JP4997180B2 - Textile processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for treating a fiber product by which excellent softening effects can be imparted even in a state in which the amount of cleaning water or rinsing water based on the fiber product is little, and the rinsing is not carried out sufficiently. <P>SOLUTION: The method for treating the fiber product includes (a) 0.1-20 ppm of a macromolecular compound containing specific monomer units (A) and (B) in a specified molar ratio, (b) 10-300 ppm of one of more kinds of compounds selected from a specific tertiary amine or an acid salt thereof and a quaternary ammonium salt, and (c) 3-200 ppm of a calcium ion and/or a magnesium ion to be contained in the rinsing water, when treating the fiber product by a cleaning step for cleaning the fiber product by using the cleaning water containing water and an anionic surfactant in a mass ratio of the fiber product to the cleaning water regulated so as to be from 1/3 to 1/15, and a rinsing step for rinsing the fiber product after the cleaning step with the rinsing water in a mass ratio of the fiber product to the rinsing water regulated so as to be from 1/3 to 1/15. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for treating textile products such as clothing.

Techniques for improving softness performance by blending a cationic polymer with a softening agent used for softening treatment of textile products such as clothing are well known (Patent Documents 1 and 2). It is also known to blend a soft polymer with a cationic polymer (Patent Document 3) or as a defloc polymer for viscosity adjustment (Patent Document 4).
International Publication No. 2004/025017 Pamphlet Special Table 2000-503735 Japanese Patent Laid-Open No. 6-228883 JP-A-4-228680

  In recent years, from the viewpoint of resource saving / energy saving, in general household washing, there is a strong tendency to reduce the amount of water used for washing and rinsing. Especially, drum-type washing machines have a small amount of washing water and rinsing water for clothes. Rinsing may not be sufficient. When the softening process is performed at a stage where rinsing is not sufficient, there arises a problem that an expected softening effect cannot be obtained. In this respect, Patent Documents 1 to 4 do not specifically mention any means that can provide an excellent softening effect even if the rinsing is not sufficient.

  Therefore, the subject of this invention is providing the processing method of the textiles which can provide the outstanding softness | flexibility effect even if the quantity of the washing water with respect to textiles and the amount of rinsing water is small and rinsing is not fully performed. .

  The present invention relates to a washing process for washing a textile product at a mass ratio of textile product / washing water = 1/3 to 1/15 using washing water containing water and an anionic surfactant, and a washing process. And a rinsing step for rinsing the subsequent textile product at a mass ratio of 1/3 to 1/15 of the textile product / rinsing water, wherein at least part of the rinsing step The fiber product is rinsed in the presence of 0.1 to 20 ppm of the following (a) component, 10 to 300 ppm of the following (b) component, and 3 to 200 ppm of the following (c) component: Regarding the method.

<(A) component>
A monomer unit (A) derived from a compound represented by the following general formula (1) or an acid salt thereof, and a monomer unit (B) derived from a compound represented by the following general formula (2) are represented by (A) / { (A) + (B)} = A polymer compound contained in a molar ratio of 0.2 to 1.0.

[In the general formula ^{(1), R 1, R} 2 each independently represent a hydrogen atom or a methyl group, R ³ is -COOM (M represents a hydrogen atom, or an alkali metal atom) is shown, or hydrogen atom. X represents —COO—R ⁶ —, —CONR ⁷ —R ⁸ —, or —CH ₂ —. R ⁴ has the general formula (3) when X is —CH ₂ —.

When X is other than that, it represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. R ⁵ represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. R ⁶ and R ⁸ each independently represents an alkyl group having 2 to 3 carbon atoms, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

In [Formula ^{(2), R 11, R} 12 are each independently a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, Y is an aryl ^{group, -O-CO-R 13,} -COO-R ^14, or an -CONR ¹⁵ -R ^16. R ¹³ , R ¹⁴ , and R ¹⁶ each independently represent a linear, branched, or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms, or an arylalkyl group having 6 to 14 carbon atoms in total, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

<(B) component>
One or more compounds selected from the following (b-1) component and (b-2) component.
(B-1) Component: Tertiary amine represented by general formula (4) or its acid salt (b-2) Component: Quaternary ammonium salt represented by general formula (5)

[Wherein, R ^10b , R ^12b , R ^15b and R ^17b are each independently an alkyl group or alkenyl group having 8 to 36 carbon atoms, and R ^11b , R ^13b , R ^16b and R ^18b are each independently An alkylene group having 1 to 6 carbon atoms, R ^14b is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a group represented by the formula R ^10b — [ ^{DR 11b} ] _c —, and R ^19b is An alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a group represented by the formula R ^15b — [F—R ^16b ] _e —, and R ^20b is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. , D, E, F and G are each independently a group selected from -COO-, -OCO-, -CONH- and -NHCO-, and c, d, e and f are each independently 0 or 1 Z ⁻ is an anionic group. ]

<(C) component>
One or more ions selected from calcium ions and magnesium ions

  ADVANTAGE OF THE INVENTION According to this invention, the processing method of the textile product which can provide the outstanding softness | flexibility effect to a textile product also by the process on washing conditions in which detergent components, such as an anionic surfactant, remain in rinsing water is provided.

<(A) component>
The component (a) is a monomer unit (A) derived from the compound represented by the general formula (1) or the acid salt thereof, and the lower limit is 20 mol% in the total of the monomer unit (A) and the monomer unit (B). Or more, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, and the upper limit is 100 mol% or less. is there. Among the compounds represented by the general formula (1) that are derived from the monomer unit (A), the compound in which X in the general formula (1) is —COO—R ⁶ — includes acrylic acid N, N— Dimethylaminoethyl, N, N-dimethylaminomethyl acrylate, N, N-dimethylaminobutyl acrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-methacrylate Dimethylaminomethyl, N, N-dimethylaminobutyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminomethyl acrylate, N, N-diethylaminobutyl acrylate , N, N-diethylaminopropyl acrylate, N, N-diethylaminoethyl methacrylate, meta Acrylic acid N, N-diethylaminomethyl, methacrylate N, N-diethylamino-butyl, methacrylate N, N-diethylaminopropyl and the like.

In addition, among the compounds represented by the general formula (1), as the compound in which X in the general formula (1) is —CONR ⁷ —R ⁸ —, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) ) Amide, N, N-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminobutylacrylic acid (or methacrylic acid) amide Etc.

Further, X in the formula (1) is -CH ₂ - For, R ⁴ is a group represented by the general formula (3). Examples of such a compound include diallylamine.

  As the compound represented by the general formula (1), an acid salt or a quaternary salt thereof can be used. Examples of the acid salt include neutral salts of inorganic salts such as primary, secondary, and tertiary amine hydrochlorides and sulfates, and neutral salts of various organic acids.

  Moreover, as a compound represented by General formula (2) from which a monomer unit (B) originates, alkyl acrylate (C1-C22) ester, such as lauryl acrylate, butyl methacrylate, methyl methacrylate, lauryl methacrylate, etc. And alkyl methacrylate (having 1 to 22 carbon atoms), styrene and the like.

  Component (a) is a monomer unit derived from a copolymerizable unsaturated bond-containing monomer [monomer (C)] [monomer unit (C)] as a monomer unit other than the monomer units (A) and (B). You may have in the range which does not impair the effect of invention. Examples of the monomer (C) include acrylamide, vinyl alcohol; (meth) acrylic acid ester having a hydroxyalkyl group having 1 to 22 carbon atoms such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylamide, or (meta ) Acrylamide; polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate (ethylene glycol polymerization degree 1 to 100), polypropylene glycol (meth) acrylate (propylene glycol polymerization degree) 1-50), polyalkylenes such as polybutylene glycol (meth) acrylate (the degree of polymerization of butylene glycol is 1-50) (alkylene having 1 to 8 carbon atoms; linear (Branch) (meth) acrylic acid ester having an oxide chain; (meth) acrylic acid ester of polyhydric alcohol such as glycerin (meth) acrylate; diacetone (meth) acrylamide; N-vinyl cyclic such as N-vinylpyrrolidone Amide; N- (meth) acryloylmorpholine; Vinyl chloride; Acrylonitrile; Vinyl compounds having a carboxyl group such as (meth) acrylic acid, maleic acid, itaconic acid, styrene carboxylic acid; 2-acrylamido-2-methylpropanesulfonic acid And vinyl compounds having a sulfonic acid group such as styrene sulfonic acid. The copolymerization amount of these monomers (C) is 80% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of monomers.

  The component (a) is a monomer unit (A) and a monomer unit (B) of (A) / {(A) + (B)} = 0.2 to 1.0, preferably 0 from the viewpoint of flexibility. It is contained in a molar ratio of 0.7 to 1.0, more preferably 0.8 to 0.95.

  The weight average molecular weight (Mw) of the component (a) is preferably 2,000 to 1,000,000, more preferably 3,000 to 500,0000, and particularly preferably 5,000 to 200,000. The ratio Mw / Mn between Mw and Mn is preferably 1.0 to 40, more preferably 1.5 to 35.

  In addition, the value by gel permeation chromatography (GPC) measurement is used for Mw and Mw / Mn of the component (a) of the present invention. As an eluent, any one of water, alcohol, chloroform, dimethylformamide, tetrahydrofuran, acetonitrile and a combination of these solvents is used, and the molecular weight is converted to polyethylene oxide or polystyrene.

At that time, when the polymer to be measured is considered to be relatively hydrophilic with a large proportion of monomer units (A), a mixed solvent of (1% acetic acid / ethanol): water = 3: 7 (mass ratio) Using a LiBr 50 mmol / L solution prepared in step 1 as a solvent, two GPC columns “α-M (manufactured by Tosoh Corp.)” for polar solvents are used in series, and the molecular weight in terms of polyethylene glycol is calculated (measurement method A). ). On the other hand, when the proportion of the monomer unit (B) such as (a-4) used as a comparative polymer in Examples described later is large and the polymer is considered to be relatively hydrophobic, Farmin DM20 (Kao ( 2) GPC column for organic solvents “K-804 (manufactured by Showa Denko KK)” was used in series with a 1 mmol / L-CHCl ₃ solution (manufactured by Kogyo Co., Ltd.), and the molecular weight in terms of polystyrene was calculated (measurement). Law B).

<(B) component>
The component (b) of the present invention is one or more compounds selected from the following components (b-1) to (b-2), and these are selected from an amino group and a quaternary ammonium group in the molecule. And a compound having a hydrocarbon group having 8 to 42 carbon atoms.

(B-1) Component: Tertiary amine represented by general formula (4) or its acid salt (b-2) Component: Quaternary ammonium salt represented by general formula (5)

[Wherein, R ^10b , R ^12b , R ^15b and R ^17b are each independently an alkyl group or alkenyl group having 8 to 36 carbon atoms, and R ^11b , R ^13b , R ^16b and R ^18b are each independently An alkylene group having 1 to 6 carbon atoms, R ^14b is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a group represented by the formula R ^10b — [ ^{DR 11b} ] _c —, and R ^19b is An alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a group represented by the formula R ^15b — [F—R ^16b ] _e —, and R ^20b is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. , D, E, F and G are each independently a group selected from -COO-, -OCO-, -CONH- and -NHCO-, and c, d, e and f are each independently 0 or 1 Z ⁻ is an anionic group. ]

In the component (b-1), R ^10b and R ^12b in the general formula (4) are each independently an alkyl group or an alkenyl group having 8 to 36, preferably 8 to 24, more preferably 13 to 24 carbon atoms. And particularly preferably an alkyl group having 8 to 18 carbon atoms, more preferably an alkyl group having 13 to 18 carbon atoms or an alkenyl group having 16 to 20 carbon atoms. R ^11b and R ^13b are each independently preferably an alkylene group having 1 to 4 carbon atoms, particularly preferably an ethylene group or a propylene group. c and d are preferably 1, and D and E are each independently preferably —COO— and / or —CONH—. R ^14b is preferably a methyl group, an ethyl group, a hydroxyethyl group, or a group represented by the formula R ^10b — [D—R ^11b ] _c —.

  The component (b-1) may be a salt (acid salt) neutralized with an inorganic or organic acid. Moreover, when using as an acid salt, the thing which neutralized the amino group with the acid agent before mix | blending with rinsing water can also be used, and when preparing and using a softening agent composition, (b- 1) After blending the components, the amino group may be neutralized with an acid agent. As the acid for neutralization, hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, hydroxycarboxylic acid, fatty acids having 1 to 12 carbon atoms, alkyl sulfuric acids having 1 to 3 carbon atoms, and aromatic sulfonic acids are preferable, particularly hydrochloric acid and sulfuric acid. Glycolic acid and p-toluenesulfonic acid are preferred. These acid agents used for neutralization may be used alone or in combination.

In the component (b-2), R ^15b and R ^17b in the general formula (5) are each independently an alkyl group or an alkenyl group having 8 to 36 carbon atoms, preferably 8 to 24 carbon atoms, particularly preferably. An alkyl group having 8 to 18 carbon atoms is more preferably an alkyl group having 13 to 18 carbon atoms or an alkenyl group having 16 to 20 carbon atoms. R ^16b and R ^18b are each independently preferably an alkylene group having 1 to 4 carbon atoms, particularly preferably an alkylene group having 2 or 3 carbon atoms. e and f are preferably 1, and F and G are each independently preferably —COO— and / or —CONH—. R ^19b is preferably a methyl group, an ethyl group, a hydroxyethyl group, or a group represented by the formula R ^15b — [F—R ^16b ] _e —. R ^20b is preferably a methyl group, an ethyl group, or a hydroxyethyl group. Z ⁻ is substituted with an anion group, preferably a halogen ion, a sulfate ion, a phosphate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. One or more selected from aryl sulfonate ions which may be present.

  As a more preferable compound among (b-1) component, as a compound represented by General formula (4-1)-(4-3) and a more preferable compound among (b-2) component, General formula ( The compounds represented by 5-1) to (5-3) can be mentioned.

[In the formula, R is an alkyl group or alkenyl group having 9 to 21 carbon atoms, preferably an alkyl group or oleyl group having 9 to 16 carbon atoms, i and j are 2 or 3, and R ′ is methyl. A group, an ethyl group, a hydroxyethyl group or a group represented by the formula R—COO (CH ₂ ) _i —, wherein R ″ is a methyl group, an ethyl group or a hydroxyethyl group, and Z ⁻ is the same as described above. Is the meaning. ]

  Furthermore, the component (b) of the present invention is selected from the group consisting of the component (b-1) and the component (b-2) from the viewpoint of the flexibility effect. Alternatively, the component (b-1) and the component (b-2) may be used in combination. When used in combination, the mass ratio of the component (b-1) / (b-2) is preferably 1/1000 to 1000/1.

Of the component (b) of the present invention, the compound represented by the general formula (5) is produced by subjecting the compound represented by the general formula (4) to a quaternization reaction using an alkylating agent. be able to. The compound represented by the general formula (4) is a hydrocarbon group of a fatty acid or a fatty acid lower alkyl (alkyl group having 1 to 3 carbon atoms) ester so that R ^10b and R ^12b have a preferable composition as described above. A composition is selected, and a raw fatty acid or a fatty acid lower alkyl (alkyl group having 1 to 3 carbon atoms) having a specific mole number having such a composition and a corresponding alkanolamine are subjected to dehydration esterification or transesterification. Can be manufactured.

  Examples of the alkanolamine include a dialkylmonoalkanolamine (preferably dimethylmonoethanolamine or dimethylmonopropanolamine), a monoalkyldialkanolamine (preferably methyldiethanolamine or methyldipropanolamine), or a trialkanolamine (preferably triethanol). Amine or tripropanolamine), but is not limited thereto. A particularly preferred alkanolamine is trialkanolamine.

  In order to obtain a fatty acid or a fatty acid lower alkyl ester having the above-mentioned preferred hydrocarbon composition, it cannot be achieved simply by using a fatty acid as commonly known in oil and fat manuals, etc., but isomerization reaction of unsaturated bonds, or those Can be obtained by mixing the fatty acids.

  Further, in order to control the content of unsaturated hydrocarbon groups having two or more double bonds in the raw fatty acid or fatty acid lower alkyl ester, for example, crystallization as described in JP-A-4-306296 A method of distilling methyl ester as described in JP-A-6-41578, a selective hydrogenation reaction as described in JP-A-8-99036, and the like can be performed.

  In the esterification reaction or transesterification reaction, the molar ratio of the fatty acid or fatty acid lower alkyl ester to the hydroxy group of the alkanolamine is preferably 0.3: 1.0 to 1.2: 1.0, 0.5: 1 0.0-1.0: 1.0 is more preferable.

  Examples of the alkylating agent used in the quaternization reaction of the compound represented by the general formula (5) include dialkyl sulfate (alkyl group having 1 to 3 carbon atoms), alkyl halide (alkyl group having 1 to 3 carbon atoms). Etc.

  In addition, the quaternization reaction using an alkylating agent can be synthesized even in the presence of a solvent (for example, ethanol), but from the viewpoint of the softening effect and / or the suppression of the generation of impurities, it is synthesized without a solvent. More preferred.

<(C) component>
The component (c) of the present invention is one or more ions selected from calcium ions and magnesium ions. Calcium ions and magnesium ions may be supplied as hardness components in tap water. As described later, in the present invention, it is important to adjust the component (c) in the rinsing water to a specific concentration. For that purpose, the water-soluble calcium salt and / or the water-soluble magnesium salt, preferably calcium chloride and It is preferable to add magnesium chloride to the rinsing water and adjust the calcium ion concentration and the magnesium ion concentration together with the hardness component. In adding calcium chloride and / or magnesium chloride to rinsing water, it is known that the hardness component varies depending on the region, environment, and season. Therefore, in order to exert a preferable softening effect in the present invention, In order to complement the hardness component of (a), even if it uses what added 0.5-10 mass% of water-soluble calcium salt and / or water-soluble magnesium salt in the composition containing (a) component and (b) component good.

<Processing method for textile products>
When using a softener in a washing process, it is common to add a softener to rinsing water and perform a softening process simultaneously with a rinsing process. The method of the present invention can be carried out accordingly. From the viewpoint of resource saving and energy saving, in recent years, washing and rinsing are performed under conditions where the mass ratio of washing water and rinsing water is low for textile products such as clothing. In such a case, the washing component remains in the rinsing water (the amount of the washing component transferred from the laundry etc. increases in the water supplied as the rinsing water), and in particular, the anionic surface activity that is the main component of the detergent When the agent is present, the expected effect cannot be sufficiently obtained even if the softening treatment is performed by adding the softening agent to the rinsing water. In particular, such a tendency is remarkable in the drum-type washing machines that have been widely used in the market in recent years. The present invention provides a method for obtaining an excellent softening effect even in such a poorly rinsed state. The method of the present invention includes washing of a textile product and softening treatment of the textile product, and can be carried out by being incorporated into a washing process in a general household. Furthermore, the method of the present invention is suitable for washing using a drum-type washing machine and flexible processing.

  That is, using a washing water prepared from a detergent containing an anionic surfactant, particularly a detergent containing 10 to 30% by mass of an anionic surfactant and water, textile product / washing water = 1/3 to 1 / 20, preferably washed at a mass ratio of 1/5 to 1/15 (washing step), followed by textile / rinsing water = 1/3 to 1/20, preferably 1/5 to 1/15 An excellent softening effect can be imparted at the time of washing having a rinsing step (rinsing step). The mass ratio of the textile product and washing water and the mass ratio of the textile product and rinsing water are washing conditions that are often employed when using a drum-type washing machine. 2 to 50 ppm, further 5 to 50 ppm, more preferably 8 to 50 ppm, particularly 8 to 30 ppm of an anionic surfactant, particularly an alkylbenzenesulfonic acid having 10 to 15 carbon atoms and / or a salt thereof, in the rinsing water. (A) It has a great influence on the flexibility effect by inhibiting the adsorption of the component. As the detergent used in the washing step of the present invention, those known as ordinary clothing detergents and the like can be used. As described above, detergents containing a predetermined amount of an anionic surfactant, A detergent containing alkylbenzene sulfonic acid or a salt thereof as an ionic surfactant is preferred.

  The present invention is a method capable of imparting an excellent softening effect even under such poor rinsing conditions. For example, when the anionic surfactant concentration in the rinsing water is 2 to 50 ppm at the start of the rinsing process It is effective for. In the present invention, the component (a) in the rinsing water is 0.1 to 20 ppm, preferably 0.3 to 15 ppm, particularly preferably 0.5 to 10 ppm, and the component (b) is 10 to 300 ppm, preferably 12 to 250 ppm. Particularly preferably, the fiber product is rinsed in the presence of 15 to 200 ppm and component (c) in the range of 3 to 200 ppm, preferably 5 to 150 ppm, more preferably 10 to 100 ppm, and particularly preferably 30 to 100 ppm. It is sufficient that these concentrations be at least at the start of the rinsing process. Further, when a plurality of rinsing steps are performed, rinsing water containing the components (a) to (c) at these predetermined concentrations may be used in at least one rinsing step. The concentration of the component (c) in the rinsing water can be measured by a chelate titration method using EDTA. Taking an actual washing process as an example, (1) using a washing water containing an anionic surfactant, washing the textile product at the textile product / washing water mass ratio in the washing machine, 2) After discharge (drainage, dehydration) of washing water, water is poured into the washing machine so that the mass ratio of the above-mentioned textile product / rinsing water is obtained, and (3) component (c) has a predetermined concentration as required. (4) The components (a) and (b) are added to water to a predetermined concentration, and the fibers are rinsed with rinse water containing the components (5) (a) to (c). A method of rinsing the product is mentioned. In the present invention, the concentration of the anionic surfactant in the rinsing water is the amount before the rinsing water comes into contact with the textile product before the components (a), (b) and (c) are present in the above-mentioned concentration range. In the stage, 2 to 50 ppm, further 2 to 30 ppm, further 5 to 30 ppm, particularly 8 to 30 ppm is preferable. In addition, this anionic surfactant density | concentration is (a)-(c) component by predetermined density | concentration, when using a rinsing bath (a rinsing bath is comprised including the textiles and water after washing | cleaning). It can be easily measured as the concentration of the water portion in the rinsing bath prior to being present.

  In adding the component (a) and the component (b) to the rinse water, it is preferable to prepare and add a composition (softener composition) containing the component (a) and the component (b). By blending the component (a) and the component (b) in the same composition and adding them to the rinsing water, an excellent softening effect is imparted without inhibiting the adsorption of the component (a) even under poor rinsing conditions. I can do it. In addition, as above-mentioned, (c) component can be mix | blended with this composition as needed. The composition may be a liquid composition containing water.

  In the present invention, the mass ratio of the component (a) to the component (b) in the rinsing water is 5/1000 to 5/10, and further 2/100 to 2/10, as the component (a) / (b). Is preferred. The molar ratio of the amino group of the component (a) to the component (b) and the anionic surfactant in the rinsing water is 100/1 to 1 / ({(a) + (b)} / anionic surfactant). 1, more preferably 50/1 to 1/1.

  The textiles processed through the washing process and the rinsing process can be dehydrated / naturally dried or heat dried. Examples of the textile product that is the subject of the present invention include clothing using towels, towels, sheets, bedding, and the like.

  The present invention relates to a washing process for washing a textile product at a mass ratio of textile product / washing water = 1/3 to 1/15 using washing water containing water and an anionic surfactant, and a washing process. And a rinsing step of rinsing the subsequent textile product at a mass ratio of 1/3 to 1/15 of the textile product / rinsing water, wherein at least part of the rinsing step As a method for washing textile products, the textile product is softened in the presence of (a) component at 0.1 to 20 ppm, (b) component at 10 to 300 ppm, and (c) component at 3 to 200 ppm. Can be implemented.

  According to the present invention, a textile product is immersed in a processing medium containing (a) component at 0.1 to 20 ppm, (b) component at 10 to 300 ppm, and (c) component at 3 to 200 ppm. Provided is a method for softening a fiber product, wherein the mass ratio of the fiber product to the processing medium is 1/3 to 1/15 of the fiber product / processing medium. Is done. Such a treatment medium may have an anionic surfactant concentration of 2 to 50 ppm.

  Further, according to the present invention, the component (a) is 0.1 to 5% by mass, preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and the component (b) is 5 to 30%. % By mass, preferably 8 to 25% by mass, more preferably 10 to 25% by mass, 0.5 to 10% by mass of water-soluble calcium salt and / or water-soluble magnesium salt as a source of component (c), preferably Is contained in an amount of 0.5 to 5% by mass, more preferably 1 to 3% by mass, and the mass ratio of the component (a) to the component (b) is 5/1000 to 5 / (a) component / (b) component. The softening agent composition which can be used suitably for the processing method of this invention which is 10 / preferably 2/100-2/10 is provided.

Below, the synthesis example of (a) component and a comparative polymer is shown.
(Synthesis Example 1)
42.37 g of N, N-dimethylaminoethyl methacrylate (molecular weight: 157.21), 7.62 g of lauryl methacrylate (molecular weight: 254.41) and 180.0 g of ethanol are uniformly mixed and put into a glass separable flask having an internal volume of 300 mL. The mixture was stirred for a certain time under a nitrogen atmosphere. Thereto was added a solution prepared by dissolving 1.41 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65; manufactured by Wako Pure Chemical Industries, Ltd.) in 20.0 g of ethanol, and around 60 ° C. The temperature was raised to. Polymerization and aging were carried out by maintaining the temperature at around 60 to 70 ° C. for a total of 8 hours. 100.0 g of ethanol was added and diluted there, and then the temperature was lowered to room temperature. This reaction solution was dropped into 4000.0 g of ion-exchanged water and purified by reprecipitation, and the precipitate was dried to obtain polymer 1. The Mw of polymer 1 was 11000. (Water / ethanol = 7/3 system, converted to polyethylene oxide) The composition of polymer 1 analyzed by ¹ H-NMR was the same as the charged monomer composition (DMAEMA / LMA = 9/1 (molar ratio)).

(Synthesis Example 2) After that, a polymer having the following composition (molar ratio) and molecular weight was obtained by changing the monomer used in the same manner as in (Synthesis Example 1).
(Synthesis example 2) Poly DMAEMA Mw: 11200, Mw / Mn: 2.5
(Synthesis Example 3) DMAEMA / LMA = 7/3, Mw: 7800, Mw / Mn: 6.5
(Synthesis Example 4) LMA alone <Comparison> Mw: 85700, Mw / Mn: 4.8

The above abbreviations have the following meanings.
DMAEMA: N, N-dimethylaminoethyl methacrylate LMA: lauryl methacrylate

<Measurement of polymers Mw and Mn>
Mw and Mn were measured by the measurement method A described above. However, (a-4) (the symbols will be described later) was performed by the above-described measurement method B.

Below, the synthesis example of (b) component is shown.
(Synthesis Example 4)
A fatty acid prepared by mixing stearic acid and palmitic acid at a molar ratio of 6/4 and N- (3-alkanoylaminopropyl) -N- (2-hydroxyethyl) -N-methylamine at a molar ratio of 1.8 / 1. After mixing, dehydration condensation was performed according to a conventional method. When the acid value reached 9, the reaction was stopped to obtain a condensate. The total amine number of this condensate was measured. This condensate was heated to 70 ° C. and melted. To this condensate, 9 times the amount of ion-exchanged water (65 ° C.) is added, and while stirring, 35% aqueous hydrochloric acid solution necessary for neutralization, calculated based on the total amine value, is added dropwise to the water. The mixture was neutralized with and stirred for 10 minutes, and then cooled to 30 ° C. Next, this compound was freeze-dried to obtain the target amine salt compound.

(Synthesis Example 5)
Perform dehydration condensation reaction according to a conventional method iodine value 90gI ₂ / 100g, a raw material fatty acid and triethanolamine from rapeseed oil having an acid value 201MgKOH / g at a reaction molar ratio 1.85 / 1 (fatty acid / triethanolamine), condensation I got a thing. Next, in the absence of a solvent, 0.95 equivalent of dimethylsulfuric acid was used for this condensate and quaternization was performed by a conventional method, followed by dilution to 90% with ethanol to obtain the desired quaternary ammonium salt. A salt mixture was obtained.

The blending components of the softener composition used in the examples are summarized below.
-(A) component:
(A-1) Polymer obtained in Synthesis Example 1 (a-2) Polymer obtained in Synthesis Example 2 (a-3) Polymer obtained in Synthesis Example 3

(B) Component (b-1): Amine salt compound obtained in Synthesis Example 4 (b-2): Quaternary ammonium salt mixture obtained in Synthesis Example 5

(C) Component source (c-1) Calcium chloride (c-2) Magnesium chloride

<Method for Preparing Liquid Softener Composition>
A 300 mL beaker was charged with 95% of the amount of ion-exchanged water necessary for the finished mass of the softening agent composition to be 200 g, and the temperature was raised to 60 ° C. in a water bath. While stirring with a turbine-type stirring blade having three stirring blades each having a length of 2 cm (300 r / m), the required amount of components (a) and (b) are added, and stirring is performed for 5 minutes. Thereafter, the pH is adjusted to 2 to 4 with a 35.5% hydrochloric acid aqueous solution, and if necessary, a source of component (c) is added, and then the amount of ions at 60 ° C. necessary for the final mass is obtained. Exchange water was added. Thereafter, the mixture was stirred for 10 minutes, the beaker was transferred to a water bath containing 5 ° C. water, and cooled to 20 ° C. while stirring.

<Flexibility evaluation method>
(Flexible processing method)
Using a face towel (100% cotton, 30cm x 75cm, approx. 70g / sheet) so as to have the mass shown in Table 1, a washing machine (Drum-type washing machine VR manufactured by Matsushita Electric Industrial Co., Ltd.) with a test detergent -1100 (abbreviated as (A) in the table) or Toshiba Corporation fully automatic washing machine AW-F80HVP (abbreviated as (B) in the table) (detergent concentration 0.0667 mass%, water temperature 20 ° C.) 10 minutes) Here, the detergent for the test is “Patent Office Gazette Known and Conventional Technique Collection (Powder Detergent for Clothing)” (issued March 26, 1998), page 57, “4.13 Composition Example”. In “Composition Example 1”, a detergent (other ingredients) using an alkylbenzenesulfonic acid Na (hereinafter referred to as LAS) having an alkyl group having 10 to 15 carbon atoms (average carbon number of 11.8) as LAS-Na Use conventional ingredients). Tap water was used as the wash water, and ion-exchanged water was used as the rinse water.After washing using the standard course of each washing machine, the rinse water was collected for LAS concentration measurement at the final rinse (2 times in total). The liquid softener composition was added so that the components (a), (b), and (c) would have the concentrations shown in the table. Evaluation was made by the following method.

The LAS concentration in the rinsing water was determined by performing HPLC analysis under the following conditions on the rinsing water collected immediately before the set amount of rinsing water was poured into the washing machine and the softener composition was added.
Column: Lichrospher100 RP-18 (e) (5μm, 4mm id × 250mm)
Mobile phase: Ammonium acetate was added to a acetonitrile / water = 55/45 solution to a final concentration of 10 mM. UV detection wavelength: 225 nm, flow rate: 1.0 ml / min, column temperature: 40 ° C., injection volume: 5 μl

(Flexibility evaluation)
The flexibility of the treated towel was determined by 10 panelists (10 men in their 30s) according to the following criteria, and the average score of 10 people was calculated. An evaluation score of 2.0 or higher shows a good flexibility effect, and a difference of 0.4 evaluation score can be recognized as a dominant difference.
-1 ... It is not finished softer than the towel treated by the method of Comparative Example 1.
0: Equivalent to the towel treated by the method of Comparative Example 1.
1 ... Finished slightly softer than the towel treated by the method of Comparative Example 1.
2 ... Finished softer than the towel treated by the method of Comparative Example 1.
3 Finished very softly compared with the towel treated by the method of Comparative Example 1.

Claims (2)

A washing process for washing a textile product with a mass ratio of textile product / washing water = 1/3 to 1/15 using washing water containing water and an anionic surfactant, and fibers after the washing process And a rinsing step for rinsing the product at a mass ratio of 1/3 to 1/15, wherein at least part of the rinsing step includes the following (a ) The fiber product is treated by rinsing the fiber product in a concentration of 0.1 to 20 ppm, the following component (b) at 10 to 300 ppm, and the following component (c) at a concentration of 3 to 200 ppm.
<(A) component>
A monomer unit (A) derived from a compound represented by the following general formula (1) or an acid salt thereof, and a monomer unit (B) derived from a compound represented by the following general formula (2) are represented by (A) / { (A) + (B)} = A polymer compound contained in a molar ratio of 0.2 to 1.0.

[In the general formula ^{(1), R 1, R} 2 each independently represent a hydrogen atom or a methyl group, R ³ is -COOM (M represents a hydrogen atom, or an alkali metal atom) is shown, or hydrogen atom. X represents —COO—R ⁶ —, —CONR ⁷ —R ⁸ —, or —CH ₂ —. R ⁴ has the general formula (3) when X is —CH ₂ —.

When X is other than that, it represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. R ⁵ represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. R ⁶ and R ⁸ each independently represents an alkyl group having 2 to 3 carbon atoms, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

In [Formula ^{(2), R 11, R} 12 are each independently a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, Y is an aryl ^{group, -O-CO-R 13,} -COO-R ^14, or an -CONR ¹⁵ -R ^16. R ¹³ , R ¹⁴ , and R ¹⁶ each independently represent a linear, branched, or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms, or an arylalkyl group having 6 to 14 carbon atoms in total, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]
<(B) component>
One or more compounds selected from the following (b-1) component and (b-2) component.
(B-1) Component: Tertiary amine represented by general formula (4) or its acid salt (b-2) Component: Quaternary ammonium salt represented by general formula (5)

[Wherein, R ^10b , R ^12b , R ^15b and R ^17b are each independently an alkyl group or alkenyl group having 8 to 36 carbon atoms, and R ^11b , R ^13b , R ^16b and R ^18b are each independently An alkylene group having 1 to 6 carbon atoms, R ^14b is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a group represented by the formula R ^10b — [ ^{DR 11b} ] _c —, and R ^19b is An alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a group represented by the formula R ^15b — [F—R ^16b ] _e —, and R ^20b is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. , D, E, F and G are each independently a group selected from -COO-, -OCO-, -CONH- and -NHCO-, and c, d, e and f are each independently 0 or 1 Z ⁻ is an anionic group. ]
<(C) component>
One or more ions selected from calcium ions and magnesium ions The anionic surfactant concentration in the rinsing water is in a stage after the rinsing water comes into contact with the textile product and before the components (a), (b) and (c) are present in the above range of concentrations, The method for treating a textile product according to claim 1, wherein the amount is 2 to 50 ppm.