JP2001288681A - Anti-soil deposition agent, and cellulosic fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-soil deposition agent which is used for cellulosic fibers and can be used during or after a fixing treatment to impart a resoiling- preventing property to the cellulosic fibers in post processing processes such as a softener treatment and a fluorescent dye-imparting treatment, in a water- washing treatment and in repeated washing treatments, while maintaining the original fastness-improving effect of a fixing agent, and to provide a cellulosic fiber product containing the anti-soil deposition agent and the fixing agent in the substrate of the cellulosic fiber product. SOLUTION: This anti-soil deposition agent characterized by containing a cationic surfactant derived from a monoamine having at least one 4 to 22C chain hydrocarbon group in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a redeposition inhibitor and a cellulosic fiber product. More specifically, the present invention is useful in the treatment of cellulosic fibers performed simultaneously with or after the fix treatment, softener treatment, post-processing steps such as fluorescent dye application treatment and water washing after treatment, in repeated washing The present invention relates to a recontamination inhibitor for cellulosic fibers that prevents or reduces reattachment of pollutants, and a cellulosic fiber product containing a recontamination inhibitor and a fixing agent in a cellulosic fiber product base material.

[0002]

2. Description of the Related Art Conventionally, in a process for producing a cellulosic fiber product, a fix treatment for improving the fastness of a dye is performed. However, in the case of fixation-treated cellulosic fiber products, the fabric products may become lightly stained, have no clear color, or have a white color when subjected to post-processing steps such as softener treatment, fluorescent dye application treatment, washing after treatment, or repeated washing. There are problems such as blackening and yellowing. The recontamination of the textile product is due to the fact that the anionic contaminants that have fallen off from the textile product during the post-processing step or washing are added to the fixing agent because the cotton and the cotton-fixing agent fixed to the textile product are cationic substances. It is thought to be due to adhesion.

In order to solve this problem, that is, to suppress the cationicity of the fixing agent,
At the same time as the fix treatment (the same bath treatment) or after the fix treatment, a method of treating the textile with an anionic compound is being studied. However, the method using the same bath treatment has a disadvantage that the fixing agent and the anionic compound form a complex. Further, when a method of performing processing after the fix processing is used, although the re-contamination prevention property is improved, there is a problem that the robustness improved by the fix processing is reduced again.

[0004] As described above, it has been extremely difficult to achieve both re-staining prevention property and fastness in cellulosic fiber products.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has been developed by treating a cellulosic fiber product base material simultaneously with or after the fix treatment. Softener treatment while maintaining the original fastness improving effect of the agent,
A post-processing step such as a fluorescent dye application treatment or water washing after the treatment, a re-staining inhibitor for cellulosic fibers capable of imparting a re-staining effect at the time of repeated washing, and the re-staining agent and the fixing agent. It is an object of the present invention to provide a cellulosic fibrous product containing the same in a cellulosic fiber product substrate.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, they have been derived from monoamines having at least one chain hydrocarbon group having 4 to 22 carbon atoms in the molecule. It has been found that the above problems can be solved by treating the cellulosic fiber simultaneously with or after the fixation treatment using a re-staining inhibitor containing a cationic surfactant. Reached.

That is, the re-staining agent for cellulosic fibers of the present invention comprises at least one carbon atom having 4 to 2 carbon atoms in the molecule.
And a cationic surfactant derived from a monoamine having a chain hydrocarbon group of No. 2.

Further, the cellulosic fiber product of the present invention comprises:
A cellulosic fiber product comprising: a cellulosic fiber product substrate; and a fixing agent and a re-staining inhibitor contained in the cellulosic fiber product substrate, wherein the re-staining agent has at least 1 It is characterized by containing a cationic surfactant derived from a monoamine having two chain hydrocarbon groups having 4 to 22 carbon atoms.

According to the present invention, a fix treatment is carried out using a redeposition inhibitor containing a cationic surfactant derived from a monoamine having at least one chain hydrocarbon group having 4 to 22 carbon atoms in the molecule. By treating the cellulosic fibrous substrate at the same time or after the fix treatment, the re-adhesion of the anionic contaminants to the fibers is prevented or reduced without reducing the effect of improving the fastness of the fix agent. Therefore, it is possible to obtain a cellulosic fiber product having a high anti-recontamination property in a post-processing step such as a softening agent treatment, a fluorescent dye application treatment, washing with water after treatment, and repeated washing.

In the present invention, the cationic surfactant is preferably a compound having a structure represented by the following general formula [1].

[0011]

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[In the formula, R ¹ represents a chain hydrocarbon group having 4 to 22 carbon atoms, and R ² and R ³ may be the same or different, and may be a chain hydrocarbon group having 1 to 22 carbon atoms. Or the following formula: — (R ⁴ O) _m — (AO) _n H (wherein R ⁴ represents a 2-hydroxypropylene group;
Represents an alkylene group having 2 to 4 carbon atoms, m represents 0 or 1, and n represents an integer such that the total number of n in the above formula [1] is 1 to 10. Wherein Z is a linear hydrocarbon group having 1 to 22 carbon atoms which may have a substituent or the following formula:-(BO) _p H (where B is an alkylene group having 2 to 4 carbon atoms) And p represents an integer of 1 to 5), or an aromatic hydrocarbon group having 7 to 10 carbon atoms which may have a substituent, and X ⁻ represents an anion. ]

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The anti-redeposition agent of the present invention contains a cationic surfactant derived from a monoamine having a chain hydrocarbon group having 4 to 22 carbon atoms, and is preferably a quaternary agent. It contains an ammonium salt type cationic surfactant, and more preferably the following general formula [1]:

[0014]

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A compound having a structure represented by the following formula: When the cationic surfactant is of a quaternary ammonium salt type, a higher anti-redeposition property tends to be obtained.

In the above formula [1], R ¹ represents a chain hydrocarbon group having 4 to 22 carbon atoms. Here, the chain hydrocarbon group may be any of a saturated hydrocarbon group and an unsaturated hydrocarbon group, and may be linear or branched. Further, the chain hydrocarbon group may have a substituent such as a hydroxyl group, or may have an ether bond in the chain. Such chain hydrocarbon group is not particularly limited, for example, butyl group, amyl group, hexyl group, 2-ethylhexyl group, octyl group, lauryl group, myristyl group, palmityl group, stearyl group, eicosyl group, Behenyl group, oleyl group, elaidyl group, 4
-Hydroxybutyl group, 2-hydroxyoctadecyl group, 3-butoxypropyl group, 3-lauryloxypropyl group and the like.

In the above formula [1], R ² and R ³ may be the same or different, and may be a chain hydrocarbon group having 1 to 22 carbon atoms or the following formula:-(R ⁴ O) _m- (AO) represents a group represented by _n H. Here, the chain hydrocarbon group is
It may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be linear or branched. Further, the chain hydrocarbon group may have a substituent such as a hydroxyl group, and may have an ether bond in the chain. Such hydrocarbon groups are not particularly limited. In addition to the hydrocarbon groups shown as specific examples of R ¹ above,
Examples include a methyl group, an ethyl group, a vinyl group, a propyl group, an allyl group, and a methylallyl group. Note that R ² , R ³
Is a hydrocarbon group, at least one of R ² and R ³ preferably has 1 to 4 carbon atoms. R
^If the carbon number of both ² and R ³ exceeds 4, the water resolubility of the anti-redeposition agent tends to be insufficient.

In the group represented by-(R ⁴ O) _m- (AO) _n H, R ⁴ represents a 2-hydroxypropylene group, and m represents 0 or 1. Here, if m is 0,
It is preferable because the re-contamination prevention property tends to be further improved. A represents an alkylene group having 2 to 4 carbon atoms. As such an alkylene group, specifically, an ethylene group,
Although a propylene group and a butylene group are mentioned, an ethylene group is particularly preferable. When the alkylene group is an ethylene group, the water solubility of the anti-redeposition agent tends to be further improved. And n is the number of moles of addition of alkylene oxide (AO), and represents an integer such that the total number of n in the general formula [1] is 1 to 10, preferably 2 to 8.

Further, in the general formula [1], Z is a linear hydrocarbon group having 1 to 22 carbon atoms which may have a substituent or the following formula:-(BO) _pH (where B is Represents an alkylene group having 2 to 4 carbon atoms, and p represents an integer of 1 to 5), or an aromatic hydrocarbon group having 7 to 10 carbon atoms which may have a substituent. And the substituent includes a hydroxyl group, an epoxy group, a methyl group, an ethyl group and the like.

[0020] Here, a chain hydrocarbon group having 1 to 22 carbon atoms which may have a substituent or a - (BO) substituent represented by _p H is branched be straight And may be, for example, a methyl group, an ethyl group, a propyl group, an amyl group, an octyl group, a lauryl group, a stearyl group, a behenyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group , An allyl group, a 2-methylallyl group, a 2,3-epoxypropyl group, a 2-hydroxyethoxyethyl group, and the like. Among these, a chain hydrocarbon group having 1 to 4 carbon atoms is particularly preferred in that the resulting surfactant has good water solubility.

Further, the compound may have 7 carbon atoms which may have a substituent.
The aromatic hydrocarbon groups of 10 to 10 are represented by the following formula [2]:

[0022]

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(Wherein R ⁵ , R ⁶ and R ⁷ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and r represents an integer of 1 to 3). It is represented. The term "C7-10" as used herein refers to the total number of carbon atoms in the aromatic ring as the main skeleton and the substituent.

There is no particular limitation on such Z,
Benzyl group, phenylethyl group, phenylpropyl group,
Examples include a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, an ethylbenzyl group, and a propylbenzyl group.

In the above Z, if any one of a methyl group, an ethyl group, a 2-hydroxyethyl group, an allyl group, a 2,3-epoxypropyl group and a benzyl group is represented by the general formula [1] It is particularly preferred because the synthesis of the compounds represented is very easy. Z can be introduced into a tertiary amine using a quaternizing agent in the method for producing a cationic surfactant described below.

Further, in the general formula [1], X ⁻ represents an anion (anion). Here, X ⁻ is not particularly limited, and examples thereof include a halide ion, an alkyl sulfate ion, a sulfate ion, a nitrate ion, a chlorite ion, a phosphate ion, a p-toluenesulfonic acid ion, a benzenesulfonic acid ion, or Sulfate ion and the like. The compound represented by the general formula [1] can be produced by a conventionally known method and comprises a tertiary amine having R ¹ and a quaternary ammonium salt for converting the tertiary amine into a quaternary ammonium salt. It can be obtained by reacting with a grading agent.

[0027] Here, although not particularly limited as tertiary amines, for example, with respect to the primary amine to 1 mole with R ^1, tertiary amines obtained by reacting an alkylating agent 2 moles, R ¹ And a tertiary amine obtained by reacting 1 mol of an alkylating agent with 1 mol of a secondary amine having the formula Incidentally, R ¹ in the tertiary amines and represent the same definition in the above formula [1].

The alkylating agent is not particularly restricted but includes, for example, a halide represented by the general formula RY (R
Is a group having 1 carbon atom corresponding to R ² or R ³ in the above formula [1].
-22, Y represents a halogen atom such as a chlorine atom or a bromine atom), dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, alkylene oxides having 2 to 4 carbon atoms, epichlorohydrin, 3-chloro And propanol and 1-chloro-2-propanol. Here, the halide represented by the general formula RY is not particularly limited, but specifically, methyl chloride, methyl bromide, ethyl chloride, ethyl iodide, butyl chloride, t chloride
Alkyl halides such as -butyl and octyl chloride; alkenyl halides such as allyl chloride; When an alkylene oxide is used as the alkylating agent, after reacting 2 moles of the alkylene oxide with respect to 1 mole of the primary amine and 1 mole of the alkylene oxide with respect to 1 mole of the secondary amine, The alkylene oxide chain can be extended in the presence of an alkali such as potassium hydroxide. Further, the quaternizing agent is not particularly limited, but specifically, a halide represented by the general formula RY [R is a hydrocarbon group (preferably having 1 to carbon atoms)
And Y represents a halogen atom such as a chlorine atom or a bromine atom]; an alkylene oxide having 2 to 4 carbon atoms; epichlorohydrin; 3-chloropropanol, 1-chloro-2-propanol and the like. Chloropropanol; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; benzyl chloride, methylbenzyl chloride, dimethylbenzyl chloride, trimethylbenzyl chloride, phenylethyl chloride, phenylpropyl chloride and the like. Here, specific examples of the halide represented by the formula RY include alkyl halides such as methyl chloride, methyl bromide, ethyl chloride, ethyl iodide, butyl chloride, t-butyl chloride, and octyl chloride; And alkenyl halides such as allyl chloride.

When an alkylene oxide is used as the quaternizing agent, the tertiary amine is converted to a nitrate, chlorite, phosphate or sulfate, and then quaternized with the alkylene oxide. Become Thereby, Z in the general formula [1] becomes-(BO) _p H,
X ^- represents a nitrate ion, a chlorite ion, a phosphate ion, and a sulfate ion, respectively.

The recontamination inhibitor of the present invention is obtained by dissolving one or more selected from the above cationic surfactants in water, an alcoholic solvent such as methanol or ethanol, or acetone, if necessary. Can be obtained. Here, the content of the cationic surfactant in the anti-redeposition agent is not particularly limited, but the content of the cationic surfactant is preferably 0.5 to 100% by weight, and particularly preferably 1 to 70% by weight. % By weight. If the content of the cationic surfactant is less than 0.5% by weight, the effect of preventing re-contamination may be insufficient. On the other hand, when the content of the cationic surfactant exceeds 70% by weight, the re-contamination inhibitor often solidifies, and the workability may be deteriorated.

The anti-redeposition agent of the present invention may further include, if necessary, a nonionic surfactant such as an ethylene oxide adduct of a higher alcohol as an emulsifier, in addition to the cationic surfactant. Other components such as a cationic surfactant such as an ammonium salt; an antifoaming agent may be contained, but the total amount of these other components is 0 to 10% by weight based on the total amount of the re-staining agent. Is preferred. Even when the total amount of these other components exceeds 10%, there is little improvement in the performance such as emulsifying property and defoaming property, and there is a possibility that the fastness is reduced.

The method for applying the anti-soil refining agent of the present invention to a cellulosic textile substrate is not particularly limited.
The treatment can be performed using a conventionally known immersion method or padding method.

The treatment bath used in these treatment methods is preferably prepared so that the concentration of the cationic surfactant in the anti-redeposition agent is 0.01 to 10% by weight. The concentration of the cationic surfactant in the treatment bath is 0.01
If the amount is less than 10% by weight, the effect of preventing re-contamination may be insufficient, and even if the amount is more than 10% by weight, the effect of preventing re-contamination tends to be insufficient. As the solvent used in the treatment bath, water or a mixed solvent of water and a water-soluble solvent such as acetone, methanol, and ethanol can be used, but water is most preferably used.

Further, the anti-redeposition agent of the present invention can be used simultaneously with or after the fix treatment. Here, the fixing agent used in the fixing process is not particularly limited, and a conventionally known fixing agent can be used. Specific examples of such a fixing agent include a polyethylene polyamine-based fixing agent, a dicyandiamide-based fixing agent, and a polycation-based fixing agent. Further, the treatment bath used for the fix treatment has a non-volatile content contained in the fix agent of 0.1%.
It is preferable to adjust the amount to be from 0.01 to 10% by weight. If the content of the non-volatile components in the fixing agent is less than 0.01% by weight, the fastness may be insufficient.
Even when used in an amount exceeding 0% by weight, there is a possibility that the effect of improving the fastness corresponding to the used amount may not be obtained.

In the present invention, as a raw material of the cellulosic fiber product substrate treated by the above method, natural fibers such as cotton and hemp; regenerated fibers such as rayon, polynosic, cupra; semi-synthetic fibers such as acetate; And the like. A fiber selected from the group consisting of a composite fiber using these cellulosic fibers; natural fibers such as silk and wool; a polyamide synthetic fiber such as nylon; a polyester synthetic fiber; an acrylonitrile synthetic fiber; And composite fibers.

[0036] The cellulosic fiber product of the present invention treated by such a method has high re-staining resistance and high fastness. The cellulosic fiber product is provided with a cellulosic fiber, a fixing agent and a redeposition inhibitor, and the content of the anti-redeposition agent in the cellulosic fiber product is such that the cationic surfactant is 0.01 to 10%.
It is preferable that the content be in the range of weight%. If the content of the anti-redeposition agent is less than 0.01% by weight, the anti-redeposition effect may be insufficient. There is a tendency that it cannot be obtained. Further, the content of the fixing agent in the cellulosic fiber product is preferably in a range where the nonvolatile content is 0.01 to 10% by weight. If the content of the fixing agent is less than 0.01% by weight, the fastness may be insufficient, and if it exceeds 10% by weight, there is a tendency that no improvement in the fastness corresponding to the amount used is observed. .

[0037]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to these examples.

(Preparation of Fabric to be Treated) In the following Examples and Comparative Examples, printed cotton twill and fluorescent whitening cotton twill obtained by the following methods were used as fabrics to be treated.

(A) Printing treatment A cotton twill (100% cotton) was printed (printed) with a printing dye having the following formulation using an automatic screen printing machine. In each printing dye including dye 1 or 2, sodium alginate, printing paste, urea,
A solution prepared so that the total amount of baking soda, dye and water was 100 parts by weight was used.

Formula of printing dye: Sodium alginate: 30.0 parts by weight Printing paste (ST-1, manufactured by Nichika Chemical Co., Ltd.): 20.0
Parts by weight Urea: 5.0 parts by weight Baking soda: 2.5 parts by weight Dye: Dye 1 (Kayacation Red P-4BN 25
% By weight): 20 parts by weight or Dye 2 (Cibacron Blue P-3R):
0.5 part by weight Next, the obtained cotton twill was dried at 100 ° C for 2 minutes, and then heat-treated at 130 ° C for 7 minutes by a high-temperature steamer. Thereafter, the cotton twill was washed with hot water at 60 ° C. for 5 minutes, washed with water for 5 minutes, and dried to obtain a printed cotton twill.

(B) Fluorescent whitening treatment In a 0.5% by weight Kayahole BRKL (fluorescent dye) solution,
A cotton twill (100% cotton) was padded using a mangle (pickup: 100%), and dried at 100 ° C. for 1 minute with a pin tenter to obtain a fluorescent whitened cotton twill.

Example 1 70.2 g of dimethylstearylamine, 60 g of water and 40 g of isopropyl alcohol were placed in a 300 ml four-necked flask, heated to 80 ° C., and 29.8 g of dimethyl sulfuric acid was added dropwise at 80 to 90 ° C. . After the completion of dropping, at 90 ° C 1
After reacting for hours, stearyltrimethylammonium methosulfate was obtained. This compound was diluted to prepare a 36% by weight aqueous solution to obtain a re-contamination inhibitor.

Next, in 97.5 parts by weight of water, 0.5 part by weight of the obtained anti-redeposition agent, Neofix KM-11 (polycationic fixing agent, nonvolatile content 25% by weight, Nichika Chemical Co., Ltd.) 2) parts by weight are mixed to prepare a treatment liquid, and the printed cotton twill (two types obtained using dyes 1 and 2) and the fluorescent whitening cotton twill are mangled with this treatment liquid. Padding was performed (pickup: 100%). Remove each cotton twill after padding using a pin tenter.
After drying at 10 ° C. for 1 minute, a test cloth was obtained.

Example 2 Stearylamine (134.5 g) was weighed into a test autoclave (manufactured by Pressure Glass Co., Ltd.) and dehydrated at 110 ° C. under reduced pressure. Thereafter, the inside of the autoclave was returned to normal pressure with nitrogen gas, and at 150 ° C., 44 g of ethylene oxide was added to the stearylamine. After completion of the reaction, the reaction solution was cooled to 60 ° C.
g was added, and dehydration under reduced pressure was again performed at 110 ° C. Then, the inside of the autoclave was returned to normal pressure with nitrogen gas, and
At 0 ° C., 44 g of ethylene oxide was further added to obtain a 4 mol ethylene oxide adduct of stearylamine. 77.8 g of this adduct, 60 g of water and 40 g of isopropyl alcohol were placed in a 300 ml four-necked flask and heated to 80, and 22.2 g of benzyl chloride was added dropwise within the range of 80 to 90 ° C, and 90 ° C was added. For 3 hours to obtain a compound represented by the following formula [3]. This compound was diluted to prepare a 36% by weight aqueous solution to obtain a re-contamination inhibitor.

[0045]

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Next, in the same manner as in Example 1 except that the antistaining agent obtained by the above synthesis was used instead of the antistaining agent obtained in Example 1, the printed cotton twill and the fluorescent A test cloth treated with whitened cotton twill was obtained.

Example 3 59.4 g of dimethyl laurylamine, 60 g of water and 40 g of isopropyl alcohol were weighed into a test autoclave (manufactured by Pressure Glass Co., Ltd.), and the weight of the solution was 62% by weight at 45 ° C. or lower. 28.3 g of nitric acid were added dropwise. After dropping, 110 ° C
And dehydrated under reduced pressure at 110 ° C. afterwards,
The autoclave is returned to normal pressure with nitrogen gas,
Then, 12.3 g of ethylene oxide was reacted to obtain a compound represented by the following formula [4]. A 36% by weight aqueous solution of this compound was prepared to obtain a re-contamination inhibitor.

[0048]

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Next, in the same manner as in Example 1 except that the redeposition inhibitor obtained by the above synthesis was used in place of the redeposition inhibitor obtained in Example 1, printed cotton twill and fluorescent A test cloth treated with whitened cotton twill was obtained.

Example 4 58 g of dimethylstearylamine, 60 g of water and 40 g of isopropyl alcohol were weighed in a test autoclave (manufactured by Pressure Glass Co., Ltd.), and paratoluenesulfonic acid was obtained at a temperature of 45 ° C. or lower. After dropping 4 g, the temperature was raised to 110 ° C, and dehydration under reduced pressure was performed at 110 ° C. Thereafter, the inside of the autoclave was returned to normal pressure with nitrogen gas, and 8.6 g of ethylene oxide was reacted at 150 ° C. to obtain a compound represented by the following formula [5]. A 36% by weight aqueous solution of this compound was prepared to obtain a re-contamination inhibitor.

[0051]

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Next, in the same manner as in Example 1 except that the antistaining agent obtained by the above synthesis was used instead of the antistaining agent obtained in Example 1, the printed cotton twill and the fluorescent A test cloth treated with whitened cotton twill was obtained.

Example 5 Stearylamine (134.5 g) was weighed into a test autoclave (manufactured by Pressure Glass Co., Ltd.) and dehydrated at 110 ° C. under reduced pressure. Then, the inside of the autoclave was returned to normal pressure with nitrogen gas, and at 150 ° C., 44 g of ethylene oxide was added to stearylamine. After completion of the reaction, the reaction solution was cooled to 60 ° C., 0.7 g of potassium hydroxide was added thereto, and dehydration was performed again at 110 ° C. under reduced pressure. Then, after returning the inside of the autoclave to normal pressure with nitrogen gas,
At 44 ° C., 44 g of ethylene oxide was further added to obtain a 4-mol adduct of stearylamine with ethylene oxide. 222.5 g of this adduct, 300 g of water and 46.3 g of epichlorohydrin were placed in a four-necked flask at 95 ° C.
For 3 hours to obtain a compound represented by the following formula [6]. A 36% by weight aqueous solution of this compound was prepared and used as a re-contamination inhibitor.

[0054]

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Next, the printed cotton twill and the fluorescent dye were prepared in the same manner as in Example 1 except that the anti-redeposition agent obtained in the above synthesis was used in place of the anti-redeposition agent obtained in Example 1. A test cloth treated with whitened cotton twill was obtained.

Example 6 A four-necked flask was charged with 84 g of AOE X-68 (1,2-epoxyalkane having 16:18 carbon atoms and 57:43, manufactured by Daicel Corporation) and heated to 120 ° C. Warm,
Diethanolamine 35 in a temperature range of 120 to 150 ° C.
After dropping g, the mixture was reacted at 150 ° C. for 1 hour. After the reaction, 150 g of water was added to the reaction solution, the temperature was raised to 90 ° C., and 42.2 g of benzyl chloride was added dropwise.
The mixture was reacted at a temperature of 3 ° C. for 3 hours to obtain a compound represented by the following formula [7]. A 36% by weight aqueous solution of this compound was prepared and used as a re-contamination inhibitor. In the following formula [7], R represents a myristyl group or a palmityl group.

[0057]

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Next, in the same manner as in Example 1 except that the anti-redeposition agent obtained by the above synthesis was used in place of the anti-redeposition agent obtained in Example 1, the printed cotton twill and the fluorescent A test cloth treated with whitened cotton twill was obtained.

Example 7 134.5 g of sterylamine and 125 g of monoglycidyl ether of tetraethylene glycol were placed in a four-necked flask and reacted at 100 ° C. for 3 hours. 260 g of the obtained reaction product was placed in a test autoclave (manufactured by Pressure-resistant Glass Industry Co., Ltd.) and dehydrated under reduced pressure at 110 ° C. Then, the inside of the autoclave is returned to normal pressure with nitrogen gas, and
At 50 ° C., 22 g of ethylene oxide was added. 282 g of this adduct and 300 g of water were put into a four-necked flask, 63 g of dimethyl sulfate was added dropwise at 95 ° C., and the mixture was reacted at 95 ° C. for 3 hours to obtain a compound represented by the following formula [8].
A 36% by weight aqueous solution of this compound was prepared to obtain a re-contamination inhibitor.

[0060]

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Next, in the same manner as in Example 1 except that the antistaining agent obtained by the above synthesis was used instead of the antistaining agent obtained in Example 1, the printed cotton twill and the fluorescent A test cloth treated with whitened cotton twill was obtained.

Comparative Example 1 Neofix KM-11 was used instead of the treating solution of Example 1.
A printed cotton twill and a cotton twill were prepared in the same manner as in Example 1 except that a 2.0% by weight aqueous solution of an aqueous solution (polycationic fixing agent, nonvolatile content: 25% by weight, manufactured by Nika Chemical Co., Ltd.) was used as a treatment liquid. A test cloth treated with a fluorescent whitening cotton twill was obtained.

Comparative Example 2 Using a 2% by weight aqueous solution of Neofix KM-11 (polycationic fixing agent, non-volatile content: 25% by weight, manufactured by Nika Chemicals Co., Ltd.) as a treatment liquid, printed cotton twill, fluorescence Whitening twill is padded with a mangle (pickup: 100%), and the whitening is performed using a pin tenter.
After drying at 1 ° C. for 1 minute, water was added to Dispatex G (Tamol-based anionic surfactant, manufactured by Nichika Chemical Co., Ltd.) to dilute it, and a re-contamination inhibitor having a nonvolatile content of 36% by weight was added. The printed cotton twill and the fluorescent whitening twill obtained by the above treatment are further padded using a 0.5% by weight aqueous solution of the re-staining inhibitor (pick-up: 100%). -Using 11
After drying at 0 ° C. for 1 minute, a test cloth was obtained.

Using the test cloths of Examples 1 to 8 and Comparative Examples 1 and 2 thus obtained, the following evaluation tests were performed.

Evaluation Test 1 for Prevention of Recontamination Using the test cloth treated with the printed cotton twill prepared using Dye 2 and obtained in Examples 1 to 7 and Comparative Examples 1 and 2, An evaluation test for the prevention of recontamination was performed.

A test cloth and 10 stainless steel hard balls were put into 200 mL of a treatment liquid prepared to be 5 g / L of artificial contaminated liquid and 0.7 g / L of attack (detergent, manufactured by Kao Corporation). It was treated at 50 ° C. for 30 minutes using an O-meter (SJK Round Lee Tester, manufactured by Showa Heavy Industries) and then dried to obtain a treated cloth. The artificial contaminants include artificial oil stains (15 parts by weight of stearic acid, 15 parts by weight of oleic acid, 15 parts by weight of bovine fatty acid, 15 parts by weight of olive oil, 10 parts by weight of cetyl alcohol, 5 parts by weight of cholesterol, and 140 F paraffin 25 A mixture of parts by weight) 5
A mixture obtained by mixing 5 parts by weight, 5 parts by weight of Tada type C-carbon, 20 parts by weight of an anionic surfactant (BH-320K, manufactured by Nika Chemical Co., Ltd.) and 70 parts by weight of water was used.

For each of the treated cloths thus obtained, an integrating sphere photometer spectrophotometer (CM-
L * value (brightness index) was determined by measuring the reflectance using 3700d (manufactured by Minolta). Table 1 shows the results.
Here, a large L * value indicates that the treated cloth is not contaminated.

Test 2 for evaluating anti-soil re-staining The test for evaluating anti-soil re-staining shown below was carried out using the test cloth treated with the fluorescent white cotton twill obtained in Examples 1 to 7 and Comparative Examples 1 and 2. went.

100 mL of a treatment solution prepared so as to have a dye decomposition solution of 10 g / L and Marcel soap of 0.7 g / L.
, A test cloth and 10 stainless steel hard balls were put therein, treated at 50 ° C. for 30 minutes using a round o meter (SJK Round Lee Tester, manufactured by Showa Heavy Industries), and then dried. It should be noted that Kayacation Red is included in the dye decomposition solution.
A solution of P-4BN (5 g / L) and soda ash (20 g / L) was heated at 90 ° C. for 1 hour, allowed to stand for 15 hours, and then neutralized to pH = 7.0-8.0 by adding acetic acid. The used solution was used.

The L ^* value of each of the treated cloths thus obtained was calculated in the same manner as in the anti-redeposition property 1. Table 1 shows the results.

Wet fastness evaluation test Using the test cloth treated with the printed cotton twill prepared using Dye 1 and obtained in Examples 1 to 7 and Comparative Examples 1 and 2, the following wet fastness was used. A degree evaluation test was performed.

In this test, the fastness to sweat and fastness over time were evaluated. Each of the fastnesses was evaluated on a 5-point scale of 1 to 5, and the larger the value, the better the fastness. In addition, the evaluation test of sweat fastness is based on JIS L-0848.
(Alkali perspiration), and the evaluation test of the fastness over time was carried out by subjecting each test cloth to a heat treatment at 115 ° C. for 1 hour with a high-pressure steamer, assuming a lapse of time.
Performed according to -0846. Table 1 shows the results.

[0073]

[Table 1]

As shown in Table 1, the test cloths using the anti-redeposition agents of Examples 1 to 7 exhibited a high level of effect on both the anti-redeposition property and the fastness. In the test cloths using the anti-redeposition agents of Nos. 1 and 2, either of the anti-redeposition property and the fastness were insufficient.

[0075]

As described above, according to the present invention,
Post-processing steps such as softener treatment and fluorescent dye application treatment by treating the cellulosic fiber product base material simultaneously with or after the fix treatment, while maintaining the original fastness improving effect of the fix agent And water washing after treatment, a recontamination inhibitor for cellulose fiber capable of imparting recontamination prevention property during repeated washing, and the recontamination inhibitor and the fixing agent in the cellulosic fiber product base material Thus, a cellulosic fiber product is obtained.

Claims (5)

[Claims] (1) at least one carbon atom having 4 to 2 carbon atoms in the molecule;
2. A re-contamination inhibitor comprising a cationic surfactant derived from a monoamine having a chain hydrocarbon group of No. 2. 2. The anti-redeposition agent according to claim 1, wherein the cationic surfactant is a compound having a structure represented by the following general formula [1]. Embedded image [Wherein, R ¹ represents a chain hydrocarbon group having 4 to 22 carbon atoms, R ² and R ³ may be the same or different, and a chain hydrocarbon group having 1 to 22 carbon atoms or the following formula: _{^{: - (R 4 O) m}} - (AO) in _n H (wherein, R ⁴ represents 2-hydroxy propylene group, a
Represents an alkylene group having 2 to 4 carbon atoms, m represents 0 or 1, and n represents an integer such that the total number of n in the above formula [1] is 1 to 10. Wherein Z is a linear hydrocarbon group having 1 to 22 carbon atoms which may have a substituent or the following formula:-(BO) _p H (where B is an alkylene group having 2 to 4 carbon atoms) And p represents an integer of 1 to 5), or an aromatic hydrocarbon group having 7 to 10 carbon atoms which may have a substituent, and X ⁻ represents an anion. ] 3. A cellulosic fiber product comprising: a cellulosic fiber product base material; and a fixing agent and a re-contamination inhibitor contained in the cellulosic fiber product base material, wherein the re-contamination prevention agent comprises: A cellulosic fiber product containing a cationic surfactant derived from a monoamine having at least one chain hydrocarbon group having 4 to 22 carbon atoms in a molecule. 4. The cellulosic fiber product according to claim 3, wherein the cationic surfactant is a compound having a structure represented by the following general formula [1]. Embedded image [Wherein, R ¹ represents a chain hydrocarbon group having 4 to 22 carbon atoms, R ² and R ³ may be the same or different, and a chain hydrocarbon group having 1 to 22 carbon atoms or the following formula: _{^{: - (R 4 O) m}} - (AO) in _n H (wherein, R ⁴ represents 2-hydroxy propylene group, a
Represents an alkylene group having 2 to 4 carbon atoms, m represents 0 or 1, and n represents an integer such that the total number of n in the above formula [1] is 1 to 10. Wherein Z is a linear hydrocarbon group having 1 to 22 carbon atoms which may have a substituent or the following formula:-(BO) _p H (where B is an alkylene group having 2 to 4 carbon atoms) And p represents an integer of 1 to 5), or an aromatic hydrocarbon group having 7 to 10 carbon atoms which may have a substituent, and X ⁻ represents an anion. ] 5. A cationic surfactant wherein the cellulosic fiber product is derived from a monoamine having at least one chain hydrocarbon group having 4 to 22 carbon atoms in a molecule at the same time as or after the fix treatment. The cellulosic fiber product according to claim 3 or 4, wherein a cellulose-based fiber product base material is impregnated with a re-contamination inhibitor containing.