JP2009174110A - Soil adsorbent sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a soil adsorbent sheet excellent in soil adsorbability, uniformity in soil adsorption, washing durability, easiness in taking out of a washing bath, and suppression in resoiling, and capable of effectively collecting soil in the washing bath. <P>SOLUTION: The soil adsorbent sheet for adsorbing the soil in the washing bath is prepared by bringing a nonwoven fabric having 20-120 g/m<SP>2</SP>basis weight to be applied or impregnated with at least either of one or more cationic high-molecular compounds or one or more amphoteric high-molecular compounds. The cationic high-molecular compounds are at least one selected from a group consisting of (a) cationized guar gum, (b) cationized cellulose, and (c) cationized starch. The amphoteric high-molecular compounds are preferably an aminoalkyl (meth)acrylate quaternary ammonium salt polymer or an acryl amide-aminoalkyl (meth)acrylate quaternary ammonium salt copolymer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a dirt adsorbing sheet that collects dirt separated from clothing during washing in the washing bath.

Laundry is an operation of separating dirt from clothes and keeping the dirt in the washing bath so that the separated dirt does not return to the clothes. As for detergents and the like that can separate dirt from clothes and can keep the separated dirt in a washing bath, many suitable ones have already been provided.
However, depending on the type and degree of dirt, the fiber type of clothes, etc., there is a problem that dirt in the washing bath adheres to the clothes again and causes re-contamination. In particular, dirt such as mud, oil and carbon tends to cause recontamination. Therefore, there is a demand for a method for collecting dirt in the washing bath and taking out the dirt outside the washing bath.
In addition, there is a demand for a method for visually and easily displaying the dirt separating action of the detergent for consumers who want to select a more excellent detergent. Therefore, a method for collecting dirt in the washing bath and presenting the collected dirt to the consumer has been proposed.

As the dirt adsorbing sheet for collecting dirt in the cleaning liquid, a sheet in which a polyfunctional quaternary ammonium compound (dirt adsorbent) is immobilized on an insoluble solid substance (sheet) is disclosed (see Patent Document 1). . However, the insoluble solid substance disclosed in Patent Document 1 is specifically a piece of cotton cloth, which adheres to clothing or is difficult to take out from a washing bath, so as a sheet used for a dirt adsorbing sheet. Is not appropriate. Moreover, it cannot be said that the combination of a cotton cloth piece and a polyfunctional quaternary ammonium compound is appropriate from the viewpoints of dirt adsorbability and dirt adsorption uniformity.
Therefore, the dirt adsorbing sheet, the uniformity of dirt adsorbing, the durability of washing, the ease of taking out from the washing bath, and the dirt adsorbing sheet that can effectively collect the dirt in the washing bath are still satisfactory. The current situation is that nothing is provided.

Japanese Patent Publication No. 63-501963

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention provides a dirt adsorbing sheet that is excellent in dirt adsorbing property, dirt adsorbing uniformity, washing durability and ease of taking out from the washing bath, and can effectively collect dirt in the washing bath. The purpose is to provide.

In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, obtained the following findings. That is, the nonwoven fabric of basis weight ^{20g / m 2 ~120g / m 2} , was impregnated applying at least one of one or more cationic polymer compound and one or more amphoteric polymer compound, dirt in the wash bath It was found that it can be effectively and uniformly adsorbed, and can be used as a dirt adsorbing sheet excellent in dirt adsorbing property, dirt adsorbing uniformity, washing durability and ease of taking out from a washing bath.

This invention is based on the said knowledge by this inventor, and as a means for solving the said subject, it is as follows. That is,
<1> A sheet for adsorbing dirt in the wash bath, at least a basis weight of 20g / m ² ~120g / m 1 or more cationic polymer compound ² of the nonwoven fabric and one or more amphoteric polymer compound Any one of them is applied or impregnated.
<2> The soil adsorbing sheet according to <1>, wherein the cationic polymer compound is a cationized polysaccharide and the amphoteric polymer compound is a quaternary ammonium salt-containing acrylic polymer.
<3> The cationized polysaccharide is at least one selected from the group consisting of cationized guar gum, cationized cellulose, and cationized starch, and the quaternary ammonium salt-containing acrylic polymer is an aminoalkyl (meth) acrylate 4 The soil adsorption sheet according to <2>, which is a quaternary ammonium salt polymer or an acrylamide / aminoalkyl (meth) acrylate quaternary ammonium salt copolymer.
<4> The soil adsorption sheet according to any one of <1> to <3>, wherein the polymer compound has a weight average molecular weight of 150,000 to 10,000,000.
<5> The dirt adsorbing sheet according to any one of <1> to <4>, wherein the nonwoven fabric is a nonwoven fabric produced by any one of a spunbond method and a chemical bond method.

  According to the present invention, the above-mentioned problems in the prior art can be solved, and it is excellent in dirt adsorbability, dirt adsorption uniformity, washing durability and ease of taking out from the washing bath, and effectively removes dirt in the washing bath. It is possible to provide a dirt adsorbing sheet that can be collected.

(Dirt adsorption sheet)
Dirt adsorption sheet of the present invention, the dirt in the washing bath a sheet to be adsorbed, basis weight 20g / m ² ~120g / m of 1 or more in the ^second nonwoven cationic polymer compound and one or more amphoteric It is characterized by being coated or impregnated with at least one of polymer compounds.

<Nonwoven fabric>
According to the definition by JIS-L-0222, the nonwoven fabric is “a fiber sheet, web or vat, in which fibers are oriented in one direction or randomly, and between fibers by alternating current and / or fusion and / or adhesion. , But excluding paper, woven fabric, knitted fabric, tufts and shredded felt. "
The nonwoven fabric mainly has a function as a sheet for supporting a cationic polymer compound or an amphoteric polymer compound in the dirt adsorbing sheet of the present invention. Furthermore, the nonwoven fabric itself has a function of adsorbing dirt.

The basis weight of the nonwoven fabric, as long as 20 to 120 g / ^{m 2,} not particularly limited and may be appropriately selected depending on the purpose, it is preferable ^{35~120g / m 2, 45~120g / m} 2 Is more preferable. When the basis weight is less than 20 g / m ² , dirt adsorbability may be reduced, dirt may not adhere uniformly, and washing durability may be poor. When the basis weight exceeds 120 g / m ² , dirt may not adhere uniformly, or fouling may occur in the nonwoven fabric after washing, and the adsorbed dirt may be detached again.
In addition, the said basic weight means the mass of this nonwoven fabric per unit area of a nonwoven fabric.

  There is no restriction | limiting in particular as thickness of the said nonwoven fabric, According to the objective, it can select suitably, 0.2-2.0 mm is preferable.

There is no restriction | limiting in particular as a raw material of the said nonwoven fabric, According to the objective, it can select suitably, For example, a hydrophilic fiber, a hydrophobic fiber, etc. are mentioned, These can be mixed and used suitably.
There is no restriction | limiting in particular as said hydrophilic fiber, According to the objective, it can select suitably. Among them, it is preferable that at least one of rayon fiber and cotton fiber is included.
Examples of the rayon fibers include regenerated fibers such as viscose rayon and copper ammonia rayon. Although there is no restriction | limiting in particular as the thickness of the said rayon fiber, 1-4 denier is preferable. Although there is no restriction | limiting in particular as the length of the said rayon fiber, 30-50 mm is preferable.
Examples of the cotton fibers include natural fibers such as rice cotton, Egyptian cotton, Upland cotton, and Indian cotton. Although there is no restriction | limiting in particular as the thickness of the said cotton fiber, 1-4 denier is preferable. Although there is no restriction | limiting in particular as the length of the said cotton fiber, 10-40 mm is preferable.

There is no restriction | limiting in particular as said hydrophobic fiber, According to the objective, it can select suitably, For example, synthetic fibers, such as polyethylene, a polypropylene, polyester, are mentioned.
The form of the fiber may be a single fiber made of the above-mentioned raw material or a composite fiber made of two or more kinds. Examples of the composite fiber include polypropylene and polyethylene, polyester and polyethylene, polyester and polypropylene, and the like. In the combination, any fiber may be selected as the core material or the sheath material.

  There is no restriction | limiting in particular as a manufacturing method of the said nonwoven fabric, According to the objective, it can select suitably, For example, a dry method, a wet method, etc. are mentioned. Specific examples of the method for producing the nonwoven fabric include a spunbond method, a chemical bond method, a thermal bond method, and a spunlace method. Of these, the spunbond method and the chemical bond method are preferable in that they exhibit excellent washing durability.

  In the spunbond method, a resin chip having a low melting temperature such as polypropylene is usually heated and melted, long fibers are extruded from a nozzle, and a plurality of the long fibers are stacked on a belt conveyor to form a web. The web is heat welded with a hot roll.

  In the chemical bond method, a relatively long short fiber is usually opened and stirred by an air flow, and a web is formed by feeding the fiber in a certain amount and in a certain direction with a needle provided on a belt conveyor. A binder (adhesive resin) is applied to the web by spraying and heated and dried to bond and bond the fiber intersections.

  In the thermal bond method, normally, relatively long short fibers are opened and agitated by an air flow, and a web is formed by feeding fibers in a certain amount and in a certain direction with a needle provided on a belt conveyor. The low melting point fibers in the web are welded with a roll or hot air to bond the fibers together.

  In the spunlace method, a relatively long short fiber is usually opened and agitated by an air flow, and a web is formed by feeding the fiber in a certain amount and in a certain direction with a needle provided on a belt conveyor. The web is laminated, and a special needle called a barb having a minute protrusion is reciprocated at high speed with respect to the laminated web to entangle the fibers.

<Cationic polymer compound>
The cationic polymer compound means a polymer compound having a cationic group. The cationic group refers to a monomer having a positively charged atom. There is no restriction | limiting in particular as said cationic group, According to the objective, it can select suitably, For example, groups which have cationic property, such as an amine group, an amino group, a quaternary ammonium group, are mentioned. The cationic polymer compound functions as a “dirt adsorbent” that adsorbs dirt in the washing bath in the dirt adsorbing sheet of the present invention.

  There is no restriction | limiting in particular as cationization degree in the said cationic polymer, According to the objective, it can select suitably, 0.1 mass%-2.0 mass% are preferable, 0.5 mass%-2. 0% by mass is more preferable, and 1.0% by mass to 1.7% by mass is particularly preferable. If the degree of cationization is less than 0.1% by mass, the dirt adsorbability may be reduced, and the effect of suppressing recontamination may not be sufficiently obtained. In some cases, the effect of suppressing recontamination may not be sufficiently obtained due to the increase. If the degree of cationization is within the particularly preferred range, it is advantageous in that the effect of adsorbing dirt is remarkably exhibited.

Here, the cationization degree can be calculated by the following equation (1).

  In the above formula (1), the method for measuring nitrogen in the cationic polymer compound can be appropriately selected from known methods. For example, “quasi-drug raw material standard”, nitrogen determination method first method micro Examples include Kjeldahl method.

  The cationic polymer compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cationized polysaccharides such as cationized guar gum, cationized cellulose and cationized starch, polyethyleneimine, and cationization. Examples thereof include natural polymer derivatives having amino groups such as polyvinyl alcohol and chitosan, and copolymers of diethylamino methacrylate and vinyl monomers having hydrophilic groups to which ethylene oxide or the like is added. Among these, cationized guar gum, cationized cellulose, and cationized starch are more preferable because they have an excellent soil adsorbing action. The cationic polymer compound may be used alone or in combination of two or more.

-Cationized guar gum-
There is no restriction | limiting in particular as said cationized guar gum, According to the objective, it can select suitably, As what is marketed, Jaguar Excel (weight average molecular weight MW: 1,200,000, cationization degree: 1.6%) , Rhodia Co., Ltd.), Labor gum CG-M8M (weight average molecular weight MW: 50,000, cationization degree: 2.0%, Dainippon Sumitomo Pharma Co., Ltd.).

-Cationized cellulose-
The said cationized cellulose means what is obtained by making a cellulose raw material and a cationizing agent react, and contains other components, such as a small amount of water, as needed.
There is no restriction | limiting in particular as said cellulose raw material, According to the objective, it can select suitably, For example, the hydroxyethyl cellulose (HEC) etc. which are obtained by adding ethylene oxide to a cellulose are mentioned.

  The cationizing agent is not particularly limited and can be selected from known cationizing agents. Examples thereof include tertiary amine compounds and quaternary ammonium compounds. Specifically, 2-diethylaminoethyl Examples include chloride, glycidyltrimethylammonium chloride, and 3-chloro-2-hydroxypropyltrimethylammonium chloride.

A preferred example of the cationized cellulose is a polymer having (halogen) -O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose (see the following general formula (1)) as a repeating unit. Can be mentioned.
[Wherein, R ^{3 to} R ⁵ are each independently a hydrogen atom or a group represented by the following structural formula (2). However, at least one of R ^{3 to} R ⁵ is a group represented by the following structural formula (2). l, m, and n each represent the average number of moles of ethylene oxide added. ]

In the general formula (1), the degree of ethylene oxide (EO) substitution per glucose ring unit is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.7 to 2.5.
Here, the degree of ethylene oxide (EO) substitution indicates the average (maximum is 3) of the number of glucose ring hydroxyl groups substituted with EO per glucose ring unit.

The cationized cellulose represented by the general formula (1) can be suitably used from among commercially available ones such as Leogard GP (cationization degree 1.8% by mass), Leogard LP (cation). 1.0% by mass), Leogard KGP (1.8% by mass cationization), Leogard MGP (1.8% by mass cationization), Leogard MLP (0.6% by mass cationization), Leogard GPS (Cationization degree 1.8% by mass), Leogard GP0 (cationization degree 1.8% by mass), Leogard LP (cationization degree 1.0% by mass) [above, trade name: Lion]; Katchinal HC-100 ( Cationization degree 1.0-2.0 mass%), kachinal HC-200 (cationization degree 1.0-2.0 mass%), kachinal LC-100 (cationization degree 0.5) 1.5 mass%), kachinal LC-200 (degree of cationization 0.5-1.5 mass%) [above, trade name: Toho Chemical Industry]; UCARE Polymer LR400 (degree of cationization 0.8-1.1) Mass%), UCARE Polymer LR30M (cationization degree 0.8-1.1 mass%) [above, trade name: Dow Chemical Company]; and the like.
In addition, the difference in the grade in the said commercially available cationized cellulose mainly depends on the molecular weight of cellulose, the average added mole number of EO, and the degree of cationization.

-Cationized starch-
The cationized starch means a product obtained by reacting starch with a cationizing agent.
The starch is not particularly limited as long as it has starch granules, and can be appropriately selected according to the purpose. For example, sweet potato, potato, tapioca, corn (for example, waxy corn), rice, wheat And starch obtained from the above. Among these, starch obtained from tapioca and waxy corn is preferable.

  The cationizing agent is not particularly limited and can be selected from known cationizing agents. Examples thereof include tertiary amine compounds and quaternary ammonium compounds. Specifically, 2-diethylaminoethyl Examples include chloride, glycidyltrimethylammonium chloride, and 3-chloro-2-hydroxypropyltrimethylammonium chloride. Among these, a quaternary ammonium compound having a glycidyl group is preferable.

  The cationized starch can be suitably used from among commercially available products, and examples thereof include sizing agents in the paper industry, compounding agents for cosmetics (for example, hair cleaners and skin cleaners), and the like. It is done.

<Amphoteric polymer compound>
The amphoteric polymer compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminoalkyl (meth) acrylate quaternary ammonium salt polymers and acrylamide aminoalkyl (meth) acrylate quaternary ammonium. Quaternary ammonium salt-containing acrylic polymer such as salt copolymer, dimethyldiallylammonium chloride polymer, dimethyldiallylammonium chloride / acrylamide copolymer, dimethyldiallylammonium chloride / acrylic acid copolymer, imidazolinium chloride / vinyl Examples include pyrrolidone copolymers. Among them, a quaternary ammonium salt-containing acrylic polymer is more preferable because it has an excellent soil adsorbing action. The amphoteric polymer compounds may be used alone or in combination of two or more.

  Examples of the cationic group-containing monomer constituting the quaternary ammonium salt-containing acrylic polymer include methacrylamidopropyltrimethyl quaternary ammonium chloride, dimethylaminoethyl acrylate methyl quaternary ammonium chloride, diallyldimethyl quaternary ammonium chloride and the like. Among them, methacrylamidopropyltrimethyl quaternary ammonium chloride and dimethylaminoethyl acrylate methyl quaternary ammonium chloride are more preferable, and methacrylamidopropyltrimethyl quaternary ammonium chloride is more preferable in terms of excellent dirt adsorption action. In addition, examples of the anion group-containing monomer include acrylic acid and methacrylic acid, and examples of the other monomer include acrylic acid ester, acrylic acid amide, methacrylic acid ester, and methacrylic acid amide. A quaternary ammonium salt-containing acrylic polymer is obtained by polymerizing these monomers.

  In the quaternary ammonium salt-containing acrylic polymer, the cation group-containing monomer content is preferably 40% by mass to 100% by mass, more preferably 50% by mass to 85% by mass, and still more preferably 60% by mass to 75% by mass. The anionic group-containing monomer content is preferably 0% by mass to 30% by mass, more preferably 5% by mass to 25% by mass, still more preferably 5% by mass to 20% by mass, and more preferably 5% by mass to 10% by mass. Particularly preferred. If the cation group-containing monomer content is less than 40% by mass or the anion group-containing monomer content is more than 30% by mass, the dirt adsorbability is lowered and the effect of suppressing recontamination may not be sufficiently obtained. is there.

  Among the quaternary ammonium salt-containing acrylic polymers, aminoalkyl (meth) acrylate quaternary ammonium salt polymers and acrylamide / aminoalkyl (meth) acrylate quaternary ammonium salt copolymers are preferred. Specifically, dimethylamino Examples thereof include ethyl methacrylate methyl chloride quaternary ammonium salt homopolymer, acrylamide / dimethylaminoethyl acrylate methyl chloride quaternary ammonium salt copolymer, acrylamide / dimethylaminoethyl methacrylate methyl chloride quaternary ammonium salt copolymer, and the like.

  Examples of the commercially available polymer include Marquat S; manufactured by Rhodia Co., Ltd. (cation group: diallyldimethylammonium chloride, cation group-containing monomer content: 50 mass%, anion group-containing monomer content: 0 mass%), Marcote 550 Manufactured by Rhodia Co., Ltd. (cation group: diallyldimethylammonium chloride, cation group-containing monomer content: 50% by mass, anion group-containing monomer content: 0% by mass), Marcote 2003; manufactured by Rhodia Co., Ltd. (cation group: methacrylamidopropyl) Trimethylammonium chloride, anionic group: acrylic acid, cation group-containing monomer content = 66 mass%, anionic group-containing monomer content 5 mass%, Marquat 2001; manufactured by Rhodia Co., Ltd. (cation group: methacrylic group) Midopropyltrimethylammonium chloride, anionic group: acrylic acid, cation group-containing monomer content = 71% by mass, anion group-containing monomer content 23% by mass, Marquat 2200; manufactured by Rhodia Co., Ltd. (cationic group: diallyldimethylammonium chloride, Cationic group-containing monomer content = 50 mass%, anionic group-containing monomer content 0 mass%), Marquat 280; Rhodia Co., Ltd. (cationic group: diallyldimethylammonium chloride, anionic group: acrylic acid, cationic group-containing monomer content = 80 mass%, anionic group-containing monomer content 20 mass%) and the like. Among these, preferred are Marquat 550, 2001, 2003, and 2200 having a weight average molecular weight in a preferred range, and Marcoat 2003 is particularly preferred.

  There is no restriction | limiting in particular as a weight average molecular weight of the said cationic polymer and an amphoteric polymer, According to the objective, it can select suitably, 150,000-10 million are preferable, 500,000-3 million are more preferable, 100 10,000 to 3,000,000 are more preferable. If it is less than 150,000, the dirt adsorbability may be reduced, and the effect of suppressing recontamination may not be sufficiently obtained.

Here, the weight average molecular weight can be determined by performing GPC (gel permeation chromatography) on the purified sample.
The conditions for the GPC, e.g., pullulan (Shodex STANDARD P-82) used as a standard sample, as a column, using a Shodex Asahipak GF-310HQ + GS- 1G7B + Shodex Asahipak GF-710HQ, mobile phase 0.3 M NaClO ₄ aqueous solution, Examples include conditions for measurement at a temperature of 40 ° C.

<Coating or impregnation>
The method for applying or impregnating the cationic polymer and / or amphoteric polymer to the nonwoven fabric is not particularly limited and may be appropriately selected from known methods for applying or impregnating a liquid according to the purpose. it can. The solution of the cationic polymer or amphoteric polymer used for the coating or impregnation is not particularly limited, but the cationic polymer and / or the amphoteric polymer can be uniformly coated or impregnated on the entire nonwoven fabric. It is particularly preferable that the cationic polymer or amphoteric polymer is uniformly dissolved in the solvent. There is no restriction | limiting in particular as said solvent, According to the selected cationic polymer or amphoteric polymer, it can select suitably.

There is no restriction | limiting in particular as content of the cationic polymer in the said dirt adsorption sheet, Although it can select suitably according to the objective, Content of the said cationic polymer (solid content) per unit area of a nonwoven fabric However, 0.1-4.0 g / m < ² > is preferable, 0.5-3.0 g / m < ² > is preferable and 1.0-2.5 g / m < ² > is especially preferable. When the content is less than 0.1 g / m ² , dirt adsorbability may be low. Moreover, even if the said content exceeds 4.0 g / m < ² >, there is no change in the adsorptivity of dirt and it cannot be said that it is preferable in terms of manufacturing cost. When the content is in the particularly preferable range, it is advantageous in that the effect of adsorbing dirt is remarkably exhibited.

The content of the amphoteric polymer in the dirt adsorbing sheet is not particularly limited and can be appropriately selected according to the purpose. However, the content of the amphoteric polymer (solid content) per unit area of the nonwoven fabric is 0.025 to 4.0 g / m ² is preferable, 0.05 to 3.0 g / m ² is preferable, and 0.5 to 2.5 g / m ² is particularly preferable. When the content is less than 0.025 g / m ² , dirt adsorbability may be low. Moreover, even if the said content exceeds 4.0 g / m < ² >, there is no change in the adsorptivity of dirt and it cannot be said that it is preferable in terms of manufacturing cost. When the content is in the particularly preferable range, it is advantageous in that the effect of adsorbing dirt is remarkably exhibited.

<Use>
The kind of dirt adsorbed by the dirt adsorbing sheet is not particularly limited and can be appropriately selected according to the purpose, but has a negative charge, and the cationic polymer and amphoteric polymer in the dirt adsorbing sheet Mud dirt, carbon dirt, protein dirt, and the like are preferable because they are easily adsorbed.

The dirt adsorbing sheet is used by being added to a washing bath. There is no restriction | limiting in particular as an area of the said dirt adsorption sheet added in a washing bath, Although it can select suitably according to the quantity of dirt and the laundry, When washing using a household washing machine, once It is preferable to add a dirt adsorbing sheet of 150 to 450 cm ² per hit. The dirt adsorbing sheet may be added as a single sheet, or may be added in multiple sheets.

  The time when the dirt adsorbing sheet is added to the washing bath may be before the start of washing, during washing, etc. Will improve. Further, when the soil adsorbing sheet is taken out from the washing bath in the same manner as described above, the convenience is improved by taking it out after dehydration. The method for determining whether or not dirt is adsorbed on the dirt adsorbing sheet is not particularly limited, and examples thereof include visual observation and measurement using spectrophotometer SE2000T (manufactured by NIPPON DENSHOKU). The dirt adsorbing sheet of the present invention is excellent in dirt adsorbing property, dirt adsorbing uniformity, washing durability, and ease of taking out from the washing bath, so that dirt in the washing bath can be effectively collected. .

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

A. Example 1 of dirt adsorption, washing durability, etc.
(1) Dirt adsorptive evaluation, (2) Uniformity evaluation of dirt adsorption, and (3) Washing durability evaluation, 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric) cut into 5 × 5 cm Prepared. Leo Guard MGP (manufactured by Lion Corporation) was used as the soil adsorbent. After impregnating and applying 0.2 g of 2.5% by mass of Leogard MGP aqueous solution to the sheet, the sheet was dried at room temperature for one day. That is, it was impregnated and applied so that the solid content of Leoguard MGP per unit area of the sheet was 2.0 g / m ² .
In addition, (4) Three sheets of 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric) cut into 10 × 15 cm were prepared for evaluation of ease of removal from the washing bath. Each of the three sheets was impregnated with 1.2 g of 2.5% by mass of Leoguard MGP aqueous solution, and then dried at room temperature for one day. That is, it was impregnated and applied so that the solid content of Leoguard MGP per unit area of the sheet was 2.0 g / m ² .

<Example 2>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Except that it was C-WJ37 (manufactured by Venus Paper Co., Ltd., non-woven fabric), and 0.37 g of a 1.4% by mass aqueous solution of Leoguard MGP was impregnated and applied to the sheet, the same as in Example 1. An adsorption sheet was produced.
Further, (4) In order to evaluate the ease of taking out from the washing bath, in Example 1, the sheet was replaced with 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric) and C-WJ37 (manufactured by Venus Paper Co., Ltd., non-woven fabric). A dirt-adsorbing sheet was produced in the same manner as in Example 1 except that the sheet was impregnated with 2.2 g of a 1.4% by mass aqueous solution of Leoguard MGP.

<Example 3>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Except that it was Syntex PS-120 (manufactured by Mitsui Chemicals, non-woven fabric), and 1.0 g of 0.5% by mass of Leoguard MGP aqueous solution was impregnated and applied to the sheet, the same as in Example 1. A dirt adsorbing sheet was produced.
(4) In order to evaluate the ease of removal from the washing bath, in Example 1, the sheet was replaced with 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric), and Shintex PS-120 (manufactured by Mitsui Chemicals, Ltd., non-woven fabric). And a soil adsorbing sheet was produced in the same manner as in Example 1 except that the sheet was impregnated with 6.0 g of 0.5% by mass of Leoguard MGP aqueous solution.

<Example 4>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Except that it was made Shintex R-214 (made by Mitsui Chemicals, non-woven fabric) and impregnated and applied 1.15% by weight of Leogard MGP aqueous solution to the sheet, the same as in Example 1. A dirt adsorbing sheet was produced.
(4) In order to evaluate the ease of taking out from the washing bath, in Example 1, the sheet was replaced with 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric), and Shintex R-214 (manufactured by Mitsui Chemicals, Ltd., non-woven fabric). And a soil adsorbing sheet was produced in the same manner as in Example 1 except that the sheet was impregnated with 2.7 g of 1.1% by mass of Leoguard MGP aqueous solution.

<Example 5>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Except that it was F850 (manufactured by Venus Paper Co., Ltd., non-woven fabric), and 0.7 g of 0.71% by mass of Leoguard MGP aqueous solution was impregnated and applied to the sheet, the dirt adsorbing sheet was the same as in Example 1. Manufactured.
Moreover, (4) In order to evaluate the ease of taking out from the washing bath, in Example 1, the sheet was replaced with 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric) and F850 (manufactured by Venus Paper Co., Ltd., non-woven fabric). A dirt adsorbing sheet was produced in the same manner as in Example 1, except that 4.2 g of 0.71% by mass of Leoguard MGP aqueous solution was impregnated and applied to the sheet.

<Example 6>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Example 1 except that it was a 100% heat-fusible fiber product (non-woven fabric manufactured by Oji Kinocross Co., Ltd.) and that 1.2 g of 0.42% by mass of Leogard MGP aqueous solution was impregnated on the sheet. Thus, a dirt adsorbing sheet was produced.
(4) In order to evaluate the ease of removal from the washing bath, in Example 1, the sheet was replaced with 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric), and 100% heat-bonded fiber (manufactured by Oji Kinocross Co., Ltd.). A non-woven fabric) and a soil adsorbing sheet were produced in the same manner as in Example 1 except that the sheet was impregnated with 7.2 g of 0.42% by mass of Leogard MGP aqueous solution.

<Example 7>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Soil adsorbing sheet in the same manner as in Example 1 except that 20GR30E (manufactured by Venus Paper Co., Ltd., non-woven fabric) and 0.5 g of 1.0% by mass of Leoguard MGP aqueous solution were impregnated and applied to the sheet. Manufactured.
Moreover, (4) In order to evaluate the ease of taking out from the washing bath, in Example 1, the sheet was replaced with 3020 (made by Venus Paper Co., Ltd., non-woven fabric) and 20GR30E (made by Venus Paper Co., Ltd., non-woven fabric). A dirt adsorbing sheet was produced in the same manner as in Example 1 except that the sheet was impregnated with 3.0 g of 1.0% by mass of Leogard MGP aqueous solution.

<Example 8>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Example 1 except that Syntex PS-116 (manufactured by Mitsui Chemicals, non-woven fabric) and 0.8 g of 0.63% by mass of Leoguard MGP aqueous solution were impregnated and applied to the sheet. A dirt adsorbing sheet was produced.
(4) In order to evaluate the ease of taking out from the washing bath, in Example 1, the sheet was replaced with 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric), and Shintex PS-116 (manufactured by Mitsui Chemicals, Ltd., non-woven fabric). And a dirt adsorbing sheet was produced in the same manner as in Example 1 except that the sheet was impregnated with 4.8 g of 0.63% by mass of Leoguard MGP aqueous solution.

<Example 9>
In Example 4, 3020 sheets were used for (1) dirt adsorption evaluation, (2) dirt adsorption uniformity evaluation, (3) washing durability evaluation, and (4) ease of removal from the washing bath. A dirt adsorbing sheet was produced in the same manner as in Example 4 except that Syntex R-016 (Mitsui Chemicals, non-woven fabric) was used instead of (nonwoven fabric manufactured by Venus Paper Co., Ltd.).

<Example 10>
In Example 7, 3020 was used for (1) dirt adsorption evaluation, (2) dirt adsorption uniformity evaluation, (3) washing durability evaluation, and (4) ease of removal from the washing bath. A dirt adsorbing sheet was produced in the same manner as in Example 7 except that 4060 (manufactured by Venus Paper Co., Ltd., non-woven fabric) was used instead of (manufactured by Venus Paper Co., Ltd., non-woven fabric).

<Comparative Example 1>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Except for using R-004 (manufactured by Mitsui Chemicals, non-woven fabric), and impregnating and applying 0.13 g of 3.9% by mass of Leoguard MGP aqueous solution to the sheet, the same as in Example 1. An adsorption sheet was produced.
Moreover, (4) In order to evaluate the ease of taking out from the washing bath, in Example 1, instead of 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric), R-004 (manufactured by Mitsui Chemicals Co., Ltd., non-woven fabric) and A dirt adsorbing sheet was produced in the same manner as in Example 1 except that 0.78 g of 3.9% by mass of Leoguard MGP aqueous solution was impregnated and applied to the sheet.

<Comparative example 2>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. A dirt adsorbing sheet was obtained in the same manner as in Example 1 except that the sheet was N15J (manufactured by Venus Paper Co., Ltd., non-woven fabric) and the sheet was impregnated with 0.15 g of 3.3% by mass of Leoguard MGP aqueous solution. Manufactured.
(4) In order to evaluate the ease of taking out from the washing bath, in Example 1, the sheet was replaced with 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric) and N15J (manufactured by Venus Paper Co., Ltd., non-woven fabric). A dirt adsorbing sheet was produced in the same manner as in Example 1, except that 0.9 g of 3.3% by mass of Leogard MGP aqueous solution was impregnated and applied to the sheet.

<Comparative Example 3>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Except that it was 18DR (manufactured by Venus Paper Co., Ltd., non-woven fabric), and 0.18 g of 2.8% by mass of Leogard MGP aqueous solution was impregnated and applied to the sheet, the dirt adsorbing sheet was the same as in Example 1. Manufactured.
Moreover, (4) In order to evaluate the ease of taking out from the washing bath, in Example 1, the sheet was replaced with 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric) and 18DR (manufactured by Venus Paper Co., Ltd., non-woven fabric). A dirt adsorbing sheet was produced in the same manner as in Example 1 except that 1.1 g of 2.8% by mass of Leogard MGP aqueous solution was impregnated and applied to the sheet.

<Comparative example 4>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Except that it was AL150CDP-H (manufactured by Venus Paper Co., Ltd., non-woven fabric) and the sheet was impregnated and coated with 0.33% by mass of Leogard MGP aqueous solution in the same manner as in Example 1, it was stained. An adsorption sheet was produced.
Moreover, (4) In order to evaluate the ease of taking out from the washing bath, in Example 1, instead of the sheet 3020 (made by Venus Paper Co., Ltd., non-woven fabric), AL150CDP-H (made by Venus Paper Co., Ltd., non-woven fabric) and A dirt adsorbing sheet was produced in the same manner as in Example 1 except that the sheet was impregnated with 9.0 g of 0.33% by mass of Leoguard MGP aqueous solution.

<Comparative Example 5>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Except that it was made high cloth A-200 (manufactured by Oji Kinocross Co., Ltd., non-woven fabric), and 2.0 g of a 0.25% by mass aqueous solution of Leoguard MGP was impregnated and applied to the sheet, the same as in Example 1. A dirt adsorbing sheet was produced.
(4) In order to evaluate the ease of taking out from the washing bath, in Example 1, instead of the sheet 3020 (made by Venus Paper Co., Ltd., non-woven fabric), Hi-Cross A-200 (made by Oji Kinocloth Co., Ltd., non-woven fabric) And a dirt adsorbing sheet was produced in the same manner as in Example 1, except that 12 g of 0.25% by mass of Leoguard MGP aqueous solution was impregnated and applied to the sheet.

<Comparative Example 6>
In Example 1, the sheet was replaced with 3020 (nonwoven fabric manufactured by Venus Paper Co., Ltd.) in order to evaluate (1) dirt adsorptivity, (2) dirt adsorption uniformity evaluation, and (3) washing durability evaluation. Soil-adsorbing sheet in the same manner as in Example 1 except that it was made of cotton (skin shirt fabric, 100% cotton) and 0.5 g of 1.0% by mass of Leogard MGP aqueous solution was impregnated on the sheet. Manufactured.
Moreover, (4) In order to evaluate the ease of taking out from the washing bath, in Example 1, the sheet was replaced with 3020 (manufactured by Venus Paper Co., Ltd., non-woven fabric) and cotton (skin shirt fabric, 100% cotton) was used. A dirt adsorbing sheet was produced in the same manner as in Example 1 except that the sheet was impregnated and applied in an amount of 0.5 g of 1.0% by mass of Leogard MGP aqueous solution.

-Evaluation method-
The dirt adsorbing sheets of Examples 1 to 10 and Comparative Examples 1 to 6 were used for washing model dirt cloth according to the following procedure.
Mikatagahara red soil dirt cloth, EMPA101 cloth (manufactured by Swiss Federal Institute of Materials), EMPA106 cloth (manufactured by Swiss Federal Institute of Materials), EMPA116 cloth (manufactured by Swiss Federal Institute of Materials), artificial dirt cloth (foundation ・Laundry Science Association, “Wet Artificial Contaminated Cloth”), 5 types of model soiled cloth (red soil only 3 × 4 cm, others 5 × 5 cm), Terg-O-Tometer and detergent (Top, manufactured by Lion Corporation) And washed with a dirt adsorbing sheet.
Washing conditions were as follows: detergent concentration: 666 ppm (mass ratio), rotation speed: 120 rpm, water temperature: 25 ° C., tap water amount: 900 mL. In addition, as a model soil cloth for red soil stain of Mikatagahara, a cotton melias cloth impregnated with a red soil dispersion (500 g of water for 15 g of red soil) and then dried at 105 ° C. for 2 hours was used.
The following (1) to (4) were evaluated for the dirt adsorbing sheets of Examples 1 to 10 and Comparative Examples 1 to 6 used for washing the model dirty cloth. The results are shown in Table 1.

(1) Adsorption of dirt The color difference (ΔZ value) before and after washing of the dirt adsorbing sheet taken out after the washing experiment was measured using a spectrophotometer SE2000T (manufactured by NIPPON DENSHOKU) to obtain the dirt adsorbing property. The evaluation criteria for dirt adsorption are as follows.
-Evaluation criteria-
ΔZ = color difference after washing−color difference before washing A: ΔZ value is −40 or less.
○: ΔZ value is larger than −40 and not larger than −15.
Δ: ΔZ value is larger than −15 and not larger than −5.
X: ΔZ value is larger than −5.
In addition, (double-circle) and (circle) were set as the pass, and (triangle | delta) and x were made disqualified.

(2) Uniformity of dirt adsorption The degree of uniformity of dirt adsorption of the dirt adsorbing sheet taken out after the washing experiment was visually evaluated. The evaluation criteria for the uniformity of dirt adsorption are as follows.
-Evaluation criteria-
A: Dirt is uniformly adsorbed on the entire sheet (including the front and back sides).
○: Dirt is adsorbed almost uniformly on the entire sheet (including the front and back sides).
Δ: Dirt is adhering to the entire sheet (including the front and back sides) somewhat unevenly.
X: Dirt is adhering to the sheet unevenly.
In addition, (double-circle) and (circle) were set as the pass, and (triangle | delta) and x were made disqualified.

(3) Washing durability Evaluation of washing durability of the dirt adsorbing sheet taken out after the washing experiment was visually evaluated. The evaluation criteria for the washing durability evaluation are as follows.
-Evaluation criteria-
A: There is no fuzz.
○: Slightly fuzzy.
Δ: It is considerably fuzzy.
X: Very fluffy. In addition, (double-circle) and (circle) were set as the pass, and (triangle | delta) and x were set as the disqualification.

(4) Ease of taking out from the washing bath Using a fully automatic washing machine (AW-F80HVP, manufactured by Toshiba Corporation), wash 4.5 kg of laundry with a dirt adsorbing sheet, and stain from the washing bath after washing. The adsorption sheet was taken out. Sensory evaluation was conducted on the ease of taking out the dirt adsorbing sheet. Washing conditions were as follows: water amount: 60 L, detergent: top (manufactured by Lion Corporation) 40 g. The evaluation criteria for the ease of taking out from the washing bath are as follows.
-Evaluation criteria-
A: All three sheets can be removed without problems.
○: Two sheets can be taken out without problems.
Δ: Only one sheet can be taken out without any problem.
×: Cannot be easily taken out with laundry.
In addition, (double-circle) and (circle) were set as the pass, and (triangle | delta) and x were made disqualified.

<Examples 11-20, Comparative Examples 7-12>
Using the dirt adsorbing sheets of Examples 1 to 10 and Comparative Examples 1 to 6, the conditions for the amount of dirt and the bath ratio were evaluated under conditions close to the real system. The results of evaluation using the dirt adsorbing sheets of Examples 1 to 10 are shown in Table 2 as Examples 11 to 20, and the results of evaluation using the dirt adsorbing sheets of Comparative Examples 1 to 6 are shown in Table 2 as Comparative Examples 7 to 12. Indicated.

-Evaluation method-
Mikatagahara red soil dirt cloth, EMPA101 cloth (manufactured by Swiss Federal Institute of Materials), EMPA106 cloth (manufactured by Swiss Federal Institute of Materials), EMPA116 cloth (manufactured by Swiss Federal Institute of Materials), artificial dirt cloth (foundation ・Laundry Science Association, "Wet Artificial Contaminated Cloth") 5 types of model soiled cloth (red soil only 1 x 1 cm, others 1 x 2.1 cm), Terg-O-Tometer and detergent (Top, Lion Co., Ltd.) And made with a dirt adsorbing sheet.
Washing conditions were as follows: detergent concentration: 666 ppm (mass ratio), rotation speed: 120 rpm, water temperature: 15 ° C., tap water amount: 450 mL, bath ratio: 15 times. In addition, as a model soil cloth for red soil stain of Mikatagahara, a cotton melias cloth impregnated with a red soil dispersion (500 g of water for 15 g of red soil) and then dried at 105 ° C. for 2 hours was used.

(1) Adsorption of dirt The color difference (ΔZ value) before and after washing of the dirt adsorbing sheet taken out after the washing experiment was measured using a spectrophotometer SE2000T (manufactured by NIPPON DENSHOKU) to obtain the dirt adsorbing property. The evaluation criteria for dirt adsorption are as follows.
-Evaluation criteria-
ΔZ = color difference after washing−color difference before washing A: ΔZ value is −10 or less.
A: ΔZ value is larger than −10 and not larger than −5.
Δ: ΔZ value is larger than −5 and not larger than −1.
X: ΔZ value is larger than −1.

(2) Uniformity of dirt adsorption The same method and evaluation criteria as those described in Examples 1 to 10 were used.

(3) Washing durability The washing durability was evaluated by the same method and evaluation criteria as those described in Examples 1-10.

(4) Ease of taking out from washing bath It carried out by the method and evaluation criteria similar to the said method of the said Examples 1-10.

<Example 21>
(1) In order to evaluate the adsorptivity of dirt, a sheet of 4060 (manufactured by Venus Paper Co., Ltd., non-woven fabric) cut to 5 × 5 cm was prepared. Takifloc C-809 (manufactured by Taki Chemical Co., Ltd.) was used as the dirt adsorbent. After 0.5 g of 1% by mass of Takifloc C-809 aqueous solution was impregnated on the sheet, it was dried at room temperature for one day. That is, it was impregnated and applied so that the solid content of Takiflock C-809 per unit area of the sheet was 2.0 g / m ² .

<Example 22>
In Example 21, the dirt adsorbent was replaced with Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) instead of Takiflock C-806 (manufactured by Taki Chemical Co., Ltd.). An adsorption sheet was produced.

<Example 23>
In Example 21, the dirt adsorbent was replaced with Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) instead of Takiflock C-805 (manufactured by Taki Chemical Co., Ltd.). An adsorption sheet was produced.

<Example 24>
In Example 21, the dirt adsorbent was replaced with Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) instead of Takiflock C-414 (manufactured by Taki Chemical Co., Ltd.). An adsorption sheet was produced.

<Example 25>
In Example 21, dirt was adsorbed in the same manner as in Example 21 except that Takiflock C-409 (manufactured by Taki Chemical Co., Ltd.) was used instead of Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.). An adsorption sheet was produced.

<Example 26>
In Example 21, dirt was adsorbed in the same manner as in Example 21 except that Takiflock C-838 (manufactured by Taki Chemical Co., Ltd.) was used instead of Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.). An adsorption sheet was produced.

<Example 27>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21 except that Jaguar Excel (made by Rhodia Co., Ltd.) was used instead of Takiflock C-809 (Taki Chemical Co., Ltd.). did.

<Example 28>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21, except that Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) was replaced with Leo Guard MGP (manufactured by Lion Corporation). did.

<Example 29>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 11 except that the dirt adsorbent was replaced with Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) and Leo Guard MLP (manufactured by Lion Corporation). did.

<Example 30>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21 except that the dirt adsorbent was replaced with Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) and Leo Guard GP (made by Lion Corporation). did.

<Example 31>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21, except that Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) was replaced with Leo Guard KGP (manufactured by Lion Corporation). did.

<Example 32>
In Example 21, a dirt adsorbing sheet was obtained in the same manner as in Example 21 except that Tyfloc C-809 (manufactured by Taki Chemical Co., Ltd.) was replaced with Cyprogum NGK (manufactured by Hita Chemical Co., Ltd.). Manufactured.

<Example 33>
In Example 21, soil adsorption was performed in the same manner as in Example 21 except that EX-3 (manufactured by Hita Chemical Co., Ltd.) was used instead of Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.). A sheet was produced.

<Example 34>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21 except that Marcote S (manufactured by Rhodia) was used instead of Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.). did.

<Example 35>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21 except that the soil adsorbent was replaced with Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) and Marcoat 550 (manufactured by Rhodia Co., Ltd.). did.

<Example 36>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21 except that Marut 2003 (Rodia Co., Ltd.) was used instead of Takiflock C-809 (Taki Chemical Co., Ltd.). did.

<Example 37>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21, except that Marut 2001 was used instead of Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.). did.

<Example 38>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21 except that the soil adsorbent was replaced with Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) and Marcoat 2200 (manufactured by Rhodia Co., Ltd.). did.

<Example 39>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21, except that Marut 280 (manufactured by Rhodia) was used instead of Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.). did.

<Example 40>
In Example 21, a dirt adsorbing sheet was produced in the same manner as in Example 21 except that the soil adsorbent was replaced with Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) and Marcoat 100 (manufactured by Rhodia Co., Ltd.). did.

<Comparative Example 13>
In Example 21, the dirt adsorbent was replaced with Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) and replaced with PVP K-30 (ISP Japan Co., Ltd.). A sheet was produced.

<Comparative example 14>
In Example 21, the soil adsorption was performed in the same manner as in Example 21 except that PVP K-90 (ISP Japan Co., Ltd.) was used instead of Takiflock C-809 (Taki Chemical Co., Ltd.). A sheet was produced.

<Comparative Example 15>
In Example 21, dirt was adsorbed in the same manner as in Example 21 except that Takiflock N-100T (manufactured by Taki Chemical Co., Ltd.) was used instead of Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.). An adsorption sheet was produced.

<Comparative Example 16>
In Example 21, except that the dirt adsorbent was changed to Takiflock C-809 (manufactured by Taki Chemical Co., Ltd.) and Laborum gum CG-M6L (manufactured by Dainippon Sumitomo Pharma Co., Ltd.), A dirt adsorbing sheet was produced.

-Evaluation method-
The dirt adsorbing sheets of Examples 21 to 40 and Comparative Examples 13 to 16 were used for washing model dirt cloth in the same manner as in Examples 1 to 10 and Comparative Examples 1 to 6.
Regarding the dirt adsorbing sheets of Examples 21 to 40 and Comparative Examples 13 to 16 used for the washing, (1) Evaluation of dirt adsorbability was performed in the same manner as described above. (5) The evaluation of manufacturability was evaluated according to the following criteria, assuming that the weight average molecular weight of each soil adsorbent is proportional to the viscosity, and the viscosity and manufacturability are inversely proportional. The results are shown in Table 3.
(Judgment criteria for manufacturability)
◎: Weight average molecular weight 2.5 million or less ○: Weight average molecular weight 2.5 million to 4 million Δ: Weight average molecular weight 4 million to 10 million ×: Weight average molecular weight 10 million or more

<1>: Acrylamide-dimethylaminoethyl methacrylate methyl chloride quaternary ammonium salt copolymer <2>: Dimethylaminoethyl methacrylate methyl chloride quaternary ammonium salt homopolymer <3>: Acrylamide-dimethylaminoethyl acrylate methyl quaternary ammonium chloride Salt copolymer <4>: Cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 0/50
<5>: Cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 0/50
<6>: Anionic group: acrylic acid, cationic group: methacrylamidopropyltrimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 5/66
<7>: Anionic group: acrylic acid, cationic group: methacrylamidopropyltrimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 23/71
<8>: Cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 0/50
<9>: Anionic group: acrylic acid, cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 20/80
<10>: Cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 0/100

<Examples 41 to 60, Comparative Examples 17 to 20>
Using the dirt adsorbing sheets of Examples 21 to 40 and Comparative Examples 13 to 16, the conditions for the amount of dirt and the bath ratio were evaluated under conditions close to the real system. The evaluation method is the same as in Examples 11-20. The results of evaluation using the dirt adsorbing sheets of Examples 21 to 40 are shown in Table 4 as Examples 41 to 60, and the results of evaluation using the dirt adsorbing sheets of Comparative Examples 13 to 16 are shown in Table 4 as Comparative Examples 17 to 20. Indicated.

<1>: Acrylamide-dimethylaminoethyl methacrylate methyl chloride quaternary ammonium salt copolymer <2>: Dimethylaminoethyl methacrylate methyl chloride quaternary ammonium salt homopolymer <3>: Acrylamide-dimethylaminoethyl acrylate methyl quaternary ammonium chloride Salt copolymer <4>: Cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 0/50
<5>: Cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 0/50
<6>: Anionic group: acrylic acid, cationic group: methacrylamidopropyltrimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 5/66
<7>: Anionic group: acrylic acid, cationic group: methacrylamidopropyltrimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 23/71
<8>: Cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 0/50
<9>: Anionic group: acrylic acid, cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 20/80
<10>: Cationic group: diallyldimethylammonium chloride, anion group-containing monomer content / cation group-containing monomer content = 0/100

B. About the adsorptivity and recontamination of dirt <Examples 61 to 69, Comparative Example 21>
The recontamination suppression property was evaluated by the method described below.
(Recontamination suppression sheet manufacturing method)
The nonwoven fabric was cut into 5 × 5 cm, and the quaternary ammonium salt-containing polymer compound shown in Table 5 was added to the nonwoven fabric at 1000% o. w. f. When applied, the concentration of the aqueous solution was adjusted so that the compound amount per unit area of the nonwoven fabric was 2 g / m ² as a pure component, and after application or impregnation, the solution was left indoors and air-dried. Then, it cut | judged to 2x2.25cm, and was set as the recontamination suppression sheet | seat of Example 61- Example 69 and the comparative example 21. FIG.

(Evaluation cloth production method)
Cotton Melias (white, non-fluorescent, 0.02 g / cm ² ) fabric using a two-layer washing machine (CW-C30A1-H, manufactured by Mitsubishi Electric Corporation), tap water (50 ° C., 3 ° DH) 30 L , And a commercial powder detergent for clothing (Top, manufactured by Lion Corporation) were added in an amount of 667 ppm and washed for 15 minutes. The cotton Melias fabric was then 100% o. w. f. After dehydration until the water content becomes, it was washed once again under the above conditions. Then, the process of rinsing with 30 L of tap water (50 ° C., 3 ° DH) for 15 minutes was repeated 5 times. Finally, the evaluation fabric is 100% o. w. f. The water content was dehydrated, and after drying, it was cut into 5 × 5 cm to obtain an evaluation cloth.

(Cleaning experiment)
Using detergent (Top, manufactured by Lion Co., Ltd.), red soil dirt, EMPA101, EMPA106, EMPA116, artificial dirt total 5 model dirt cloths (red earth only 1 x 1 cm, others 1 x 2.1 cm) Along with 1 pollution control sheet, 5 evaluation cloths, charge cloth (finely cut skin shirt (manufactured by BVD), bath ratio 15 times), it was washed using a Terg-O-Tomometer. Washing conditions were as follows: tap water (15 ° C., 3 ° DH) 450 mL and commercially available powder detergent for clothing (Top, manufactured by Lion Corporation) were added in an amount of 667 ppm, followed by stirring for 1 minute and washing for 10 minutes. Then 100% o. w. f. After dehydration until the water content became, the step of rinsing with 450 mL of tap water (15 ° C., 3 ° DH) for 3 minutes was repeated twice. Finally 100% o. w. f. After dehydration until the water content became, it was left indoors and air-dried. This washing experiment was repeated three times. In addition, the re-contamination suppression sheet used a new thing every time, and the evaluation cloth used the same thing 3 times, and accumulated dirt. The red soil stain was obtained by impregnating a cotton melias cloth with a red soil dispersion of Mikatagahara (500 g of water with respect to 15 g of red soil) and then drying at 105 ° C. for 2 hours. In addition, the color difference (ΔZ _B ) before and after cleaning of the evaluation fabric when cleaning was performed under the above conditions without inserting a sheet was used as a blank.

(Recontamination inhibition evaluation method)
The color difference (ΔZ value) before and after cleaning of the five evaluation cloths taken out after the three cleaning experiments was measured using a spectrophotometer SE200T (manufactured by NIPPON DENSHOKU), and the recontamination suppression property was measured using the average value of the five color differences. The results are shown in Table 5. The criteria for recontamination control were as follows.

(Judgment criteria for recontamination suppression)
A: ΔZ _B −ΔZ ≧ 1
○: 1> ΔZ _B −ΔZ ≧ 0.5
Δ: 0.5> ΔZ _B −ΔZ ≧ 0.1
×: 0.1> ΔZ _B −ΔZ

a-1 Cationized guar gum: Jaguar Excel, Rhodia Co., Ltd. (nitrogen content N: 1.6)
a-2 Cationized cellulose: Leogard MGP, Lion Corporation (nitrogen content N: 1.8)
a-3 Cationized cellulose: Leogard GP, Lion Corporation (nitrogen content N: 1.8)
a-4 Cationized cellulose: Leogard KGP, Lion Corporation (nitrogen content N: 1.8)
a-5 Marcote 550, Rhodia Co., Ltd. (anion group-containing monomer content / cation group-containing monomer content = 0/50, cation group: diallyldimethylammonium chloride)
a-6 Marcote 2003, Rhodia Co., Ltd. (anion group-containing monomer content / cation group-containing monomer content = 5/66, anion group: acrylic acid, cationic group: methacrylamidopropyltrimethylammonium chloride)
a-7 Marcote 2001, Rhodia Co., Ltd. (anion group-containing monomer content / cation group-containing monomer content = 23/71, anion group: acrylic acid, cation group: methacrylamidopropyltrimethylammonium chloride)
a-8 Marcote 2200, Rhodia Co., Ltd. (anion group-containing monomer content / cation group-containing monomer content = 0/50, cation group: diallyldimethylammonium chloride)
a-9 Marcote 280, Rhodia Co., Ltd. (anion group-containing monomer content / cation group-containing monomer content = 20/80, anion group: acrylic acid, cation group: diallyldimethylammonium chloride)
a-10 Cationized guar gum: Labor gum CG-M6L, Dainippon Sumitomo Pharma Co., Ltd. (nitrogen content N: 2)

<Examples 70 to 82>
<Evaluation method based on base impregnation>
(Recontamination suppression sheet manufacturing method)
1000% o. w. f. When applied, the base solution concentration is adjusted so that the amount of cationized polysaccharide (Jaguar Excel) converted into per unit area of the nonwoven fabric is as shown in Table 6 as a pure component, and recontamination is suppressed by the above method. Sheets were produced and designated as Examples 70 to 75. Similarly, the base solution concentration is adjusted so that the quaternary ammonium salt-containing acrylic copolymer (Mercoat 2003) has a supported amount shown in Table 7 as a pure component, and a recontamination suppression sheet is prepared by the above method. Example 76 to Example 82 were used.

(Evaluation cloth production method)
An evaluation fabric was prepared by the above method.
(Recontamination inhibition evaluation method)
After cleaning by the above cleaning method, the recontamination suppression property was evaluated by the above recontamination suppression evaluation method, and are shown in Tables 6 and 7.

The dirt adsorbing sheet of the present invention is excellent in dirt adsorbing property, dirt adsorbing uniformity, washing durability, ease of taking out from the washing bath, and recontamination inhibiting property, and effectively collects dirt in the washing bath. For example, it can be suitably used as a laundry auxiliary material.
Further, the dirt adsorbing sheet of the present invention is excellent in dirt adsorbing property, dirt adsorbing uniformity, washing durability and ease of taking out from the washing bath, and can effectively collect dirt in the washing bath. It can be suitably used for visualizing dirt separated from clothing, and for example, can be suitably used for performance evaluation of detergents.

Claims (5)

Dirt in the wash bath a sheet to be adsorbed, at least one of basis weight 20g / m ² ~120g / m 1 or more cationic polymer compound ² of the nonwoven fabric and one or more amphoteric polymer compound A dirt adsorbing sheet characterized by being applied or impregnated.   The soil adsorbing sheet according to claim 1, wherein the cationic polymer compound is a cationized polysaccharide and the amphoteric polymer compound is a quaternary ammonium salt-containing acrylic polymer.   The cationized polysaccharide is at least one selected from cationized guar gum, cationized cellulose and cationized starch, and the quaternary ammonium salt-containing acrylic polymer is an aminoalkyl (meth) acrylate quaternary ammonium salt polymer or The dirt adsorbing sheet according to claim 2, which is an acrylamide-aminoalkyl (meth) acrylate quaternary ammonium salt copolymer.   The dirt adsorbing sheet according to any one of claims 1 to 3, wherein the polymer compound has a weight average molecular weight of 150,000 to 10,000,000.   The dirt adsorbing sheet according to any one of claims 1 to 4, wherein the nonwoven fabric is a nonwoven fabric produced by any one of a spunbond method and a chemical bond method.