JP2001239086A - Cleaning assistant for washing and clothing washing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cleaning assistant for washing capable of easily and surely removing a dye eluted in washing and capable of improving cleaning power and a clothing washing method using it. SOLUTION: Clothes are washed by using this cleaning assistant for washing including fiber having an ion exchange group and a detergent composition including a nonionic surface active agent of HLB 10 to 17.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a washing aid for washing and a method for washing clothes using the same, and more particularly to a method for easily and surely removing dyes eluted during washing. Also, the present invention relates to a washing aid capable of improving washing power and a method for washing clothes using the same.

[0002]

2. Description of the Related Art Hitherto, in the field of cleaning, developments have been made mainly in terms of detergent compositions with respect to the prevention of dyeing of clothes (dyes) in clothes in a cleaning system. JP-A-151596 discloses a detergent having an effect of preventing dye transfer, comprising a surfactant having a structure in which an alkylene oxide is added to a higher aliphatic amine or β-naphthol. As for the detergency,
Conventionally, various inorganic substances (for example, zeolite) have been added to a detergent composition to trap divalent metal ions, particularly magnesium ions and calcium ions, in tap water in pores of zeolite, thereby improving detergency.

[0003] However, it has been found that the detergent composition has a problem in that the transfer of color to clothing such as white is not sufficiently prevented, and that the detergent composition used has a problem that metal ions (Ca ^{+ +} , Mg ⁺⁺ ) is not sufficient.

Further, Japanese Utility Model Laid-Open No. 1-168280 discloses that in order to prevent black spots due to recontamination during washing of a polyester-based cloth, the cloth is put in the same bath at the time of washing.
As a material that adsorbs these stains, a laundry adsorbent made of a fiber containing a modified polyester component obtained by copolymerizing isophthalate, which is dyed with a disperse dye at 80 ° C. or lower, is disclosed. However, this laundry adsorbent absorbs oily stains, and has a problem in that dyes eluted during washing cannot be easily removed.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has been made in order to solve the above-mentioned problems. Various dyes such as acid dyes and reactive dyes which are eluted during washing of clothes are disclosed. ) Can be easily and reliably removed in a short period of time, and can also sufficiently capture and remove metal ions that could not be captured by the conventional detergent composition, and washing of clothes using the same. The aim is to provide a method.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the above-mentioned conventional problems and the like. As a result, by using fibers containing fibers having a specific functional group, the above-mentioned washing aid for washing for the above-mentioned purpose was obtained. The present inventors have found that a method for washing materials and clothes using the same can be obtained, and have completed the present invention. That is, the present invention resides in the following 1 to 5. 1. A washing aid for washing, comprising a fiber having at least an ion exchange group. 2. 2. The washing aid for washing according to 1 above, wherein the fiber having an ion exchange group is a fiber having a cation exchange group and / or a fiber having an anion exchange group. 3. The above-mentioned 1 wherein the washing aid for washing comprises a sheet or a bag.
Washing aid for washing as described. 4. Washing clothes using the washing aid for washing and the detergent composition for clothes according to any one of the above 1 to 3, and collecting the washing aid for washing during or after washing. A method for washing clothes, characterized by the following. 5. The method for washing clothes according to the above item 4, wherein the detergent composition for clothes contains a nonionic surfactant having an HLB of 10 to 17.

[0007]

Embodiments of the present invention will be described below in detail. The laundry cleaning aid of the present invention is characterized by containing at least a fiber having an ion exchange group.

In the present invention, the fiber having an ion exchange group is at least a fiber having an ion exchange group.
There is no particular limitation, and examples include fibers containing fibers having a cation exchange group and / or fibers having an anion exchange group. Examples of the cation exchange group include a sulfone group and a carboxyl group, and examples of the anion exchange group include an amino group (1 to 3) and a quaternary ammonium base functional group. Preferably contains one or more of the various functional groups described above. The use form of the washing aid of the present invention is not particularly limited, but mainly includes a sheet or a bag. Examples of the form of the bag include a bag with an opening or a bag without an opening, but a shape appropriately required by the application,
It is desirable to select the thickness, the type of fiber and the combination thereof. The same applies to the sheet body.

In the present invention, the washing aid for washing (for example,
The sheet body or the bag body) is selected from a nonwoven fabric, a woven fabric, and a knitted fabric, and one or two or more of these can be combined. Further, the sheet or bag and the plastic film may be combined. That is, the form of the sheet body or the bag body may be a nonwoven fabric type, a woven fabric type, a knitted fabric type alone, a nonwoven fabric or a woven fabric / plastic sheet combined system, a nonwoven fabric / woven fabric combined system, a nonwoven fabric / woven fabric type A mixed system such as a non-woven fabric / plastic sheet / woven fabric combined system, and a mixed system having a two-layer structure, a three-layer structure, and a multi-layer structure are exemplified. The shape of the sheet or the bag is not particularly limited, and examples thereof include a circle, a polygon, a square, and a triangle. In addition, the thickness of the sheet body or the bag body is, in particular,
About 0.5 mm to 10 mm, preferably 0.5 mm
５5 mm is desirable.

[0010] The surface structure of the sheet or bag is not particularly limited, and for example, a planar structure, an embossed shape, an uneven shape, a pile shape and the like are desirable. In particular, protrusions such as embossing, uneven shapes, and pile shapes may be present on the sheet surface. The height of the projection is optimized depending on the material of the projection and the thickness of the sheet, but is preferably 0.5 mm to 20 mm, particularly preferably 1 mm to 1 mm.
10 mm. Further, the sheet body or the bag body may be of a mesh type. The size of the mesh is 16
１００100 mesh, preferably 20 to 80 mesh.

In the present invention, the washing aid for washing is preferably a sheet or bag containing fibers having at least a cation exchange group and / or fibers having at least an anion exchange group. Some are desirable. Examples of the fiber having a cation exchange group and / or an anion exchange group include a polyvinyl alcohol-based synthetic resin fiber and an acrylate-based resin mainly containing a copolymer of acrylonitrile and an acrylate (or methacrylate). And a covalent bond of a basic group and / or an acidic group having a cation exchange ability or an anion exchange ability within a synthetic resin fiber consisting of
The functional group of the fiber having a cation exchange group or an anion exchange group is one that is positively or negatively charged.

The functional groups contained in the fiber having a cation exchange ability include the following functional groups.

Embedded image In particular, among these cation exchange groups, preferably
Sulfone group (-SO ₃ H), carboxyl (-COO
H), -COONa, -COOM (M: metal salt, Na,
K, _{etc.), - SO 3 H, -SO} 3 Na, -SO 3 M (M: metal salts, Na, functional groups preferably consisting of K, etc.). One or more of these functional groups may be included.

The functional groups contained in the fibers having an anion exchange ability include the following functional groups.

Embedded image In particular, among the anion exchange groups, amino groups (1 to 3),
Quaternary ammonium ^{_{bases, -NH 2, -N + H 3}} , -N + (C
H ₃ ) ₃ , —N ₊ (R ₁ , R ₂ , R ₃ ) [R _{1 to} R ₃ are a hydrogen atom,
These are a methyl group and an ethyl group. The same applies hereinafter), = NH, ≡
N, -NHR _1, functional group -NHR ₂ are preferred. One or more of these functional groups may be included.

In addition, the washing aid for washing in the present invention may further contain a hydrophilic fiber or a hydrophobic fiber in addition to the fiber having a functional group having an ion exchange ability. As the hydrophilic fiber, for example, rayon, pulp,
Examples include cellulose fiber, polyvinyl alcohol (PVA) fiber, acrylic fiber, acrylate fiber, polyarylsulfone fiber, promix fiber, silk fiber, protein fiber, and paper. Examples of the hydrophobic fiber include polyolefin (polyethylene, polypropylene), polyester, polyethylene terephthalate, polyamide, polyimide, polyvinyl chloride, polyvinylidene chloride (vinylidene, vinylidene chloride), polyacrylonitrile, modacrylic fiber, polyurethane, and acrylic fiber. , Polystyrene, nylon, acetate fibers, polyalkylenes, and combinations and copolymers thereof. These fibers may be selected from one or more fibers. The other fibers include wool fiber, activated carbon fiber, fiber having a hollow structure, fiber containing charcoal, fiber having a core-sheath structure, fiber having a split fiber, fiber having an eccentric structure, and charcoal. Fibers may be used. In addition, hydrophilic fibers or hydrophobic fibers that can be contained in the washing aid for washing,
In addition, the total content of the other fibers is appropriately determined within a range not impairing the effects of the present invention, but is preferably 0 to 60% by mass based on the total amount of the washing aid for washing. .

The washing aid for washing in the present invention includes:
For example, a mixed spinning (mix) containing one kind or two or more kinds of various fibers having the above-mentioned ion-exchange groups, or a laundry having a multilayer structure composed of two or three layers of the fibers (for example, a nonwoven fabric or a woven fabric). Cleaning aids;
Further, it may be produced by chemically cross-linking a compound having a functional group having ion exchange ability on the fiber surface.

The distance between fibers of a sheet or a bag is not particularly limited, but is preferably in the range of 10 μm to 600 μm in consideration of the strength and durability of the sheet.
In particular, 20 μm to 300 μm is desirable. In consideration of usability, 35 μm to 200 μm is more preferable. The method for producing the nonwoven fabric is not particularly limited, but a production method in which no or little oil agent is added to the nonwoven fabric during production is desirable. In particular, when used in the laundry field or the like, it is preferable that the safety of the used oil agent (an oil agent approved by FDA) can be ensured. Examples of the method for producing a sheet using a nonwoven fabric include spunlace, spunbond, melt blow, thermal bond, needle punch, and wet method. Of these, spunlace, spunbond, meltblown, and wet are particularly preferred. The size of the sheet used in the washing machine is not particularly limited, but is preferably from 10 cm × 10 cm (100 cm ² ) to 30 cm.
A range of cm × 30 cm (900 cm ² ) is desirable. The mass of the sheet body is 10 g to 100 g (thickness is 1 mm to 2 g).
0 mm) is more desirable.

In the present invention, a method for producing each of the above-mentioned fiber products, that is, a fiber having at least an ion exchange group (for example, a fiber having at least a cation exchange group and / or a fiber having at least an anion exchange group) is conventionally known. Known and commercially available products can also be used. For example, in a method for producing a polyvinyl alcohol-based ion-exchangeable fiber, JP-A-63-69835 discloses anion-exchange fiber and a method for producing the same.
Regarding the cation exchange fiber and the method for producing the same, JP-B-56-10932, JP-A-63-309621, JP-A-8-12774, and JP-A-9-873.
No. 99 has been proposed.

For example, 95 to 40 mol% of an acidic group and / or a basic group having an anion or cation exchange ability is H-type, and the remaining 5 to 60 mol% is Na, K, Ca, M
It may be a type of one or more metal salts selected from g, Al, Ag, Fe, halogen and the like. As a method for producing a fiber product having a functional group capable of exchanging anions or cations, a monomer having an ion exchange group is resinified by a polycondensation reaction or a chain polymerization reaction to form a fibrous body, or a polycondensation reaction Alternatively, it can be obtained by introducing a functional group capable of exchanging anions or cations into a resin or fibrous body having a three-dimensional structure obtained by a chain polymerization reaction.

Specifically, on the surface of the polyvinyl alcohol fiber, a compound having a chemically functional group (fiber having a functional group having ion exchange ability) is introduced by a sulfuric acid esterification reaction with a residual hydroxyl group. Alternatively, a crosslinked structure may be introduced by treating the acrylic fiber with hydrazine, and then a carboxyl group or an amide group may be introduced into the remaining nitrile by hydrolysis. In this case, a hydrazine treatment is applied to the acrylic fiber to introduce a crosslinked structure (nitrogen content in the range of 1.0 to 10.0% by weight), and the amount of the remaining nitrile group is 1.0 to 6.5 meq / by hydrolysis. A carboxyl group is introduced into g, and an amide group is introduced into the remainder. Next, if necessary, 50 to 90 mol% of the carboxyl group is added to Na, K, Ca, Cu, Mg, Zn, Al, Ag,
It may be a type of one or more metal salts selected from Fe. Further, it may be formed by chemically cross-linking a compound having a functional group (fiber having a functional group having ion exchange ability) on the fiber surface.

Here, when a sulfone group is introduced into a fiber (when a cation exchange fiber is used), for example, as an example of introducing a sulfone group into a polyvinyl alcohol-based fiber,
PVA and vinyl polymer having a sulfone group (weight ratio 4 /
A description will be given of a case in which a dehydration catalyst is added to a spinning dope containing 1 to 1/5), dry spinning is performed, and then water-insoluble by heat treatment to obtain a cation exchangeable fiber. In this case, (1) a spinning solution comprising a PVA and a vinyl polymer having a sulfonic acid group and a dehydration catalyst for PVA is prepared,
(2) Using this stock solution, a fiber comprising PVA and the vinyl polymer as a substantial constituent is formed by a dry spinning method, and (3) the obtained fiber is made water-insoluble by heat treatment.

The raw material used here is PV
A, a vinyl polymer having a sulfonic acid group, and a dehydration catalyst. First, as PVA, general commercial products can be used, but those having a saponification degree of 90 mol% or more and a polymerization degree of 500 to 2,000 are applied in view of spinnability. As the vinyl polymer having a sulfonic acid group, a vinyl polymer having a sulfonic acid group of 1 mol / kg or more is preferable. Specifically, homopolymers made from vinyl monomers having a sulfonic acid group such as vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid and the like, and copolymers with other vinyl monomers copolymerizable with these vinyl monomers, etc. Is mentioned. Although the preferred degree of polymerization of the polymer having a sulfonic acid group varies depending on the individual polymer, in the case of polystyrene sulfonic acid, the degree of polymerization is from 1,000 to 600.
It is in the range of 0.

As a catalyst for dehydrating PVA, generally, a strongly acidic substance can be used. Such substances include sulfuric acid, sulfamic acid, organic sulfonic acids (eg, benzenesulfonic acid,
Naphthalene sulfonic acid, p-toluene sulfonic acid, etc.) or a vinyl polymer having an acid type sulfonic acid group. These dehydration catalysts are mixed in the yarn in advance. Alternatively, when these dehydration catalysts are not mixed into the yarn in advance, hydrogen chloride gas may be coexisted as a dehydration catalyst during the heat treatment.

As the spinning solution, an aqueous solution in which the above-mentioned raw materials, that is, PVA, a vinyl polymer having a sulfonic acid group, and a dehydration catalyst are uniformly dissolved is used. Mixing ratio of PVA and the vinyl polymer PVA / the vinyl polymer is 1/4 to 1/5 (weight)
Is suitable. The amount of the strongly acidic substance serving as a dehydration catalyst is 2 to 10% by weight, more preferably 4 to 10% by weight based on PVA.
~ 7% by weight. The solid concentration of the spinning dope satisfying the above conditions is suitably 20 to 50%. The spinning method for obtaining the fibers from the spinning solution thus adjusted is preferably a dry method. The shape of the fiber obtained after spinning, that is, the cross-sectional shape,
There are no restrictions on fiber length, fineness, and the like.

Regarding the anion exchange fiber and the method for producing the same, for example, when an amino group is introduced into the fiber, the procedure is as follows. For example, it can be produced by mixing and spinning a polymer having an amino group and polyvinyl alcohol, and performing a dehydration reaction of polyvinyl alcohol in the presence of a strongly acidic substance. Raw materials used include polymers having an amino group, PVA, and strongly acidic substances. First, as a polymer having an amino group, a polymer having sufficient chemical resistance is required, and includes a main chain and a bond weak to an acid or an alkali such as an ester or amide bond between the main chain and the amino group. Not good. Further, in order to have a practically usable ion exchange capacity, the polymer needs to be a polymer having an amino group of 1 mol / kg or more. Examples of the types of amino groups include primary, secondary, tertiary amino groups, and quaternary ammonium groups, and these may be used alone or as a mixture. Specifically, polyvinylamine, polyallylamine, polylysine, polyvinylpyridine, polyamines such as polyethyleneimine and derivatives thereof, and further,
A polymer obtained by introducing an amino group into a polymer capable of introducing an amino group such as polystyrene is exemplified. Regarding the degree of polymerization of these polyamines, the higher the degree of polymerization, the greater the degree of entanglement between PVA and the molecules, so that the spinning property is not impaired, and the effect of preventing falling off works more effectively. For example, in the case of polyethyleneimine, the degree of polymerization is required to be 500 or more, preferably 30
The range is from 00 to 6000.

On the other hand, as for PVA, a degree of saponification of 90 mol% or more and a degree of polymerization of 500 or more are used in consideration of spinnability. Preferably, the degree of saponification is 95 mol% or more and the degree of polymerization is 1000 to 2000. Use the ones in the range. PV
The strongly acidic substance as the dehydration catalyst of A is coexisted at the time of heat treatment with hydrogen chloride gas, or heat treatment is performed after the strongly acidic substance is attached to the fiber before heat treatment. As the strongly acidic substance to be attached before the heat treatment, a substance called a so-called strong acid such as phosphoric acid or hydrochloric acid, or a Lewis acid such as aluminum chloride is used, and hydrogen chloride gas is most preferably used. In this case, uneven reaction and a decrease in yarn quality are likely to occur.

As the stock solution for spinning, use is made of the above-mentioned materials, that is, a stock solution obtained by uniformly dissolving a polymer having an amino group, PVA and, if necessary, a strongly acidic dehydration catalyst. Depending on the mixing ratio of the polymer having an amino group and PVA, the thread quality after the heat treatment and the amount of the polymer having the amino group falling off change, and the mixing ratio (polymer having the amino group / PVA) is 2 / If it is 1 or more, the yarn quality deteriorates, the amount of falling off increases, and it cannot be used.
Conversely, as the PVA increases, the effect of preventing falling off increases, but on the other hand, the ion exchange capacity is limited. Therefore, the mixing ratio needs to be in the range of 1/5 to 2/1, and preferably 1/2. 4 to 1/1. The solid content concentration of the spinning dope satisfying the above conditions is suitably 20% to 50%. The spinning method may be any of dry, semi-dry, semi-wet and wet spinning, but dry spinning is most preferred. In the case of semi-dry semi-wet spinning and wet spinning, it is necessary to consider the coagulation bath composition in order to avoid phase separation between the polymer having an amino group and PVA. For example, when polyallylamine is used as the polymer having an amino group, an acetone-based coagulation bath is suitable. There is no limitation on the shape of the fiber obtained by these spinning methods, that is, the cross-sectional shape, fiber length, fineness, and the like.

The heat treatment should be selected in consideration of the heat resistance of the raw material polyamine.
In the range of 0 ° C., the time is 5 minutes to 4 hours, but preferably, the temperature is in the range of 100 to 130 ° C., and the time is 30 minutes to 2 hours.
Time. It is most preferable to perform the heat treatment in a hydrogen chloride gas atmosphere. However, when a strongly acidic substance is adhered, the heat treatment may be performed in the air. Preferably, an oxygen-free inert gas (for example, nitrogen gas ) Medium is good. This heat treatment causes PVA to undergo a dehydration reaction. PV at this time
The dehydration weight reduction rate of A is in the range of 10 to 40%. Various derivatives can be synthesized utilizing the reactivity of the amino group. For example, an anion exchange fiber having a primary amino group is reacted with an aldehyde to synthesize a Schiff base,
A strongly basic anion exchange fiber can be synthesized by reacting an anion exchange fiber having a 3-amino group with a quaternizing agent. When the fiber thus obtained is used in the form of a cloth, a string, a total shape, a cut thread, or the like, it can be processed into those forms. There is also.

The washing aid for washing of the present invention is, as described above,
Any fiber containing at least a fiber having an ion exchange group can adsorb and remove various dyes (dyes), which are the effects of the present invention, and can also capture and remove metal ions that could not be captured in a conventional detergent composition. Although it is possible, a fiber having a cation exchange group and / or a fiber having an anion exchange group is preferable.
More preferably, it is desirable to contain a fiber having a cation exchange group, or a fiber having a cation exchange group and a fiber having an anion exchange group. In addition to ion-exchange fibers, hydrophilic fibers such as rayon fibers and PP
Fibers and hydrophobic fibers such as polyester fibers may be contained. In particular, fibers made of fibers having a cation exchange group are more excellent in the performance of adsorbing and removing various dyes (dyes), and can further capture and remove metal ions that could not be captured in the conventional detergent composition. . It is particularly preferable to use a mixed type of the fiber (A) having a cation exchange group and the fiber (B) having an anion exchange group, and to use the cation exchange group in the mixed type fiber. The content of the fiber (A) is 50% or more, specifically, A: B is 50:50 to 8
A washing aid for washing with a ratio of 0:20 is desirable.

Next, in the method of washing clothes according to the present invention, the clothes are washed using the washing aid and the detergent composition having the above-mentioned structure, and the washing is completed during the washing, for example, during the washing step. The washing auxiliary material is collected before the rinsing step is started or after the washing is completed, for example, after the washing step is completed. The detergent composition for clothing used in the washing method of the present invention is not particularly limited, and a detergent composition for clothing having an ordinary powder or liquid composition can be used. A powder or liquid detergent composition containing ~ 17 nonionic surfactants is preferred. The clothing to be washed in the present invention is not particularly limited as long as it is to be washed. In the washing method of the present invention, since the washing aid used for washing contains at least an ion exchange group, the effect on the ion exchangeable fibers, that is, the ion exchange performance (adsorption ability of dyes and the like) by the detergent composition. It is preferable to use a nonionic surfactant having an HLB of 10 to 17 as a surfactant to be contained in the detergent composition for clothing in order to prevent a decrease in the water content.

Examples of the nonionic surfactant of HLB 10 to 17 include, for example, an EO adduct or a PO adduct of a linear or branched alcohol ethoxylate, or an E adduct.
O / PO adducts (block bodies, random bodies) and the like can be mentioned. Specifically, the following are mentioned. An aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms and an alkylene oxide having 2 to 4 carbon atoms having an average of 3 to
Examples of the polyoxyalkylene alkyl (or alkenyl) ether to which 30 mol, preferably 7 to 20 mol are added include polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether. Ter is preferred. Polyoxyethylene alkyl (or alkenyl) phenyl ether. Fatty acid alkyl quister alkoxylate represented by the following general formula (I) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester R ₁ CO (OA) nOR ₂ (I) (R ₁ CO: carbon number 6-22, preferably is a fatty acid residue of 10~18, OA: OCH ₂ CH ₂ carbon atoms, such as 2
4, preferably 2 to 3 additional units of alkylene oxide, n: average number of moles of alkylene oxide added,
3 to 30, preferably 5 to 20, R ₂ : carbon number 1
3 lower alkyl groups). Polyoxyethylene sorbite fatty acid ester. Glycerin fatty acid esters. A sugar ester nonionic surfactant comprising an ester of a fatty acid having 6 to 18 carbon atoms and a monosaccharide having 5 to 6 carbon atoms or a monoalkyl ether thereof. A sugar alkyl ether nonionic surfactant represented by the following general formula (II). R ₂ O (CH ₂ CH ₂ O) n (Z) X (II) (R ₂ : an alkyl group having 8 to 18 carbon atoms, n: 0 to 12,
Z: sugar residue having 5 to 6 carbon atoms, X: 1.2 to 10) Among these nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ether, fatty acid methyl ester obtained by adding ethylene oxide to fatty acid methyl ester Ethoxylate is particularly preferably used in terms of detergency.

As other nonionic surfactants that can be used, those containing an ethylene oxide group / propylene oxide group are preferred. Specifically, the following are mentioned. The following general formula (III): R ₃ —O— (CH ₂ CH ₂ O) n—H (III) (wherein, R ₃ represents an alkyl group or an alkenyl group having 10 to 16 carbon atoms, n is an average addition mole number of ethylene oxide (EO).), and (a) the average addition mole number n of the ethylene oxide group (EO) is 3 to 20. , (B) the amount of unreacted alcohol where n = 0 is 10% by mass or less, and (c)
The average number of moles of the most abundant nonionic surfactant is n
And _MAX, the total amount of the average molar number of addition of nonionic surfactant n _{MAX +2} from n _{MAX -2} at that time when the Yi, Y
a nonionic surfactant having i ≧ 55% by mass, the following general formula (IV), R ₄ —O— (CH ₂ CH ₂ O) n—H (IV) wherein R ₄ is carbon A nonionic surfactant represented by the following formula (10), wherein n represents an alkyl group or alkenyl group, and n represents an average number of moles of ethylene oxide (EO) added. )) Has an average addition mole number n of 3 to 20, and (b) the average addition mole number of the nonionic surfactant having the largest amount is n _MAX, and the average addition of n _{MAX -2} to n _{MAX +2} at that time. When the total amount of the nonionic surfactant in moles is Yi, a nonionic surfactant satisfying Yi ≦ 50% by mass is represented by the following general formula (V): R ₅ -O- (EO) n- (PO) m-H ......... (V) (wherein, R ₅ is an alkyl or alkenyl group having 10 to 16 carbon atoms, EO is It indicates Chi alkylene oxide group, PO represents a propylene oxide group, n represents 3
The average addition mole number of ethylene oxide in the range of 15 is shown, and m shows the addition mole number of propylene oxide in the range of 1 to 3. ), A compound obtained by adding an average of 5 to 15 mol of ethylene oxide to a secondary alcohol having 10 to 16 carbon atoms, a total of 8 to 8 carbon atoms having the shortest branched chain having 5 or less carbon atoms Nonionic surfactants obtained by adding an average of 5 to 15 moles of ethylene oxide to a primary alcohol having 22 branched alkyl groups or alkenyl groups.

As nonionic surfactants which can be further used, there may be mentioned nonionic surfactants of HLB10-16 having a fatty acid ester or hydrogenated castor oil as a basic skeleton. Hydrophilic groups are added, for example, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol monosteprate, polyethylene glycol isosteprate, polyoxyethylene glyceryl isosteprate, polyoxyethylene glyceryl triisostealicylate , Polyoxyethylene glyceryl trioleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated isosterate Oil or the like is used.

In the method of the present invention, HLB is 10 to 17
Nonionic surfactants out of the range are unfavorable because the effect of washing various stains is reduced. HLB10-1
The content of the nonionic surfactant of No. 7 is preferably 10 to 60% by mass based on the total amount of the detergent composition. In addition, the detergent composition for clothing used in the method of the present invention includes, in addition to the various nonionic surfactants of HLB 10 to 17 described above, components usually blended in detergent raw materials, for example, a porous material such as amorphous silica. Inorganic oxide powder, clay compounds such as montmorillonite and hectorite, inorganic alkali builders such as aluminosilicate and sodium carbonate, fluorescent agents, enzymes,
Tallow soap, a grinding aid, a fluidity improver, and the like can be appropriately blended.

When the clothes and the like are washed by using the washing aid of the present invention thus constituted and by the washing method of the present invention, a dye (dye) eluted from the clothes and the like during washing, In particular, basic dyes (cationic dyes) that elute during washing, and basic dyes (cationic dyes)
It can be easily and reliably removed in a short period of time even in the washing water or the like of both the dyes and the acid dyes (anionic dyes), and can prevent the transfer to white clothing. In addition, when clothes and the like are washed using the washing aid for washing of the present invention and the washing method of the present invention, metal ions (Ca ⁺⁺ , Mg ⁺⁺ ) can be captured, and the detergency of clothing can be improved. Furthermore, by putting the laundry aid into the dye-containing solution in the wastewater that is discarded during washing, the dye is removed in advance before draining and then drained to reduce the burden on the environment (BOD, COD, etc.).

[0035]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Examples 1 to 3 and Comparative Examples 1 to 3 Sheets made of fibers having anion-exchange groups shown in Table 1 below and cellulose fibers, rayon fibers and polyester fibers instead of the fibers having anion-exchange groups The effect of preventing dye transfer to cotton cloth (the effect of removing the dye) was evaluated by the following evaluation method using the sheet composed of The evaluation results are shown in Table 1 below.

(Evaluation method for the effect of preventing dye transfer to cotton cloth) 100 ppm of dye (basic dye or acid dye) and 500 ppm of detergent (Lion Corporation, "Super Top" standard)
Each sheet shown in the following Table 1 [32 g of nonwoven fabric (15 cm × 18 cm)] in a 1 L beaker containing 500 cc of the solution of
And 2.5 g of white cotton cloth (15 cm × 16 cm) were simultaneously added, and the effect of preventing dye transfer to cotton cloth after stirring (at room temperature) for 30 minutes with a stirrer was evaluated. The sheet body contains 30% by mass of PET (polyester fiber). The thickness of the sheet is 9 mm. Water used was ion-exchanged water.

The effect of preventing dyeing on cotton cloth (changes before and after immersion) was visually evaluated by the following evaluation criteria. Evaluation criteria: ○: Almost no dyeing on white cotton cloth (has an effect of preventing dye transfer) △: Little dyeing on white cotton cloth (has a slight effect of preventing dye transfer) ×: Dyeing on white cotton cloth There is no effect of preventing dye transfer

[0039]

[Table 1]

As is evident from the results in Table 1, the sheets made of the fibers containing ion exchange groups (anion exchange groups) of Examples 1 to 3 which fall within the scope of the present invention fall outside the scope of the present invention. Compared with Comparative Examples 1 to 3, it was found that there was an effect of preventing migration.

[Examples 4 to 6] The same as in Example 1 described above, except that each sheet ((32 g of nonwoven fabric (15 cm × 18 cm)) comprising fibers having an anion exchange group and a cation exchange group shown in Table 2 below was used. The effect of preventing dye transfer to cotton cloth (effect of removing dye) was evaluated as shown in Table 2 below.

[0042]

[Table 2]

As is evident from the results in Table 2 above, the sheet composed of the fibers containing the ion exchange groups (anion exchange groups and cation exchange groups) of Examples 4 to 6 which fall within the scope of the present invention is not resistant to migration. It turned out to be effective.

Examples 7 to 10 and Comparative Examples 4 to 6 Sheets made of fibers containing ion-exchange groups (cation-exchange groups, cation-exchange groups and anion-exchange groups) shown in Table 3 below, and the ion-exchange groups Using a sheet made of cellulose fiber, rayon fiber and polyester fiber instead of the fiber having the following, the change in hardness and the detergency were evaluated by the following evaluation methods. The amount of ion exchange base fiber added is 500p
pm (15 g of fiber is added to 30 L of water). That is, the sheet body is made of polyester fiber (PE
Since 30% by mass of T) was contained, the sheet body actually added was evaluated by putting 21 g in 30 L of water. The results of these evaluations are shown in Table 3 below.

(Method of Evaluating Change in Hardness) Fiber was added to hard water (Ca ⁺⁺ ) for a predetermined time (10 minutes, 3 minutes).
After 0 min), the remaining metal ions were measured by chelate titration. The solution used was a solution (Ca ⁺⁺ ) containing a hardness of 4.5.

(Method for Evaluating Detergency) A standard amount of supertop and a sheet made of a fiber having a cation exchange group or the like are added to hard water (Ca ⁺⁺ ), and the cleaning effect of the artificial soil cloth shown below is washed. Testing machine (US, test
The detergency was evaluated using a Terg-O-Tometer manufactured by Inng Corporation. The detergent concentration was evaluated by adding 15 g of a detergent (standard use amount of Super Top) to 30 L of hard water (hardness of 4.5) and evaluating the detergency.

(Preparation of Artificial Soil Cloth) Washing cloth (Japan Oil Chemical Association cotton cloth No. 600 × 5 × 5) was placed in a soil bath having the following artificial soil composition.
cm) was immersed and dried at 105 ° C. for 30 minutes, and the surface of the cloth was rubbed left and right 25 times. Among them, the reflectance 42 ± 2
% Was used as a dirty cloth. Soil composition (mass)% Oleic acid 28.3% Triolein 15.6% Cholesterol 13.8% Liquid paraffin 2.5% Squalane 2.5% Gelatin 7.0% Inorganic soil 29.8% Carbon black ( 0.5%

[0048]

[Table 3]

As is evident from the results in Table 3, a sheet comprising fibers containing ion-exchange groups (cation-exchange groups or a cation-exchange group and anion-exchange groups) according to Examples 7 to 10 within the scope of the present invention. Was found to be capable of sufficiently capturing and removing metal ions (Ca ⁺⁺ ) and excellent in detergency, as compared with Comparative Examples 4 to 6, which are outside the scope of the present invention. .

[Examples 11 to 20 and Comparative Examples 9 to 10]
Using the artificial soil cloth shown in Example 7 above, each of the detergent compositions for clothing and each sheet shown in Tables 4 and 5 below were simultaneously placed in a washing machine, and the detergency was evaluated by the following method. Water was tap water. The evaluation results are shown in Tables 4 and 5 below.

(Evaluation Method of Detergency) A 10-tub washing machine (Mitsubishi Electric Co., Ltd.)
W-225) at 15 ° C and 30L of water (3 ° D
H) was washed for 10 minutes, and as an evaluation of detergency, the degree of falling of the artificially soiled cloth was evaluated according to the following evaluation criteria. Evaluation criteria: 5: Completely stained 4: Slightly stained 3: Proportionally stained 2: Slightly stained 1: Slightly stained

[0052]

[Table 4]

[0053]

[Table 5]

As is clear from the results shown in Tables 4 and 5, Example 11 was obtained by washing using the detergent composition for clothing falling within the scope of the present invention and a sheet made of fibers containing ion-exchange groups. Comparative Examples 9 to 20 are out of the range of the present invention.
It turned out that it is excellent in detergency compared with -10.

[0055]

According to the present invention, various dyes (pigments) eluted during washing of clothes can be easily and reliably removed, and metal ions which cannot be captured by conventional detergent compositions can be sufficiently removed. A laundry cleaning aid that can be trapped and removed and a method for washing clothes using the same are provided.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshikazu Fukumoto 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation (72) Inventor Hideo Kuroda 1-3-7, Honjo, Sumida-ku, Tokyo No. Lion Corporation F term (reference) 3B155 AA01 AA03 BA10 CD06 CD11 CD17 4H003 AB03 AC08 AC12 BA19 BA28 DA01 DC02 EA12 EA15 EA16 EA28 EC01 FA06 FA07

Claims (5)

[Claims] 1. A washing aid for laundry, comprising a fiber having at least an ion exchange group. 2. The washing aid according to claim 1, wherein the fiber having an ion exchange group is a fiber having a cation exchange group and / or a fiber having an anion exchange group. 3. The washing aid according to claim 1, wherein the washing aid comprises a sheet or a bag. 4. Washing clothes using the washing aid according to any one of claims 1 to 3 and the detergent composition for clothes, and washing the clothes during or after washing. A method for washing clothes, comprising collecting auxiliary materials. 5. The clothing detergent composition according to claim 1, wherein the HLB is from 10 to 17%.
5. The method for washing clothes according to claim 4, which comprises the nonionic surfactant.