JP2001288680A - Anti-soil redeposition agent, and cellulosic fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-soil redeposition 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 process 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 redeposition agent and the fixing agent in the substrate of the cellulosic fiber product. SOLUTION: This anti-soil redeposition agent characterized by containing an amphoteric 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 re-staining agent for cellulosic fibers which prevents or reduces reattachment of pollutants, and a cellulosic fiber product containing the re-staining agent 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, the cellulosic fiber products that have been subjected to the fix treatment may have softening treatments, fluorescent dye application treatments, and other post-processing steps, and during washing with water or repeated washing after the treatment, the textiles may become lightly stained, have no clear color, or have a white spot. There are problems such as darkening 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 is intended to improve the original robustness of the fixing agent by performing the processing simultaneously with or after the fixing processing. While maintaining the improvement effect, a softening agent treatment, a post-processing step such as a fluorescent dye application treatment or a 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, It is another object of the present invention to provide a cellulosic fiber product containing the re-staining agent and the fixing agent in a cellulosic fiber product base material.

[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 a cellulosic fiber simultaneously with or after fixation treatment using a re-staining inhibitor containing an amphoteric 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.
2. An amphoteric surfactant derived from a monoamine having two chain hydrocarbon groups.

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 an amphoteric surfactant derived from a monoamine having two linear hydrocarbon groups having 4 to 22 carbon atoms.

According to the present invention, a fix treatment is carried out using an anti-staining agent containing an amphoteric 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 fibers at the same time or after the fix treatment, the re-attachment 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 amphoteric surfactant is preferably a compound having any one of the following general formulas [1] to [3].

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

[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 a chain hydrocarbon group having 1 to 22 carbon atoms. Or the following formula:-(BO) _m H (wherein B represents an alkylene group having 2 to 4 carbon atoms, and m represents an integer such that the total number of m in the formula [1] is 1 to 10. ) represents a substituent represented by, R ⁴ represents an alkylene group having 1 to 4 carbon atoms which may have a substituent, R ⁵
Represents a hydrogen atom or a chain hydrocarbon group having 1 to 22 carbon atoms; R ⁶ represents an alkylene group having 2 to 4 carbon atoms which may have a substituent; n represents 0 or 1; Is carbon number 2
Represents an alkylene group of 4 to 4, p represents an integer of 1 to 10, and M represents a hydrogen atom or an alkali metal atom. ]

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The redeposition inhibitor of the present invention contains an amphoteric surfactant derived from a monoamine having a chain hydrocarbon group having 4 to 22 carbon atoms, and is preferably a betaine-type amphoteric surfactant. It contains a surfactant or an amino acid type amphoteric surfactant. When the amphoteric surfactant is a betaine-type amphoteric surfactant or an amino acid-type amphoteric surfactant, a higher anti-redeposition property tends to be obtained.

Here, the betaine-type amphoteric surfactant is an internal salt type surfactant having a quaternary ammonium (cation) and a carboxyl group (anion) in the molecule, and is preferably a surfactant. The following general formula [1]:

[0017]

Embedded image

A compound having a structure represented by the following formula:

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 a chain hydrocarbon group is not particularly limited, for example, butyl group, amyl group, hexyl group, 2-ethylhexyl group, octyl group, lauryl group,
Myristyl, palmityl, stearyl, eicosyl, behenyl, oleyl, elaidyl, 4-hydroxybutyl, 2-hydroxyoctadecyl, 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 each is represented by a chain hydrocarbon group having 1 to 22 carbon atoms or represented by the following formula:-(BO) _m H. Represents a group to be formed. 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-(BO) _m H, B represents an alkylene group having 2 to 4 carbon atoms. Specific examples of such an alkylene group include an ethylene group, a propylene group, and a butylene group, and 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 m is the number of moles of alkylene oxide (BO) added, and the total number of m in the general formula [1] is 1 to
Represents an integer such as 10, preferably 2 to 8.

Further, in the general formula [1], R ⁴ represents an alkylene group having 1 to 4 carbon atoms which may have a substituent.
Such alkylene groups are not particularly limited,
Examples include a methylene group, an ethylene group, a propylene group, and a group represented by the following formula: —CH (COOM) CH ₂ — (M represents a hydrogen atom or an alkali metal atom).

The compound represented by the general formula [1] can be produced by a conventionally known method. For example, a tertiary amine obtained by reacting 1 mol of a primary amine having R ¹ with 2 mol of an alkylating agent, and reacting 1 mol of a primary amine having R ¹ with 1 mol of an alkylating agent the compound obtained Te further tertiary amine obtained by adding ethylene oxide to the primary amine or secondary amine having R ¹ tertiary amine obtained by adding an alkylene oxide, the R ¹ A tertiary amine obtained by reacting 1 mol of a secondary amine having 1 mol of an alkylating agent,
It can be obtained by reacting one or more tertiary amines selected from tertiary amines having R ¹ with an amphoteric agent. In the above tertiary amines, R ¹ has the same definition as in the above formula [1]. The alkylating agent is not particularly limited, for example,
A halide represented by the general formula RY (R: a chain hydrocarbon group having 1 to 22 carbon atoms described in R ² and R ³ , Y:
Halogen atoms such as chlorine and bromine atoms), dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, and C2-C2
Alkylene oxide of 4, epichlorohydrin, 3-
Chloropropanol, 1-chloro-2-propanol and the like can be mentioned. The halide represented by the above general formula RY is not particularly limited, and examples thereof 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.

Here, the amphoteric agent used in the above-mentioned production method is not particularly limited, and specifically, monochloroacetic acid, monochlorobutyric acid, monochlorosuccinic acid, maleic acid, fumaric acid, salts and acid anhydrides thereof, β-propiolactone and the like.

The amino acid type amphoteric surfactant, which is another preferred amphoteric surfactant according to the present invention, comprises:
The following general formula [2] or [3]:

[0026]

Embedded image

[0027]

Embedded image

It is preferable that the compound has a structure represented by the following formula.

Here, R ¹ in the above formulas [2] and [3]
And R ⁴ represent the same definitions as R ¹ and R ⁴ in the above formula [1], respectively.

In the above formula [2], R ⁵ represents a hydrogen atom or a chain hydrocarbon group having 1 to 22 carbon atoms, and the chain hydrocarbon group is represented by R ² and R ³ in the above formula [1]. This is the same definition content as. Here, R ⁵ is a hydrogen atom or carbon number 1 to
It is preferably a chain hydrocarbon group of No. 4. When R ⁵ is a chain hydrocarbon group having 5 or more carbon atoms, the water solubility of the anti-redeposition agent tends to be insufficient.

In the above formula [3], R ⁶ is an alkylene group having 2 to 4 carbon atoms which may have a substituent.
A 2-hydroxypropylene group. N represents 0 or 1. A is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group. p is the number of moles of the alkylene oxide added, and is an integer of 1 to 10, preferably 2 to 8.

The compound represented by the general formula [2] can be obtained by a conventionally known method. Specifically, R ¹
And 1 mol of at least one amine selected from the group consisting of a primary amine having R ¹ and a secondary amine obtained by reacting 1 mol of a primary amine having R ¹ with 1 mol of an alkylating agent. A method of reacting 1 mol of an amphoteric agent with one or more amines selected from the group consisting of the above and the above amines and an acrylate such as acrylonitrile or methyl acrylate, and then an alkali such as sodium hydroxide. And a reaction method. Here, the amphoteric agent is not particularly limited, and specific examples thereof include monochloroacetic acid, monochlorobutyric acid, monochlorosuccinic acid, maleic acid, fumaric acid, salts and acid anhydrides thereof, and β-propiolactone. Can be

The compound represented by the general formula [3] is
It can be obtained by a conventionally known method. In particular,
First with R ^1; acrylonitrile to a primary amine having the R ^1, is reacted with acrylic acid esters such as methyl acrylate, a method of reacting by adding an alkali such as sodium hydroxide after further adding an alkylene oxide A method of reacting an acrylate ester such as acrylonitrile or methyl acrylate with a secondary amine, further reacting monoglycidyl ether of polyethylene glycol with an alkali such as sodium hydroxide, and the like.

When the amphoteric surfactant contained in the anti-redeposition agent of the present invention is a compound having a structure of any of the above formulas [1] to [3], the effect of improving the fastness of the fixing agent is improved. It is preferable because a higher effect of preventing re-contamination can be obtained without reducing the amount. Among these amphoteric surfactants, the compound represented by the above formula [1] is particularly preferable.

The recontamination inhibitor of the present invention may comprise one or more selected from the amphoteric surfactants, if necessary,
Water; an alcoholic solvent such as methanol and ethanol; and acetone. here,
The content of the amphoteric surfactant in the anti-redeposition agent is not particularly limited.
It is preferably from 5 to 100% by weight, especially from 1 to 70% by weight.
% By weight. When the content of the amphoteric surfactant is less than 0.5% by weight, the effect of preventing re-contamination may be insufficient. When the content of the amphoteric surfactant is 7
If it exceeds 0% by weight, the re-staining agent often solidifies, and the workability may deteriorate.

The anti-redeposition agent of the present invention may further comprise, if necessary, a nonionic surfactant such as an ethylene oxide adduct of a higher alcohol as an emulsifier in addition to the amphoteric 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.

There is no particular limitation on the method of applying the anti-redeposition agent of the present invention to a cellulosic fiber product base material.
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 amphoteric surfactant in the restaining inhibitor is 0.01 to 10% by weight. The concentration of the amphoteric surfactant in the treatment bath is 0.01% by weight
If it is less than 10%, the effect of preventing re-contamination may be insufficient, and even if it is used in an amount of more than 10% by weight, the effect of preventing re-contamination may not be obtained in proportion to the amount used. 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 at the same time as 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 tendency that the effect of improving the fastness corresponding to the used amount cannot 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.

The cellulosic fiber product of the present invention treated by such a method has a high anti-recontamination property and a high fastness. The cellulosic fiber product is provided with a cellulosic fiber, a fixing agent and a redeposition inhibitor, and the content of the redeposition inhibitor in the cellulosic fiber product is such that the content of the amphoteric surfactant is 0. .0
The content is preferably in the range of 1 to 10% by weight. When the content of the amphoteric surfactant is less than 0.01% by weight, the anti-redeposition property may be insufficient.
When used in excess, the effect of preventing re-contamination corresponding to the amount used tends not to be obtained. The content of the fixing agent in the cellulosic fiber product is preferably such that the non-volatile content contained in the fixing agent 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, the improvement of the fastness corresponding to the amount used tends not to be obtained. In addition, the form of such a cellulosic fiber product base material is not particularly limited, and examples thereof include yarn, woven fabric, mixed woven fabric, knitted fabric, and nonwoven fabric.

[0042]

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 Cloth 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 cloth 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 dye for printing: Sodium alginate: 30.0 parts by weight Paste for printing (ST-1, manufactured by Nichika Chemical Co., Ltd.): 20.0 parts by weight Urea: 5.0 parts by weight Baking soda: 2 0.5 parts by weight Dye: Dye 1 (25% by weight aqueous solution of Kayacation Red P-4BN): 20 parts by weight, or Dye 2 (Cibacron Blue P-3R): 0.5 parts 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 using 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 92.5 parts by weight of laurylamine was placed in a test autoclave (manufactured by Pressure Glass Co., Ltd.), dehydrated under reduced pressure at 110 ° C., and then nitrogen gas was used to remove the inside of the autoclave. Was returned to normal pressure, and 44 parts by weight of ethylene oxide was added to the laurylamine at 150 ° C. to obtain a 2-mol ethylene oxide adduct of laurylamine. This compound 66.1
g and 30 g of water were placed in a 300 mL four-necked flask and heated to 90 ° C., and then sodium monochloroacetate 3 was added.
An aqueous solution in which 3.9 g was dissolved in 70 g of water was added dropwise. After the completion of the dropwise addition, the mixture was reacted at 95 to 100 ° C. for 3 hours to obtain lauryl dihydroxyethyl betaine. 3 of this compound
A 6% by weight aqueous solution was prepared to obtain a recontamination inhibitor.

Next, 0.5 parts by weight of the obtained anti-redeposition agent, 97.5 parts by weight of water, and Neofix KM-11
(Polycationic fixing agent, nonvolatile content: 25%, manufactured by Nichika Chemical Co., Ltd.) was added to prepare 2 parts by weight of a treatment liquid, and cotton twill printed with this treatment liquid (using dyes 1 and 2) The obtained two types) and the fluorescent whitening cotton twill were padded with a mangle (pickup: 100%). Each cotton twill after padding is treated with a pin tenter.
After drying at 0 ° C. for 1 minute, a test cloth was obtained.

Example 2 Stearylamine (134.5 parts by weight) was weighed in a test autoclave (manufactured by Pressure Glass Co., Ltd.) and dehydrated at 110 ° C. under reduced pressure. Thereafter, the pressure inside the autoclave was returned to normal pressure with nitrogen gas, and at 150 ° C., 44 parts by weight of ethylene oxide was added to the stearylamine to obtain a 2-mol ethylene oxide adduct of stearylamine. 71.7 g of this compound and 40 g of water were placed in a 300 mL four-necked flask, heated to 90 ° C., and an aqueous solution in which 28.3 g of sodium monochloroacetate was dissolved in 60 g of water was added dropwise. After the completion of the dropwise addition, the mixture was reacted at 95 to 100 ° C. for 3 hours to obtain stearyl dihydroxyethyl betaine. A 36% by weight aqueous solution of this compound was prepared to obtain a recontamination inhibitor.

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 Stearylamine (134.5 parts by weight) 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 parts by weight of ethylene oxide was added to the stearylamine. After completion of the reaction, the reaction solution was cooled to 60 ° C., 0.7 parts by weight of potassium hydroxide was added thereto, and dehydration was performed again at 110 ° C. under reduced pressure. After the inside of the autoclave was returned to normal pressure with nitrogen gas, 44 parts by weight of ethylene oxide was further added at 150 ° C. to obtain ethylene oxide 4 of stearylamine.
A molar adduct was obtained. 76 g of this compound and 50 g of water
The temperature was raised to 90 ° C. in a 00 mL four-necked flask, and then an aqueous solution in which 24 g of sodium monochloroacetate was dissolved in 50 g of water was added dropwise. After dropping, 95-100
The reaction was carried out at 3 ° C. for 3 hours to obtain stearyldi (hydroxyethoxyethyl) betaine. 36% by weight of this compound
An aqueous solution was prepared to obtain a recontamination inhibitor.

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 4 40 g of laurylamine was placed in a four-necked flask at 40 ° C.
After 18.8 g of methyl acrylate was added dropwise thereto, the mixture was reacted at 100 ° C. for 3 hours. After completion of the reaction, 123 g of water was added to the contents to form an aqueous solution.
Temperature, and 18.2 g of 48% sodium hydroxide
Was added and a saponification reaction was carried out at 70 ° C. for 3 hours to obtain sodium laurylaminopropionate. A 36% by weight aqueous solution of this compound was prepared to obtain a recontamination inhibitor.

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 92.5 g of laurylamine was placed in a four-necked flask, and
After the temperature was raised to 0 ° C., 43 g of methyl acrylate was added dropwise thereto, and then the temperature was raised to 100 ° C. and reacted for 3 hours. After completion of the reaction, all of the obtained compounds were transferred to 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 then, at 150 ° C., 22 g of ethylene oxide
Was reacted. After completion of the reaction, 160 g of water was added to make an aqueous solution. This aqueous solution was heated to 70 ° C., 41.7 g of a 48% aqueous sodium hydroxide solution was added, and a saponification reaction was carried out at 70 ° C. for 3 hours to give N-hydroxyethyl-lauryl. Sodium aminopropionate was obtained. 36% by weight of this compound
An aqueous solution was prepared to obtain a recontamination inhibitor.

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

Example 6 92.5 g of laurylamine was placed in a four-necked flask, and
After the temperature was raised to 0 ° C. and 43 g of methyl acrylate was added dropwise,
The temperature was raised to 100 ° C. and reacted for 3 hours. Next, 125 g of monoglycidyl ether of tetraethylene glycol was added to the reaction solution, and reacted at 90 ° C. for 3 hours. After the reaction is completed, 260 g of water is added to make an aqueous solution.
The temperature was raised to 0 ° C., 41.7 g of 48% sodium hydroxide was added, and a saponification reaction was performed at 70 ° C. for 3 hours to obtain a compound represented by the following formula [4]. A 36% by weight aqueous solution of this compound was prepared to obtain a recontamination inhibitor.

[0058]

Embedded image

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 7 AOE X-68 (C16: C18 = 57: 4
Α-alkylene oxide 3 (manufactured by Daicel Corporation) 8
4 g in a four-necked flask and heated to 120 ° C.
After dropping 35 g of diethanolamine at 20 to 150 ° C, the mixture was reacted at 120 to 150 ° C for 1 hour. After completion of the reaction, 77 g of water was added to the reaction solution, the temperature was raised to 90 ° C., and then, an aqueous solution in which 38.8 g of sodium monochloroacetate was dissolved in 83 g of water was added dropwise. After dropping, 95-10
The mixture was reacted at 0 ° C. for 3 hours to obtain a compound represented by the following formula [5]. A 36% by weight aqueous solution of this compound was prepared to obtain a recontamination inhibitor. In the formula [5], R represents a myristyl group or a palmityl group.

[0061]

Embedded image

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 8 Stearylamine (134.5 parts by weight) was weighed in a test autoclave (manufactured by Pressure Glass Industry 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 parts by weight of ethylene oxide was added to the stearylamine. After completion of the reaction, the reaction solution was cooled to 60 ° C., 0.7 parts by weight of potassium hydroxide was added thereto, and dehydration was performed again at 110 ° C. under reduced pressure. Thereafter, the inside of the autoclave was returned to normal pressure with nitrogen gas, and 44 parts by weight of ethylene oxide was further added at 150 ° C. to obtain a 4-mol ethylene oxide adduct of stearylamine. 222.5 g of this compound, water 34
0 g and 58 g of maleic acid were placed in a four-necked flask, and 9 g
The reaction was carried out at 5 ° 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 to obtain a recontamination inhibitor.

[0064]

Embedded image

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

[0066] 2 wt% Neofix K instead of the treatment liquid in Comparative Example 1 Example 1
M-11 (polycationic fixing agent, nonvolatile content 25
%, Manufactured by Nikka Chemical Co., Ltd.) in the same manner as in Example 1 except that an aqueous solution containing only 2% by weight was used as the treatment liquid.
A test cloth treated with printed cotton twill and fluorescent whitening cotton twill was obtained.

Comparative Example 2 Printed cotton twill using an aqueous solution containing only 2% by weight of Neofix KM-11 (polycationic fixing agent, non-volatile content: 25%, manufactured by Nikka Chemical Co., Ltd.) as a treatment liquid Fluorescent white cotton twill was padded with a mangle (pickup: 100%), dried at 110 ° C. for 1 minute using a pin tenter, and then treated with Dispatex G (Tamol-based anionic surfactant, Nichika Corporation). Diluted by adding water to Chemical Co., Ltd.)
Is prepared.
Using a 5% by weight aqueous solution, the printed cotton twill and the fluorescent whitening twill obtained by the above treatment are further padded (pickup: 100%) and dried at 110 ° C. for 1 minute using a pin tenter. Then, 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 by using Dye 2 and obtained in Examples 1 to 8 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 so as to have an artificial contaminated liquid of 5 g / L and an attack (detergent, manufactured by Kao Corporation) of 0.7 g / L. 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.

Evaluation Test of Anti- Resoil Prevention 2 Using the test cloth treated with the fluorescent whitening twill obtained in Examples 1 to 8 and Comparative Examples 1 and 2, the evaluation test of anti-soil redeposition shown below was carried out. 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 was calculated for each of the thus treated cloths 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 8 and Comparative Examples 1 and 2, the following wet fastness was used. A degree evaluation test was performed.

In this test, the sweat fastness and the 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.

[0077]

[Table 1]

As shown in Table 1, the test cloths using the anti-redeposition agents of Examples 1 to 8 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.

[0079]

As described above, according to the present invention,
By processing at the same time as or after the fixing process, while maintaining the original fastness improving effect of the fixing agent, a post-processing process such as a softening agent treatment, a fluorescent dye applying process or a water washing after the process, repeated. A re-staining inhibitor for cellulosic fibers capable of imparting anti-re-staining property at the time of washing, and a cellulosic fiber product containing the re-staining agent and the fixing agent in a cellulosic fiber product base material. Can be

Claims (5)

[Claims] (1) at least one carbon atom having 4 to 2 carbon atoms in the molecule;
2. A recontamination inhibitor comprising an amphoteric surfactant derived from a monoamine having a chain hydrocarbon group of 2. 2. The amphoteric surfactant according to the following general formula [1]
The anti-redeposition agent according to claim 1, which is a compound having a structure of any one of [3] to [3]. Embedded image Embedded image 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: :-(BO) _m H (wherein B represents an alkylene group having 2 to 4 carbon atoms, and m represents an integer such that the total number of m in the formula [1] is 1 to 10). is a substituted group, R ⁴ represents an alkylene group having 1 to 4 carbon atoms which may have a substituent, R ⁵
Represents a hydrogen atom or a chain hydrocarbon group having 1 to 22 carbon atoms; R ⁶ represents an alkylene group having 2 to 4 carbon atoms which may have a substituent; n represents 0 or 1; Is carbon number 2
Represents an alkylene group of 4 to 4, p represents an integer of 1 to 10, and M represents a hydrogen atom or an alkali metal atom. ] 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 an amphoteric surfactant derived from a monoamine having at least one chain hydrocarbon group having 4 to 22 carbon atoms in a molecule. 4. The amphoteric surfactant according to the following general formula [1]-
The cellulosic fiber product according to claim 3, which is a compound having any one of the structures of [3]. Embedded image Embedded image 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: :-(BO) _m H (wherein B represents an alkylene group having 2 to 4 carbon atoms, and m represents an integer such that the total number of m in the formula [1] is 1 to 10). is a substituted group, R ⁴ represents an alkylene group having 1 to 4 carbon atoms which may have a substituent, R ⁵
Represents a hydrogen atom or a chain hydrocarbon group having 1 to 22 carbon atoms; R ⁶ represents an alkylene group having 2 to 4 carbon atoms which may have a substituent; n represents 0 or 1; Is carbon number 2
Represents an alkylene group of 4 to 4, p represents an integer of 1 to 10, and M represents a hydrogen atom or an alkali metal atom. ] 5. An amphoteric surfactant wherein said cellulosic fiber product is derived from a monoamine having at least one chain hydrocarbon group having 4 to 22 carbon atoms in the molecule at the same time as or after the fix treatment. The cellulosic fiber product according to claim 3, wherein the cellulosic fiber is impregnated with a re-contamination inhibitor containing, and the amphoteric surfactant is adsorbed on the cellulose fiber. .