiliteE-01, manufactured by Nisshinbo Chemical Co., Ltd.), and then the padding machine was used at a rate of 100%. extrusion. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth.

(comparative example 7)

After using the same method as in Example 1 to obtain a hydrophilized cotton fabric, in a treatment solution containing 3% by mass of a durable cationic softener (Solusoft 1200, produced by Clariant Company), the obtained hydrophilized cotton fabric was soaked, and then, Squeeze with a padding machine at a squeeze rate of 100%. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth.

(comparative example 8)

In the treatment solution containing 1% by mass of anionic softener (Sansoftener MAX-90A, produced by Sanyo Chemical Co., Ltd.), soak cotton fabric (100% cotton, 40/1 (40 single yarn) cylindrical rib fabric), and then , using a padding machine to extrude at a rate of 100%. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth.

(comparative example 9)

Immerse cotton fabric (cotton 100%, 40/1 (40-count single yarn) cylindrical rib fabric in a treatment solution containing 3% by mass of durable silicone-based softener (TK Silicon EP-301E, manufactured by Takamatsu Shishishi Co., Ltd.) ), and then extruded using a padding machine at a squeeze rate of 100%. Then, it dried at 120 degreeC for 3 minutes, and obtained the treated cloth.

(evaluate)

The treated cloths obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 1.

(1) Oleic acid cleansing test

After attaching 10% o.w.f. oleic acid and 2.5% o.w.f. gelatin to the treated cloth, use an ordinary household washing machine (manufactured by Sharp Corporation, ES-S4A) with only water and add detergent at a concentration of 0.67g/L (manufactured by Kao, Attack) for washing.

After drying the washed test cloths under sunlight, the oleic acid remaining on the test cloths was extracted with methanol, and the residual amount of oleic acid was measured by gas chromatography (manufactured by Shimadzu Corporation, GC-17A) to obtain the oil Acid residual rate (%).

(2) Rigidity

The hardness and softness are measured by the method based on JIS L 1018. First, prepare three specimens with a specimen width of 200 mm and a specimen length of 200 mm for the obtained treated cloth, and place the test specimens in a gap of 10 mm in width using a texture measuring instrument (manufactured by Daiei Science Seiki Seisakusho Co., Ltd.). , When pressing the sample into the gap with the arm, measure the maximum required cN force at four positions in the vertical and horizontal directions on the front and back of the sample, and obtain the total value. The average value of three test pieces was taken as the stiffness. Among them, the stiffness and softness were measured for the state immediately after the treatment (L0), after washing 30 times (L30), after washing 50 times (L50), and after washing 100 times (L100). In addition, the obtained rigidity and softness were evaluated according to the following criteria.

◎Stiffness less than 40cN

○Riffness is 40～60cN

× Rigidity over 60cN

(3) Repeated washing test

In artificial sweat mainly composed of 40.6% by mass of oleic acid, 22.4% by mass of triolein, 17.5% by mass of cholesterol oleate, 3.6% by mass of liquid paraffin, 2.3% by mass of cholesterol, and 10.0% by mass of gelatin, at a liquor ratio of 1 :30 impregnated treatment cloth, then squeezed at a squeeze rate of 130%, and dried at 105° C. for 30 minutes.

Washing was performed using an ordinary household washing machine (manufactured by Sharp Corporation, ES-S4A) with only water and a detergent (manufactured by Kao, Attack) at a concentration of 0.67 g/L.

The washed individual treated cloths were dried in the sun. This operation was repeated three times, and the change in the whiteness of the treated cloth was investigated for each time. The whiteness was measured using a colorimeter (manufactured by Macbeth, White eye 3000). In addition, the difference between the whiteness before washing and the whiteness after 3 washes (reduced whiteness) was calculated. The obtained reduced whiteness was evaluated according to the following criteria.

◎Reduce whiteness less than 10 points

○Reduce whiteness to 10-12.5 points

△Reduce whiteness to 12.5～15.0 points

×Reduce the whiteness more than 15.0

(4) Deodorization effect test

Put a magnetic stirring bar in a 500mL (actual volume: 625mL) Erlenmeyer flask, tie a thread on a test cloth cut into 4cm×5cm, and fix the end of the thread to the outside of the Erlenmeyer flask with cellophanetape, thus, The test cloth is hung in the Erlenmeyer flask. Next, use a micropipette to take 5 μL of a 2% ammonia solution in the case of ammonia deodorization, and 5 μL of a 3% acetic acid solution in the case of acetic acid deodorization, and drop them on the inner wall of the Erlenmeyer flask. The Erlenmeyer flask was immediately sealed with a silicon stopper double-covered with plastic wrap, and then sealed with a rubber ring covered with three layers of the plastic wrap. Then, it was left to stand at 20 degreeC for 120 minutes, stirring with the magnetic stirring bar.

After standing for 120 minutes, set the plastic wrap to prevent the silicon plug from falling off, and use a detection tube with a silicon plug for measurement (produced by Gastec Company, No. 3La/for ammonia, produced by Gastec Company, No. 81/acetic acid Use) to measure the gas concentration in the Erlenmeyer flask.

The same test was performed in the state which did not suspend the test cloth in the Erlenmeyer flask, and this was used as a blank measurement value. The deodorization rate (%) was calculated|required using the following formula. In addition, the obtained deodorization rate was evaluated by the following criteria.

◎The deodorization rate is 90~100%

○The deodorization rate is 80-90%

△The deodorization rate is 70-80%

×Deodorization rate is less than 70%

Deodorization rate (%)={(measured value of blank-measured value of test cloth)/measured value of blank}×100

[Table 1]

As shown in Table 1, in Comparative Example 5, the following phenomenon was observed: washing durability (stiffness at L100) was poor, but the decrease in whiteness after repeated washing tests was small, and the detergent-free washing function could be maintained. This is considered to be because the softening agent without durability does not have a high affinity with the oily stains that cause problems in cellulose fibers or cellulose fiber products, and the softening agent with stains attached to it itself takes a small number of washings. Just come off, so just can reach the same state as the case of comparative example 4 not treated with softening agent with very few number of times of washing.

In Comparative Example 6, Comparative Example 7, and Comparative Example 9, the washing durability (stiffness of L100) was good, but the whiteness decreased significantly after repeated washing tests, and the non-detergent washing function was poor. This is considered to be because conventional durable softeners have a high affinity for oily stains that cause problems in cellulose fibers or cellulosic fiber products, and the softeners themselves that adhere to stains are difficult to peel off by washing.

Thus, in the case of using the conventional softening agent, the washing durability and the non-detergent washing function tend to be opposite, and it is difficult to balance both. On the other hand, in the example, washing durability superior to or equivalent to the case of using a conventional softening agent is realized, and the detergent-free washing function is maintained, so that the washing durability and the detergent-free washing function are two opposite functions able to stand side by side.

Industrial availability

According to the present invention, it is possible to provide the function of imparting cellulose fiber or cellulose fiber products with almost the same cleaning effect as when using a detergent even when washing without using a detergent, and it is possible to achieve high A method for treating cellulosic fibers or cellulosic fiber products having softness and washing durability, and cellulosic fibers or cellulosic fiber products.

Claims (10)

1. A processing method for cellulose fiber or cellulose fiber product, characterized in that, comprising: A process of hydrophilizing cellulosic fibers or cellulosic fiber products; and, A process of crosslinking cellulose fibers or cellulose fiber products subjected to a hydrophilic treatment using an ester finishing agent and a carbodiimide crosslinking agent, The ester finishing agent contains: an ester compound generated by the esterification reaction of oxidation-modified or acid-modified polyethylene and ethylene oxide and/or propylene oxide adducts of aliphatic alcohols or aliphatic amines . 2. the processing method of cellulose fiber or cellulose fiber product as claimed in claim 1, is characterized in that: The ester finishing agent also contains a water-soluble polyester resin represented by the following general formula [1], the weight-average molecular weight of the water-soluble polyester resin is 3000-60000,

In formula [1], R ₁ represents a HO-group or HO(R ₂ O) _a -group, R ₂ represents an alkylene group having 2 to 4 carbon atoms, a represents an integer of 1 to 200, and a is 2 or more In this case, R ₂ O may be the same or different, and when there are two or more R ₂ Os, they may be random addition or block addition, b represents an integer from 1 to 100, and R ₄ may be the same or different. Can be different, respectively represent a hydrogen atom or _-SO3X group, wherein, X is a hydrogen atom, an alkali metal or an amine, and _R3 is a hydrogen atom or a group shown in the following general formula [2],

In general formula [2], R ₄ represents the same group as R ₄ in formula [1]. 3. the processing method of cellulose fiber or cellulose fiber product as claimed in claim 1 or 2, it is characterized in that: The hydrophilization treatment is performed by a method selected from a method of introducing a hydrophilic group, a method of introducing a hydrophilic molecule, a method of physically modifying the surface, and a method of coating with a coating agent containing a hydrophilic substance. at least one method. 4. the processing method of cellulose fiber or cellulose fiber product as claimed in claim 1,2 or 3, it is characterized in that: The moisture absorption rate of the cellulose-based fibers is adjusted to 7.1% or more by the hydrophilization treatment. 5. the processing method of cellulosic fiber or cellulosic fiber product as claimed in claim 3, it is characterized in that: Carboxymethylation is performed to introduce carboxyl groups into cellulose fibers. 6. the processing method of cellulose fiber or cellulose fiber product as claimed in claim 5, is characterized in that: Treatment of cellulose fibers or cellulose fiber products and alkali metal hydroxides at a concentration of 20 to 100 g/L, monochloroacetic acid or an alkali metal salt of monochloroacetic acid at a concentration of 100 to 400 g/L The solution is contacted at 10-40°C for 6-48 hours. 7. the processing method of cellulose fiber or cellulose fiber product as claimed in claim 5 or 6, it is characterized in that: The degree of carboxymethylation is set at 0.1 to 10 mol%. 8. the processing method of cellulose fiber or cellulose fiber product as claimed in claim 4, it is characterized in that: Grafting and polymerizing at least one monomer selected from methacrylamide, hydroxyethyl acrylate, acrylic acid and methacrylic acid in cellulose fibers or cellulose fiber products. 9. the processing method of cellulosic fiber or cellulosic fiber product as claimed in claim 8, it is characterized in that: The graft ratio is set at 1 to 20%. 10. A cellulose fiber or a cellulose fiber product, characterized in that: It is obtained by using the method for treating cellulosic fibers or cellulosic fiber products described in claim 1, 2, 3, 4, 5, 6, 7, 8 or 9.