JPH0551718B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to deodorizing wet nonwoven fabrics, specifically diapers,
The present invention relates to a wet-laid nonwoven fabric that can be used for sanitary materials such as napkins, masks, toilet paper, and wrapping paper, and has excellent deodorizing properties. [Prior art] As a wet non-woven fabric with deodorizing effect,
Typical examples include mixed paper containing activated carbon fibers as shown in Japanese Utility Model Publication No. 3282, and deodorant-impregnated paper for filth as shown in Japanese Utility Model Publication No. 59-32389. [Problems to be solved by the invention] The deodorizing properties of the mixed paper described in Utility Model Publication No. 53-3282 depend on the adsorption capacity of activated carbon fibers, so the adsorption effect of unspecified gases is poor. Yes, it is very versatile. On the other hand, the durability of the deodorizing effect is not fully satisfactory. Moreover, the deodorant-impregnated paper described in Utility Model Publication No. 59-32389 is made by impregnating paper with a mixture mainly composed of ferrous sulfate, sodium bicarbonate, and burnt alum, which has the property of generating carbon dioxide gas. It is what it is. The problem is that the deodorizing effect is not achieved unless the mixture is dissolved and reacted in the liquid to generate carbon dioxide gas, and its use is very specific. The present invention solves these difficulties and eliminates hydrogen sulfide,
The present invention provides a deodorizing wet nonwoven fabric that exhibits an excellent deodorizing effect against all kinds of bad odors such as mercaptan, ammonia, and various amine compounds, and that lasts for a long time. [Means for Solving the Problems] A first invention for solving the above problems is a first short fiber carrying 1% by weight or more of metal phthalocyanine/polycarboxylic acid, and copper ions and cobalt ions. , 0.1 or more metal ions selected from iron ions, nickel ions, calcium ions, barium ions, and magnesium ions.
It is a deodorizing wet-laid nonwoven fabric containing second short fibers supported at ~20% by weight. Similarly, the second invention comprises 1% by weight or more of metal phthalocyanine polycarboxylic acid and ions of one or more metals selected from copper ions, cobalt ions, iron ions, nickel ions, calcium ions, barium ions, and magnesium ions.
This is a deodorizing wet-laid nonwoven fabric containing short fibers carrying 0.1 to 20% by weight. The above-mentioned metal complexes, which are deodorizing components supported on fibers, are metal porphyrins, metal porphyrazines, and derivatives thereof, which have redox ability, and are supported in physical contact with fiber components or chemically It is bonded and supported to form a polymer metal complex. Metalporphyrin and its derivatives are represented by the structural formula shown in FIG.
Metal porphyrazine is a metal phthalocyanine represented by the structural formula shown in FIG. In both formulas, M is, for example, Fe, Co, Mn, Ti, V, Ni,
Examples include metals such as Cu, Zn, Mo, and W. Among these metals, iron and cobalt are preferred from the viewpoint of deodorizing effect. In both formulas, X represents hydrogen or a substituent. Examples of substituents include alkyl groups, substituted alkyl groups (e.g. chloromethyl group), halogen groups, nitro groups, amino groups, azo groups, thiocyanate groups, carboxyl groups, carbonyl chloride groups, carboxylamide groups, nitrile groups, hydroxyl groups, Examples include alkoxyl groups, phenoxyl groups, sulfonic acid groups, sulfonyl chloride groups, sulfonamide groups, thiol groups, alkyl silicon groups, vinyl groups, and alkali salts of carboxyl groups and sulfonic acid groups. These can be used alone or in combination
More than one species is used. Among these, carboxyl groups, sulfonic acid groups, alkali salts thereof, amino groups, halogen groups, hydroxyl groups, and the like are preferably used. The most preferred specific examples of metal phthalocyanine polycarboxylic acids are cobalt phthalocyanine octacarboxylic acid, cobalt phthalocyanine tetracarboxylic acid, iron phthalocyanine octacarboxylic acid, or iron phthalocyanine tetracarboxylic acid. The above metal phthalocyanine polycarboxylic acids may be used alone or in combination of two or more. The required amount of metal phthalocyanine polycarboxylic acid supported is generally 1% by weight or more. The larger the supported amount, the more deodorizing activity will be obtained; if the supported amount is smaller, the desired level of deodorizing activity will not be obtained, and the sustainability of the deodorizing activity will also be poor. However, there is a limit to the amount of metal phthalocyanine polycarboxylic acid that can be supported on the fibers, and the preferred amount is in the range of 1 to 20% by weight. The metal ions that are the deodorizing component supported on the fibers are transition metal ions, such as copper ions, iron ions, cobalt ions, and nickel ions, but metal ions other than transition metals include calcium ions, barium ions, and magnesium ions. Ion is good. The metal ions to be supported may be used alone or in combination of two or more. It is desirable that the amount of metal ions supported be as large as possible;
From the viewpoint of economy and the strength and shape retention of the supported fibers, the appropriate amount is about 0.1 to 20% by weight.
The above-mentioned metal ions may be supported by directly physically contacting the fibers, or may be supported by being chemically bonded to the polymers of the fibers. In the latter example, a polymeric metal complex is formed of an intramolecular chelate complex of polyvinyl alcohol and copper ions, a complex of polyvinylamine and iron ions, etc. Further, the compound containing the metal ion may be carried by physically contacting the fiber, or may be carried by being chemically bonded to the polymer of the fiber. Examples of fibers carrying metal phthalocyanine/polycarboxylic acids and fibers carrying metal ions include wood pulp, regenerated cellulose fibers, hygroscopic synthetic fibers, porous fibers, and porous hollow fibers. is 150-500
% regenerated cellulose fiber, unripe cotton or acetate rayon is preferred. [Function] The deodorizing wet-laid nonwoven fabric of the present invention oxidizes and decomposes subodor substances such as hydrogen sulfide and mercaptans, making them odorless due to the action of the metal phthalocyanine polycarboxylic acid supported on the constituent fibers. . That is, the metal coordinated with the porphyrin and porphyrazine rings serves as an active center, and the oxidation reaction proceeds. For example, taking the oxidation of mercaptan as an example, the oxidation is shown by the following chemical reaction formula. 2R−SH＋2OH ⁻ →2R−S ⁻ +2H ₂ O …(1) 2R−S ⁻ +2H ₂ O＋O ₂ →R−S−S−R+H ₂ O ₂ +2OH ⁻ …(2) Produced by the reaction of formula (1) The thiolate anion coordinates with oxygen to porphyrin and porphyrazine to form an active species that is a ternary complex. The thiolate anion coordinated to this active species is dimerized into a disulfide shown in formula (2) via a thiyl radical, and is incorporated into the fiber, making it odorless. In the case of hydrogen sulfide, it decomposes into odorless sulfur and water as shown in the following formula. 2H ₂ S + O ₂ →2S + 2H ₂ O This reaction is very similar to in vivo enzymatic oxidation reactions. All oxidation reactions by enzymes are aerobic reactions. In other words, most of them perform oxygen oxidation reactions. Examples of oxidation reactions of odor-like substances by oxidizing enzymes include those shown below.

〔Example〕

Example 1 (Example of the first invention) A rayon staple with a primary swelling degree of about 200%, a length of 10 m/m, and a thickness of 4 denier was prepared using an aqueous solution of iron phthalocyanine/polycarboxylic acid (aqueous solution concentration of 3 g/m).
PH12) and then dehydrated and dried to obtain fibers (hereinafter referred to as first fibers) carrying approximately 2.5% by weight of iron phthalocyanine polycarboxylic acid. On the other hand, the same rayon staple as above was immersed in an aqueous copper acetate solution (concentration 5 g/) and then dehydrated and dried to obtain fibers (hereinafter referred to as second fibers) carrying about 2.5% by weight of copper acetate. 100 parts by weight of equivalent first and second fibers, and 7 parts by weight of a polyvinyl alcohol fibrous binder (trade name: Fibribond 343, manufactured by Sansho Co., Ltd.) with a length of 3 m/m and a thickness of 1 denier. A deodorizing crepe paper with a basis weight of 20 g/m ² was obtained by making paper using a circular wire paper machine from a paper making liquid in which the above components were dispersed. A sanitary napkin is made by stacking four sheets of crepe paper and interposing them between absorbent layers. When this napkin and a sanitary napkin without deodorant crepe paper were subjected to a practical test, the former sanitary napkin had an excellent deodorizing effect and eliminated the leakage of unpleasant odors when worn. Ta. Example 2 (Example of the first invention) 100 parts by weight of mixed fibers consisting of equivalent amounts of first fibers and second fibers in Example 1 and beaten wood pulp
Paper was made using a fourdrinier paper machine from a paper making liquid in which 10 parts by weight were dispersed to obtain thin paper for home use with a basis weight of 15 g/m ² . When this tissue paper was used as a diaper, the odor of excrement was significantly reduced. Example 3 (Example of the first invention) The first fiber of Example 1 is 30% by weight, the second fiber is 30% by weight, and the core is made of polypropylene (melting point
Example 1: 100 parts by weight of a mixed fiber consisting of 40% by weight of core-sheath type thermoadhesive composite fiber (length 10 m/m, thickness 2 denier) whose sheath part is polyethylene (melting point 134°C) (167°C) A deodorizing wet-laid nonwoven fabric having a basis weight of 60 g/m ² was obtained by making paper using a circular mesh paper machine from a paper making solution in which 7 parts by weight of a polyvinyl alcohol-based fibrous binder was dispersed. This nonwoven fabric was heat-treated at 140°C to obtain a nonwoven fabric sheet in which the low melting point components of the composite fibers were melted. When a simple mask was made from this non-woven fabric sheet and used by cleaning workers in public toilets, it received high praise for its effectiveness in removing toilet odors, and it was confirmed that the mask could eliminate the bad odor emanating from excrement and urine. Example 4 (Example of the second invention) The first fiber of Example 1 above was mixed with a copper acetate aqueous solution (concentration 5
After soaking in g/l, dehydrate and dry. As a result, fibers carrying about 2.5% by weight of iron phthalocyanine polycarboxylic acid and about 2.5% by weight of copper acetate were obtained.
A deodorizing crepe with a basis weight of 20 g/m ² was made from a paper making liquid in which 100 parts by weight of these fibers and 7 parts by weight of the polyvinyl alcohol-based fibrous binder of Example 1 were dispersed. Got paper. When this crepe paper was subjected to the same usage test as in Example 1, it was confirmed that it had substantially the same deodorizing effect. Example 5 (Example of the second invention) 100 parts by weight of fibers carrying about 2.5% by weight of iron phthalocyanine polycarboxylic acid and about 2.5% by weight of copper acetate obtained in Example 4 above, and 10 parts by weight of beaten wood pulp. A fourdrinier paper machine was used to make paper from the paper making liquid in which the above was dispersed to obtain thin paper for home use with a basis weight of 15 g/m ² . When this thin paper was subjected to the same usage test as in Example 2, it was confirmed that it had substantially the same deodorizing effect. [Effects of the Invention] As explained above, the deodorizing wet-laid nonwoven fabric to which the present invention is applied has the ability to oxidize and decompose malodorous components through a reaction similar to biological oxidase of metal phthalocyanine polycarboxylic acid supported on fibers, and Based on the metal amine complex formation reaction of metal ions supported on the fibers, the deodorizing effect is large and lasts for a long period of time. It has a deodorizing effect that is different from conventional deodorizing effects using activated carbon or carbon dioxide, and because the fibers with a large surface area carry the metal phthalocyanine/polycarboxylic acid and metal ions that are the deodorizing ingredients, it is a deodorizing agent. The odor effective area is large and the deodorizing effect is also large. The wet-laid nonwoven fabric of the present invention can be finished into various shapes, such as a filter for removing bad odor,
It can be widely applied to fields for removing or alleviating bad odors, such as undermats for bedding, mats for pet animals, disposable diapers, toilet paper, sanitary napkins, and wrapping paper.

[Brief explanation of the drawing]

Figure 1 shows the structural formula of metal porphyrin.
FIG. 2 is a diagram showing the structural formula of metal porphyrazine.

Claims (1)

[Claims] 1. A first short fiber carrying 1% by weight or more of metal phthalocyanine/polycarboxylic acid, copper ions,
One or more metal ions selected from cobalt ions, iron ions, nickel ions, calcium ions, barium ions, and magnesium ions.
1. A deodorizing wet-laid nonwoven fabric characterized by comprising second short fibers supported in an amount of 0.1 to 20% by weight. 2 1% by weight or more of metal phthalocyanine/polycarboxylic acid and 0.1 to 20% by weight of one or more metal ions selected from copper ions, cobalt ions, iron ions, nickel ions, calcium ions, barium ions, and magnesium ions. A deodorizing wet nonwoven fabric characterized by containing supported short fibers.