JPH01311008A - Composition for processing - Google Patents

Abstract

PURPOSE:To obtain a composition for antimicrobial and antifungal processing, containing zeolite holding antimicrobial metallic ions and capable of maintaining high antimicrobial and antifungal properties of processed materials, such as paper, heat-sensitive recording sheets, carpets or mats, for a long period. CONSTITUTION:A composition for processing, containing preferably 0.01-30wt.% zeolite holding antimicrobial metallic ions, especially silver, copper, and/or zinc ions, preferably the above-mentioned zeolite in which part or all of ions capable of exchange thereof with ammonium ions and antimicrobial metallic ions, especially containing 0.5-15wt.% ammonium ions as an essential ingredient and further preferably a resin, such as an acrylic resin, vinylidene chloride resin-based resin and/or vinyl chloride-based resin, having the afore-mentioned effects and especially capable of reducing fading properties of processed materials with time to low values and providing high durability in the case of the zeolite containing the ammonium ions.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a processing composition having antibacterial and antifungal properties, which is obtained by dispersing zeolite containing antibacterial metal ions, such as paper, heat-sensitive The present invention relates to processing compositions used for recording sheets, carpets, mats, woven and knitted fabrics, nonwoven fabrics, natural leather, synthetic leather, water-based paints, and the like.

[Conventional technology]

As is well known, various processing compositions contain various additives, etc., and have the disadvantage that they are easily attacked by microorganisms such as bacteria and mold. Pulp is composed of cellulose fibers, and the additives used in its production, ie, dyes, pigments, and sizing agents, are organic and inorganic substances, and both have the disadvantage of being easily attacked by bacteria and mold.

Coating compositions and impregnation compositions used for secondary processing of manufactured paper, ie coating and impregnation processing, include various natural and synthetic resins, pigments, dyes, surfactants, hydrophilic solvents, and thickeners. , and other additives, all of which have the disadvantage of being easily attacked by bacteria and mold. Paper made of these materials is also attacked by bacteria and mold, resulting in problems such as paper deterioration, quality deterioration, and mold growth.

In addition, the heat-sensitive coloring paint used for heat-sensitive recording sheets includes
It contains acidic substances called color developers, aggravating agents, stabilizers, and other additives. Sizing agents are also used for sheet base materials such as paper, synthetic paper, synthetic resin films, and nonwoven fabrics.
Surfactants, resin processing agents, oils, etc. are attached. All of these additives have the disadvantage that they are easily attacked by microorganisms such as bacteria and fungi.

Compositions for carpet banking include rubber latex, urethane, or acrylic aqueous emulsion resins, foaming agents, foaming aids, crosslinking agents, anti-aging agents, thickeners, foam stabilizers, dispersants, gelling agents, and fillers. Banking agents have been used that are made by appropriately combining various additives such as . In recent years, with changes in lifestyle and diversification of needs, banking agents have become widely used in entrance cloaks, kitchen mats, bathroom cloaks, center rugs, hot carpets, etc. There is a problem in that mold tends to form on the backing surface and floor surface if it is left in place for a long time in contact areas or other areas. Furthermore, banking agents containing various additives are susceptible to the propagation of bacteria or mold and have the problem of spoilage during storage.

Water-based resins for adhering fibers used in clothing and shoes include acrylic ester copolymer emulsion, rubber latex,
In addition to urethane emulsion and EVA, it contains surfactants, cellulose glue, sealants, and other additives. In addition, surfactants, warp glues, oils, etc. are also attached to the knitted and woven fabrics that are processed. All of these additives have the disadvantage that they are easily attacked by microorganisms such as bacteria and fungi, and that they generate odor and mold after the processed product is used.

Acrylic ester copolymer emulsions and acrylic ester copolymer emulsions are used in resin processing liquid compositions used to bond webs during the production of nonwoven fabrics, and processing compositions used in resin processing to impart functions such as flame retardance and strength to nonwoven fabrics. It contains emulsions such as styrene-butadiene copolymer latex, surfactants, cellulose thickeners, hydrophobic organic solvents, pigments, and other additives. In addition, surfactants, warp glues, oils, etc. are also attached to fibers, nonwoven fabrics, etc. that are subject to resin processing. All of these additives have the disadvantage that they are easily attacked by microorganisms such as bacteria and fungi.

In particular, non-woven resin processed products are used in a wide range of applications such as clothing, bedding, etc. that may come into direct contact with the human body, food contact, and filters for air and liquids, so low toxicity is insufficient. Consideration is required. Durability is also important, as they are often recycled and washed.

Natural leather has excellent mechanical properties such as abrasion resistance and tensile strength, has moisture absorption, I3 moisture, and heat retention functions, and has excellent flexibility and texture, so it is used for clothing such as shoes, clothing, and bags. It is a favorite material. However, sweat while wearing, moisture contained, proteins and fats originally contained, and toughness,
The surfactants, oils, resins, etc. that are attached or impregnated during the fatliquing and dyeing processes tend to breed bacteria and fungi, leading to problems such as deterioration in shelf life and aesthetics, and the occurrence of emergency illnesses.

Like Machi, natural leather finishing compositions include acrylic resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, cellulose resins, protein resins, surfactants, dyes, pigments, Contains other additives such as waxes and oils. Natural leather is mainly composed of collagen protein and always contains about 30% water, so it has the disadvantage that it is easily soaked by microorganisms such as bacteria and fungi. In particular, clothing, gloves, shoes, bags, etc. are contaminated with sweat while being worn and oils and fats in the leather.
Depending on the temperature conditions, bacteria and mold can easily grow.

Urethane leather has excellent mechanical properties such as bending resistance, abrasion resistance, and tensile strength, is highly flexible, and has little change in modulus depending on temperature, so it is used as a substitute for leather for shoes, clothing, miscellaneous goods, and furniture sheets. It is used for such things. As is well known, urethane leather compositions contain surfactants, hydrophobic organic solvents, pigments, and additives therefor. All of these have the disadvantage that they are easily attacked by microorganisms such as bacteria and fungi.

Water-based paints include emulsion type and water-soluble resin type paints. The coating composition consists of various resins (typical resins include acrylic, vinyl acetate, ethylene-vinyl acetate, urethane, etc.), surfactants, hydrophilic solvents, pigments, Contains antifoaming agents and other additives. All of these additives have the disadvantage that they are susceptible to microorganisms such as bacteria and mold. Particularly in the case of water-based paints, there are problems such as contamination during the manufacturing process, decay due to bacteria and mold that grow during storage, and mold that grows on the painted surface after painting.

[Problem to be solved by the invention]

To overcome these drawbacks, various antibacterial and antifungal agents are applied to paper, heat-sensitive recording sheets, carpets, man),! [:cloth,
It has been added to manufacturing and processing compositions of nonwoven fabrics, natural leather, synthetic leather, water-based paints, etc.

That is, chlorine-based and sulfur-based compounds have been used, but it cannot be said that their antibacterial properties, anti-mold properties, and low toxicity are necessarily satisfied.

PO3 attached to food packaging like a heat-sensitive recording sheet
When used for labels, etc., and when used for cloth, leather, etc. that may come into direct contact with the human body, such as clothing, shoes, bags, gloves, etc., sufficient consideration must be given to low toxicity.
Problems such as the generation of mold due to sweat and moisture during wear, the resulting odor, and durability must also be resolved.

Furthermore, since banking materials, cloak materials, etc. are subjected to washing, drying in the sun, etc., durability against repeated washing is also important.

[Means to solve problems]

In order to prevent the occurrence of such bacteria and fungi, the present inventors have conducted intensive studies on antibacterial and antifungal agents for various processing compositions, and have found that they retain antibacterial metal ions. Processing compositions containing zeolite and processed products thereof are
It has high antibacterial activity not only against fungi but also against general bacteria (,
In addition, the antibacterial activity is sustained over a long period of time, and in particular, as a zeolite that retains antibacterial metal ions, some or all of the ion-exchangeable ions in the zeolite are replaced with ammonium ions and antibacterial metal ions. The present inventors have found that the use of the above-mentioned composition is particularly preferable because a processing composition with little discoloration over time can be obtained, and the present invention has been completed based on this finding.

That is, the present invention provides a zeolite holding antibacterial metal ions (hereinafter referred to as antibacterial zeolite), preferably a part or all of the ion exchangeable ions in the zeolite are replaced with ammonium ions and antibacterial metal ions. de1
The present invention provides an antibacterial and antifungal processing composition containing the converted antibacterial zeolite.

In the present invention, as the "zeolite", both natural zeolite and synthetic zeolite can be used.

Zeolite is an aluminosilicate that has a three-dimensional skeleton structure in -m, and has the general formula XLz, IO・A1□
0.・YSiJ ・Displayed as ZH,O. Here M
represents an ion exchangeable ion, which is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion. X and Y are respective metal oxides, silica coefficients,
Z indicates the number of crystallized water. Specific examples of zeolites include A-type zeolide, X-type zeolide, and Y-type zeolide.
- type zeolide, T-type zeolide, high silica zeolite, sodalite, mordenite, analcyme, clinoptilolite, chabasite, erionite and the like. However, the ion exchange capacity of these exemplary zeolites is, but not limited to, 1 meq/g for 8-type zeolide and 6.4 m for X-type zeolite.
eq/g SY-type zeolide 5meq/g, T-type zeolide 3.4meq/g, sodalite 11.5me
q/g, mordenite 2.6+seq/g, analcyme 5n+eq/g 1 clinoptilolite 2.6me
q/g, Chahasite 5aeq/g, Erionite 3.
8 meq/g, and both have sufficient capacity for ion exchange with antibacterial metal ions.

The antibacterial zeolite used in the present invention includes ion exchangeable ions in the zeolite, such as sodium ions,
Part or all of calcium ions, potassium ions, magnesium ions, iron ions, etc. are replaced with antibacterial metal ions, preferably ammonium ions and antibacterial metal ions. As examples of antimicrobial metal ions, mention may be made of ions of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or krylam, preferably ions of silver, copper or zinc.

From the viewpoint of antibacterial properties, it is appropriate that the antibacterial metal ions are contained in the zeolite in an amount of 0.1 to 15%.

More preferred are antibacterial zeolites containing 0.1-15% of ammonium ions and 0.1-8% of copper or zinc ions, while ammonium ions are present at 20% in the zeolite.
However, the content of ammonium ions in zeolite is 0.5 to 5%, preferably 0.
．． A content of 5 to 2% is appropriate from the viewpoint of effectively preventing discoloration of the zeolite. In this specification, % refers to % by weight on a 110''C dry basis.

The method for producing the antibacterial zeolite used in the present invention will be described below. For example, the antibacterial zeolite used in the present invention contains antibacterial metal ions such as silver ions, copper ions, and zinc ions prepared in advance, and preferably further contains ammonium ions. The zeolite is brought into contact with the mixed aqueous solution to replace the ion-exchangeable ions in the zeolite with the ions.

Contacting is carried out at 10-70°C, preferably 40-60°C for 3-30°C.
It can be carried out for 24 hours, preferably for 10 to 24 hours, by a batch method or a continuous method (for example, a column method).

The pH of the above mixed water solution is 3 to 1O1, preferably 5 to 1O1.
It is appropriate to adjust it to 7. This adjustment is preferable because it can prevent silver oxides and the like from being deposited on the zeolite surface or in the pores, and each ion in the mixed aqueous solution is usually supplied as a salt.

For example, ammonium ions include ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium perchlorate, 1,000 6A M ammonium, ammonium phosphate, etc., and silver ions include silver nitrate, sulfur Mt! , silver perchlorate, silver acetate, diammine silver nitrate, diammine silver sulfate, etc. Copper ions include copper nitrate (■), perchlorate steel, copper acetate, potassium tetracyano V4 acid, copper sulfate, etc., zinc ions include zinc nitrate (
■), zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate, etc., mercury ions include mercury perchlorate, mercury nitrate, mercury acetate, etc., tin ions include tin sulfate, etc., lead ions include lead sulfate, Lead nitrate, etc., bismuth ions include bismuth chloride, bismuth iodide, etc., cadmium ions include cadmium perchlorate, cadmium sulfate, cadmium nitrate, cadmium acetate, etc., chromium ions include chromium perchlorate, chromium sulfate, ammonium chromium sulfate, As the thallium ion such as chromium nitrate, thallium perchlorate, thallium sulfate, thallium nitrate, krillam acetate, etc. can be used.

The content of ammonium ions and the like in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed aqueous solution.

For example, when antibacterial zeolite contains ammonium ions and root ions, the ammonium ion concentration in the mixed aqueous solution is 0.2M/1 to 2.5F'l/1, and the silver ion concentration is 0.002? I/f-0,15M/
1, an antibacterial zeolite having an ammonium ion content of 0.5 to 5% and a silver ion content of 0.1 to 5% can be obtained as appropriate. Moreover, when the antibacterial zeolite further contains copper ions and zinc ions, the degree of copper ion in the mixed aqueous solution is 0.1? ! / 1~0.8
5M/1, zinc ion 1 degree is 0.15M/IL ~
By setting 1 or 2 gates/1, copper ion content i
Antibacterial zeolite with t 0.1-8% and zinc ion content 0.1-8% can be obtained.

In the present invention, in addition to the mixed aqueous solution as described above, an aqueous solution containing each ion alone is used, and each water ? Ion exchange can also be carried out by sequentially bringing the liquid 8 into contact with zeolite. The concentration of each ion in each aqueous solution can be determined based on the concentration of each ion in the mixed aqueous solution.

After ion exchange, the zeolite is thoroughly washed with water and then dried. Drying is preferably carried out at 105° C. to 115° C. under normal pressure or at 70° C. to 90° C. under reduced pressure (1 to 30 torr).

Ion exchange of ions without suitable water-soluble salts, such as lead, bismuth, etc., or organic ions can be carried out using a 1M medium solution such as alcohol or acetone to avoid precipitation of sparingly soluble basic salts. .

Examples of the processing composition of the present invention include compositions used in the production and processing of paper, fibers, leather, and water-based paints, and compositions for post-processing of these. For example, coating liquid compositions, impregnating liquid compositions, and thermosensitive coloring paints are used for paper, banking compositions are used for carpets, fiber adhesive compositions are used for textiles, resin processing liquid compositions are used for nonwoven fabrics, and resin processing liquid compositions are used for natural leather. ,
Examples of antibacterial leather treatment compositions, finishing compositions, and synthetic leathers include urethane resin coating compositions, and examples of coatings include water-based coating compositions.

Coating liquid compositions and impregnating liquid compositions for paper include, for example, those comprising resins, extender pigments, colorants, dispersants, antibacterial zeolites, and water.

As the resin used here, acrylic acid ester emulsion, styrene-butadiene latex, acrylonitrile-butadiene latex, vinyl acetate emulsion, textile resin, etc. are used, and the amount added is usually determined as the resin solid content. It is between 2.5 and 15%.

Known extender pigments such as clay, kaolin, talc, and calcium carbonate can be used, and the amount added is usually 5 to 30% in the composition.

Coloring agents include dyes, inorganic pigments such as titanium oxide and carbon blank, and organic pigments. The amount added varies depending on the hue and density of the target paper, but is usually 5% or less.

As the dispersant, nonionic and anionic dispersants can be used.

The amount of antibacterial zeolite added in the composition is 0.01 to 50
%, preferably 0.02 to 20%. If the amount of antibacterial zeolite added is less than 0.01%, the antibacterial and antifungal effects will decrease. Even if the amount added exceeds 30%, the antibacterial and antifungal effects remain the same. Even if solid particles are added as they are, antibacterial zeolite can be used as a sea urchin cake before the drying process during the production of antibacterial zeolite. Alternatively, an antibacterial zeolite paste that has been kneaded in advance with a dispersant may be added.

The coating composition is used when producing coated paper. Coated paper refers to paper on which a coating composition is uniformly applied using a knife coater, roll coater, reverse coater, air knife coater, or the like.

Examples of the coating paper include printing paper, wrapping paper, writing paper, decorative paper, and miscellaneous paper.

The impregnating composition is used to produce impregnated paper, and the impregnated paper is produced using an impregnation processing machine and used for wrapping paper, decorative paper, and the like.

The heat-sensitive coloring composition includes a coloring lactone compound, an acidic substance, a '48 adhesive, and an antibacterial zeolite, preferably replacing some or all of the ion-exchangeable ions in the zeolide with ammonium ions and seedling-resistant metals. Examples include those containing antibacterial zeolite substituted with ions.

Examples of the above-mentioned color-forming lactone compounds include, but are not limited to, those listed below.

3.3-bis(p-dimethylaminophenyl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-
Dimethylaminophthalide (also known as crystal violet lactone = CVL), 3,3-bis(p-dimethylaminophenyl)-6-aminophthalide, 3,3-bis(p
-dimethylaminophenyl)-6-nitrophthalide, 3
．． 3-bis(p-dimethylaminophenyl)phthalide,
3,3-bis3-dimethylamino-7-methylfluoran, 3-diethylamino-7-chlorofuran, 3-diethylamino-6-chloro-7-methylfluoran, 3-
Diethylamino-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-
Piveridino-6-methyl-7-anilinofluorane, 3
-(N-ethyl-p-toluidino)-7-(N-methylanilino)fluorane, 3-(N-ethyl-p-1luidino)-6-methyl-7-anilinofluorane, 3-N
-Ethyl-N-isoamylamino-6-methyl-7-anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-
Fluorane phthalides such as N,N-diethylamino-7-0-chloroanilinofluorane, lactams such as rhodamine B lactam, 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3-benzyl Examples include spiropyrans such as spironaphthopyran.

Of course, these compounds must be colorless or light-colored and develop color when reacting with acidic substances.

In addition, acidic substances are solid at room temperature and have a molecular weight of 60 to 180
Any compound may be used as long as it melts and liquefies when heated to about °C, opens the lactone ring of the color-forming lactone compound, and develops color. Examples include, but are not limited to, these.

4-phenylphenol, 4-hydroxyacetophenone, 2,2゛-dihydroxydiphenyl, 2゜2゜
-Methylenebis(4-chlorophenol), 2゜2''-
Methylenebis(4-methyl-6-t-butylphenol), 4.4°-isopropylidenediphenol (also known as bisphenol A), 4.4'-isopropylidenebis(2-chlorophenol), 4゜4゛-isopropylidene Bis(2-methylphenol), 4.4'-
Ethylene bis(2-methylphenol), 4.4° −
Thiobis (6-t-butyl-3-methylphenol),
1.1-bis(4-hydroxyphenyl)-cyclohexane, 2.2'-bis(4-hydroxyphenyl)
-n-hebutane, 4゜4''-cyclohexylidene bis(
2-isopropylphenol), 4.4°-sulfonyldiphenol, salicylic acid anilide, novolak type phenol resin, benzyl p-hydroxybenzoate, and the like.

These acidic substances are usually used in an amount of 10 to 1.000 parts by weight per 100 parts by weight (hereinafter simply referred to as parts) of the color-forming lactone compound.
parts, preferably 100 to 500 parts.

The sensitizer may be any one of carboxylic acid ester type, phosphoric ester type, ether type, acid amide type, hydrocarbon type, etc., and is not particularly limited.

Sensitizers are acidic! Usually 1-1,000 per 100 copies
0 parts, preferably 30-100 parts are used.

The color-forming lactone compound, the acidic substance, and the sensitizer are all used in the form of fine particles, preferably fine particles having a particle diameter of several microns or less.

Both aqueous and oil-based binders can be used in the thermosensitive color-forming composition of the present invention, and there are no particular limitations. Examples of aqueous binders include polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, starches, and styrene. -maleic acid copolymers and the like. On the other hand, examples of the oil-based binder include petroleum resin, polyurethane, vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer, polyester, polyamide, etc., but are not particularly limited.

In addition, in order to improve performance, the composition may contain ultraviolet absorbers such as benzophenone and triazole, fillers such as calcium carbonate, polyethylene wax, etc.
A lubricant such as paraffin wax, a waterproofing agent, and various other chemicals can be added. Furthermore, various dispersants for dispersing various drugs in water or solvents can be added to the above composition.

The amount of antibacterial zeolite added in the thermosensitive coloring composition is 0.
01 to 50% by weight, preferably 0.02 to 20% by weight. If the amount of antibacterial zeolite added is less than 0.01%, the antibacterial and antifungal effects will decrease. On the other hand, the amount added is 50
Even if the amount of M exceeds %, the antibacterial and antifungal effects do not change.

As the sheet base material, paper is generally used, but synthetic paper, synthetic resin film, nonwoven fabric sheet, etc. can also be used as appropriate.

The three-thermal recording sheet of the present invention can be applied to all conventional thermal recording sheets. Particularly effective applications include fields that require strict antibacterial and anti-mold properties, such as labels such as POS labels attached to food packaging, or filter carpets for image-sensitive printers used in medical diagnosis. Backing compositions include, for example, resins, fillers, foam stabilizers, foaming agents, thickeners, antimicrobial zeolites, and water.

The resin used here includes, for example, 0.1 to 40% of a carboxyl group-containing polymerizable monomer and/or 0.1 to 10% of a crosslinkable functional group-containing polymerizable monomer and other polymerizable monomers. 99.9 to 50% of polymerizable jmLI compound, preferably 0.5 to 20% of carboxyl group-containing polymerizable jmLI compound and/or 0.2 to 5% of crosslinkable functional group-containing polymerizable monomer and other polymerizable monomers. Examples include resins consisting of 99.8 to 75%.

Copolymerizing a carboxyl group-containing monomer into a copolymer increases the mechanical stability of the polymer and promotes intramolecular crosslinking with the crosslinkable functional group-containing polymerizable monomer, thereby improving water resistance. Improves sex. However, if the content of the carboxyl group-containing polymerizable carmer exceeds 40%, the hydrophilicity of the resin increases and the water resistance decreases. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and vinylbenzoic acid, of which acrylic acid, methacrylic acid, and itaconic acid are preferred.

Copolymerizing a crosslinkable functional group-containing polymerizable monomer can improve hydrophilicity by intramolecularly crosslinking with the carboxyl group-containing polymerizable monomer or itself and increasing the crosslink density. I can do it. However, if the content of the crosslinkable functional group-containing polymerizable monomer exceeds 10%, the crosslinking reaction progresses during polymerization to form a gelled product, making it impossible to obtain a normal aqueous emulsion. As the crosslinkable functional group-containing polymerizable i-mer, N-methylol (meth)acrylamide,
(meth)glycidyl acrylate, (meth)acrylic acid 2
-hydroxyethyl, maleic anhydride, (meth)acrylamide, 2-hydroxypropyl (meth)acrylate, (meth)acrylic aN, and N-dimethylaminoethyl. Other polymerizable monomers include (meth)
Examples include alkyl acrylate (C: 1-12), acrylonitrile, styrene, vinyl acetate, vinyltoluene, butadiene, and the like.

The proportion of resin in the banking composition is usually between 5 and 55%.
%, preferably 30-55%.

As fillers, commonly used extender pigments such as calcium carbonate, clay, talc, kaolin, zeolite, silicon oxide, alumina silicate, titanium oxide, etc. are used, and the amount added is usually 5 to 40% of the above composition. %, preferably 6-25%.

Foam stabilizers include stearic acid or oleic acid with 16 to 2 carbon atoms, such as sodium, potassium or ammonium salts.
Alkali metal or ammonium salts of zero saturated or unsaturated aliphatic carbon atoms are used.

As a foaming agent, sodium alkylbenzenesulfonate,
Anionic activators such as sulfate ester soda salts of higher alcohols are used.

As the thickener, ammonium salts of polyacrylic acid, cellulose compounds such as hydroxyethyl cellulose, etc. are used. The amount added is usually 1% or less, but it varies depending on the amount of resin and filler added.

The amount of antibacterial zeolite added in the backing composition is 0.
．． 01 to 50 circles, preferably 0.02 to 20%.

If the amount of antibacterial zeolite added is less than 0.01%, antibacterial and antifungal performance will decrease. On the other hand, even if the amount added exceeds 30%, the antibacterial and antifungal effects remain the same. At the same time, it is preferable that the backing composition is applied to the workpiece in an amount of antibacterial metal ions of 0.1 B/m to Ig/rd.

The method and order of addition of the antibacterial zeolite into the puffing composition are not particularly limited (it may be added into the copolymer, it may be added into the banking composition, and the antibacterial zeolite may be added into the puffing composition). The form of zeolite may be a powder, an aqueous paste made by grinding the powder with an activator, or a wet cake of zeolite before the drying process, and it can be uniformly mixed in a backing agent. There is no problem as long as it is dispersed.

The antibacterial zeolite-containing backing composition thus obtained not only has antibacterial and antifungal properties, but also contains well-known resin emulsions such as acrylic, urethane, and rubber resins, latex, etc. for the purpose of improving various properties. In addition to neutralizing agents such as water-soluble resins, ammonia, and various amines, use appropriate crosslinking agents such as softeners, lubricants, thickeners, surfactants, viscosity modifiers, extender pigments, melamine resins, epoxy resins, and isocyanates. can be used.

The backing composition is particularly suitable for use as a foam banking composition, and the foaming is performed mechanically to form a pasty foam using a conventional continuous foamer or batch foamer. This is applied to the back of a base material such as a carpet, dried and hardened to form banking.

The foam can also be applied using a coating machine such as a doctor knife or roll coater, or by hand.

Examples of fiber adhesive compositions include those consisting of a resin, antibacterial zeolite, and water, which can be used to bond fibers together, to bond woven or knitted fabrics to polystyrene, polypropylene, etc. resin films and sheets, and to paper. , refers to a composition for adhesion of wood, etc.

The resin here includes, for example, 0 crosslinkable polymerizable monomers.
．． 1-20% by weight, other polymerizable monomers 99.9-80%
% by weight, preferably 1-15% by weight of crosslinkable polymerizable monomer
and other aqueous resin compositions containing a copolymer consisting of 99 to 85% polymerizable S-mer.

Examples of the crosslinkable polymerizable monomer include acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, crotonic acid, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. , (meth)acrylamide, 2-hydroxypropyl (meth)acrylate, dimethyl (diethyl) methacrylate
Examples include aminoethyl ester.

The carboxyl group-containing monomer contributes to the mechanical stability of the resin composition, and is preferably 0.5 to 10% by weight. Preferably from 0.5 to 0.5, since water resistance and adhesion can be improved by crosslinking within the molecule itself and increasing the crosslink density.
Use 5% by weight.

Other polymerizable jl1 bodies include alkyl (meth)acrylates (C1-12), acrylonitrile, styrene,
Examples include vinyl acetate and butadiene.

The amount of resin contained in the fiber adhesive composition is 5 to 60%, preferably 10 to 55% as resin solid content.

The content is 10 to 30% to give a soft texture, and 30 to 55% to make it hard by molding. Further, the form of the resin may be an emulsion resin or a water-soluble resin.

The amount of antibacterial zeolite added in the resin composition is 0.01~
30%, preferably 0.1-10%. If the amount of antibacterial zeolite added is less than 0.01%, the antibacterial effect will decrease, and if it is more than 30%, the antibacterial effect will not change.
~Ig/n() is preferable.

The method and order of addition of the antibacterial zeolite into the resin composition is such that the powder is kneaded with an activator in advance and uniformly dispersed.

The antibacterial zeolite-containing resin composition obtained in this way can be used as a water-soluble thickener, alkali, warming agent, anti-drying agent, softener, viscosity modifier, foaming agent, foam stabilizer, and antifoaming agent during processing. agent,
Optical brighteners, pigments, aqueous color pastes, crosslinking agents such as melamine resins, EVA, comb latexes, urethane emulsions, and preservatives such as TBZ and carpendazine can be used in combination.

A resin processing liquid composition for nonwoven fabrics is a processing liquid composition for manufacturing a cloth-like crosspiece by treating a web formed of fibers by coating, spraying, or impregnating, and adhering the fibers in the web. Alternatively, it refers to a processing liquid composition used for resin processing of nonwoven fabric manufactured by a known method.

Resin processing for non-woven fabrics? The main components of the composition are resin and water, and depending on the purpose of processing, colorants such as dyes and pigments, organic solvents,
Contains auxiliary agents such as crosslinking agents.

The form of the resin can be either an emulsion or an aqueous resin solution; commonly used resins include acrylic ester copolymer emulsion, butadiene copolymer latex, vinyl acetate latex, vinyl chloride or chloride. Emulsion resins such as vinylidene latex and urethane resin emulsions, which are used individually or in combination. More specifically, the polymerizable monomers used in these resin emulsions include alkyl acrylates (C1-Cl8), alkyl methacrylates (C1-018), acrylonitrile, styrene, vinyl acetate, vinyltoluene, and butadiene. , vinyl chloride, vinylidene chloride polymers and copolymers, and these polymerizable monomers and acrylic acid, methacrylic acid, iconic acid,
Carboxyl group-containing polymerizable monomers such as fumaric acid, maleic acid, and vinylbenzoic acid, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, maleic anhydride,
It is a copolymer of polymerizable polymers containing crosslinkable functional groups such as (meth)acrylamide, 2-hydroxypropyl (meth)acrylate, and N,N-dimethylaminoethyl.

The amount of resin contained in the resin processing liquid composition is 1 to 40%, preferably 2 to 12% as solid content.

As the amount of resin in the resin processing liquid increases, the number of antibacterial zeolites appearing on the surface of the nonwoven fabric decreases, and the antibacterial and antifungal properties decrease when a certain amount of antibacterial zeolite is added. On the other hand, if it is less than 1%, the ability to fix the antibacterial zeolite to the nonwoven fabric is lost, and the durability against washing, amount, and friction is lost.

The amount of antibacterial zeolite added in the resin processing fluid composition is 0.
It is 1 to 50% by weight, preferably 0.02 to 20% by weight. If the amount of antibacterial zeolite added is less than 0.01% by weight, the antibacterial and antifungal effects will decrease. On the other hand, even if the amount added exceeds 50% by weight, the antibacterial and antifungal effects remain the same. at the same time,
It is preferable that the amount of antibacterial metal ions in the resin processing of the resin processing liquid composition to be applied to the nonwoven fabric is from o, log/g to 1.0 g/d. If the amount added is small, it is necessary to increase the amount of resin processing liquid attached to the object. Also, existing TB
It is also possible to use it in combination with fungicides such as Z and carpendazine.

The method and order of addition of the antibacterial zeolite into the resin processing fluid are not particularly limited, and the antibacterial zeolite may be added into the resin or into the resin processing fluid composition. The form of zeolite may be a powder, an aqueous paste prepared by kneading the powder with an activator in advance, or a wet cake of zeolite before the drying process, and it may be uniform in the resin processing liquid composition. There is no problem as long as it is dispersed.

The antibacterial zeolite-containing resin processing fluid composition obtained from this oak has not only antibacterial and anti-alkali functions, but also a water-based processing pigment can be added to the composition to color the object to be processed. In addition, acrylic type for the purpose of improving various properties,
Well-known resin emulsions such as vinyl acetate, urethane, and rubber, latex, water-soluble resins, mineral turpentine, hydrophobic organic solvents such as kerosene, water-soluble Il solvents such as alcohol and glycols, ammonia, and various amines. Neutralizers, wetting agents, anti-drying agents, softeners, lubricants, thickeners, glues, surfactants, viscosity modifiers, antifoaming agents, matting agents, polishing agents, film-thickening agents, dyes, extender pigments,
Various additives such as organic acids such as tartaric acid, inorganic salts such as ammonium chloride and magnesium chloride, optical brighteners, crosslinking agents such as melamine resins, epoxy resins and isocyanates, and dyeing aids can be used as appropriate.

The processing method is to directly impregnate the nonwoven fabric with the resin processing liquid composition, squeeze it with a mangle, etc., and dry it, or foam the resin processing liquid composition 2 to 20 times with a foaming machine, and then apply it to the nonwoven fabric. There are methods of coating or impregnating, squeezing with a mangle and drying, and methods of attaching the resin processing liquid composition to the fabric using an auto screen, rotary screen printing machine, roller printing machine, gravure printing machine, etc.

It can also be used as a resin processing liquid composition for adhering webs during the production of nonwoven fabrics, and can impart antibacterial and antifungal properties simultaneously with the production of nonwoven fabrics.

A method of immersing the web in a resin processing liquid composition and bonding the entire surface by roll squeezing, a method of spraying the resin processing liquid composition onto the web, a printing method using a well-known textile printing machine or a printing machine, a method of foaming with a foaming machine, and then applying. Alternatively, there is a method of impregnation.

The resin processing liquid composition of the present invention can be used for all objects conventionally used for resin processing of fibers.

Particularly effective for purposes such as antibacterial, antifungal, and deodorizing purposes. For example, diapers, interlining, underwear, slippers, shoe linings and insoles, neckties, etc. for clothing, pillow stuffing, cushions, etc. for household use. Fillings, furniture linings, bed sheets, carpet underlays, curtains, cover cloths, wall cloths, carpet base cloths, napkins, blankets, hats, carpets, sleeping bags, jackets, etc. Medical bandages, wipes, pillow cases It is used for filters such as air filters, sanitary masks, gas masks, and gas cleaning, as well as wallpaper, book cloths, automobile interior materials, tea banks and sausage cases, and food packaging.

Natural leather treatment compositions include resins, pigments, dyes, glues,
Wed, 8! Those consisting of solvents, antibacterial zeolites and additives may be mentioned. Examples of the resins used here include acrylic resins, butadiene resins, vinyl chloride resins, vinyl acetate resins, urethane resins, protein resins, and cellulose resins.

The amount of resin contained in the natural leather treatment composition is 1% to 40%, preferably 2% to 30% as resin solid content.

If the resin solid content in the natural leather treatment composition increases, the finished product will lose its flexibility, aesthetic appearance, graininess, etc. As the amount of resin in the natural leather treatment composition increases, the number of antibacterial zeolites appearing on the surface of the finished product decreases, and the antibacterial and antifungal properties when a certain amount of antibacterial zeolite is added decrease. On the other hand, if it is less than 1%, the effect of fixing the antibacterial zeolite to the finished workpiece is lost, resulting in water resistance, friction,
Durability against wear is lost.

As the pigment, commonly used organic pigments and inorganic pigments are used. The amount added is usually 0.1 to 30%, preferably 1 to 0%, based on the above composition.

As the dye, basic dyes, acidic (metal-containing) dyes, reactive dyes, alcoholic dyes, etc. are used. The amount added is usually 0.01 to 50%, preferably 0.05 to 2%, based on the above composition.
It is 0%.

As the thickening agent, natural products such as milk casein, albumin, shellac, and chitinous starch, and synthetic resins such as carboxy-modified cellulose are used. The amount added is 0.1-30%
, preferably 1 to 30%. As the organic solvent, water-soluble solvents such as alcohol, organic solvents such as esters, ketones, and aromatic solvents are used.

The natural leather treatment composition (eg, coating agent) may be water-based or oil-based, and may be a laminate of these.

The content of zeolite that retains antibacterial metal ions in the coating agent is 0.01 to 50% (based on the resin solid content), preferably 0.02 to 20%.

That is, if the content of antibacterial zeolite is less than 0.01%, the antibacterial and antifungal effects will decrease, and even if the combined content exceeds 30%, the effect will not change. It is also possible to add pigments or dyes to color the natural leather, as well as softeners, lubricants, and matting agents to improve texture, flexibility, surface texture, and various physical properties. Additives such as the following can also be used as appropriate.

That is, the present invention provides a composition for natural leather that has antibacterial and antifungal functions that is attached to the surface of natural leather or contained therein, and a zeolite that retains antibacterial metal ions. It also includes a coating agent composition for natural leather that improves the antibacterial and antifungal functions of the natural leather by treatment.

Natural leather finishing compositions include, for example, resins, pigments,
Examples include those consisting of a thickening agent, water, an organic solvent, an antibacterial zeolite, and additives.

The resins used here include acrylic resins, butadiene resins, vinyl chloride resins, vinyl acetate resins, urethane resins, protein resins, and cellulose resins. For example, carboxyl group-containing polymerizable monomers and/or 0.1 to 40% of polymerizable monomers containing crosslinkable functional groups and 100 to 50% of other polymerizable monomers, preferably 0.5 to 40% of polymerizable monomers containing carboxyl groups. It is an aqueous resin containing a copolymer consisting of 20% and/or 0.2 to 5% of a crosslinkable functional group-containing polymerizable monomer and 99.8 to 75% of other polymerizable 11 monomers. Copolymerizing carboxyl group-containing #mers into the copolymer increases the mechanical stability of the polymer and promotes intramolecular crosslinking with the crosslinkable functional group-containing polymerizable monomer. Improves water resistance. However, when the content of the carboxyl group-containing polymerizable monomer exceeds 40%, the hydrophilicity of the resin increases and the water resistance decreases. Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, vinylbenzoic acid, etc. Among them, acrylic acid, methacrylic acid, and itaconic acid are preferred. By copolymerizing the contained polymerizable monomer, water resistance can be improved by intramolecularly crosslinking with the carboxyl group-containing polymerizable monomer or itself and increasing the crosslinking density.

However, the content of crosslinkable functional group-containing polymerizable monomer is 10
%, a crosslinking reaction will proceed during polymerization and a gelled product will be produced, making it impossible to obtain a normal aqueous emulsion.

Examples of the crosslinkable functional group-containing polymerizable carmer include N-methylol (meth)acrylamide, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, maleic anhydride, (meth)acrylamide, and (meth)acrylate. 2-hydroxypropyl acrylate, (meth)acrylic liN
, N-dimethylaminoethyl. Other polymerizable monomers include alkyl (meth)acrylate (C
:1-12), acrylonitrile, styrene, vinyl acetate, vinyltoluene, butadiene, etc.

The amount of resin contained in the natural leather finishing composition is 1% to 40%, preferably 2% to 30% as resin solid content. When the resin solid content in the natural leather finishing composition increases, the finished product loses its flexibility, aesthetic appearance, graininess, etc.

As the amount of resin in the finishing composition increases, the number of antibacterial zeolites appearing on the surface of the finished workpiece decreases, and the antibacterial and antifungal properties decrease when a certain amount of antibacterial zeolite is added. On the other hand, if it is less than 1%, the effect of fixing the antibacterial zeolite to the finished workpiece is lost, and the durability against water resistance, friction, and abrasion is lost.

As the pigment, commonly used organic pigments and inorganic pigments are used. The amount added to the above composition is usually 0.1 to 30%, preferably 1 to 10%.

As the dye, basic dyes, acidic (metal-containing) dyes, reactive dyes, alcoholic dyes, etc. are used. The amount added is usually 0.01 to 50%, preferably 0.05 to 20%, based on the above composition.
%.

As the thickening agent, natural substances such as milk casein, albumin, shellac, and chitinous starch, and synthetic thickening agents such as carboxy-modified cellulose are used. The amount added is 0.1-30%
, preferably 1 to 30%. Yes W1? As the container, a water-soluble solvent such as alcohol, or an organic solvent such as ester, ketone, or aromatic solvent is used.

The amount of antibacterial zeolite added in the natural leather finishing composition is 0.01 to 50%, preferably 0.02 to 20%.

If the amount of antibacterial zeolite added is less than 0.01, the antibacterial and antifungal properties will decrease. On the other hand, even if the amount added exceeds 30%, the antibacterial and antifungal effects remain the same. At the same time, the amount of antibacterial metal ions applied to the finishing composition is Q.
, lag/m to Ig/nl. That is, if the amount of antibacterial zeolite added to the finishing composition is small, it is necessary to increase the amount of coating. Furthermore, the antibacterial and antifungal effects are as high as possible when the entire surface of the finished product is uniformly coated. In this case, it is also possible to use the conventionally used TBZ and carpendazine in combination.

The method and order of addition of the antibacterial zeolite into the finishing composition are not particularly limited, and it may be added into the resin or into the finishing composition.

The antibacterial zeolite may be in the form of a powder, a paste prepared by kneading the powder with a surfactant, or a wet cake of zeolite before the drying process. It is good if it is evenly distributed.

In addition, with the aim of improving various properties, aromatic solvents such as ketones and esters, hydrophobic organic solvents such as BTX, well-known resin emulsions such as casein and rubber, latex, water-soluble resins, hydrocarbons, ketones, and esters are used. hydrophobic organic solvents such as alcohols, water-soluble organic solvents such as glycols, neutralizing agents such as ammonia, various amines, wetting agents,
Anti-drying agents, softeners, lubricants, thickeners, glues, surfactants, viscosity modifiers, antifoaming agents, matting agents, polishing agents, film forming aids, dyes, extender pigments, optical brighteners , crosslinking agents such as melamine resins and epoxy resins, and various additives such as dyeing aids can be used as appropriate.

There are 21 well-known machines for painting, including spray paint machines, curtain coaters, roll coaters, and mangles. Coating can also be performed using a coating machine such as a doctor knife or an air knife, a gravure printing machine, a textile printing machine, etc.

The finishing composition of the present invention can be used on all conventionally coated natural leathers. Especially antibacterial,
Applications for anti-mildew, anti-odor purposes, such as blazers, jumpers, skirts, jackets, pants, etc. in the clothing field.
Gloves, etc., in the shoe field, shoes, shoe linings, insoles, slippers, etc.; in the industrial materials field, chair upholstery, car seats, book cloths, table tops, etc.; in the daily necessities field, bags, bags, wallets, bags, belts, etc. can be given.

The urethane resin coating composition in the present invention consists of a urethane resin, a pigment, a filler, an additive, a solvent, and an antibacterial zeolite.

The urethane resin referred to herein is obtained by reacting a polyisocyanate compound having two or more isocyanate groups with a polyamineyaphoriol having two or more active hydrogen-containing groups, as is known. As the polyisocyanate compound, aromatic polyisocyanates and aliphatic and alicyclic polyisocyanates can be used alone or in combination. As a polyol compound, polyester polyol,
Polyether polyols and polycarbonate polyols may be used alone or as a mixture. Further, urethane resins modified with acrylic resins, styrene resins, and silicone resins can also be used as the urethane resins referred to in the present invention.

Pigments include inorganic pigments such as titanium oxide, yellow lead, carbon, and iron oxide, organic pigments such as phthalocyanine pigments, azo pigments, and quinacridone pigments, singly or in mixtures, or these pigments dispersed in a urethane resin solvent solution. There are oil-based processed pigments.

Fillers include calcium carbonate, barium sulfate, kaolin, clay, talc, and antimony oxide.

Additives include surfactants, ultraviolet absorbers, mold release agents,
There are anti-color separation agents, plasticizers, etc.

The solvent includes hydrophobic organic solvents such as toluene, xylene, and cyclohexanones, and water-soluble organic solvents such as alcohol, methyl ethyl ketone, and dimethyl formamide.

Furthermore, in order to improve the performance of the urethane leather composition that is the final processed product, we use resins such as acrylic resin, salt-vinyl acetate resin, silicone resin, and styrene resin, as well as matting agents, feel modifiers, and antioxidants. can also be used as appropriate.

The component ratio of the urethane leather composition in the present invention is urethane resin 10 to 80% by weight (hereinafter abbreviated as %),
Pigment O ~ 50%, filler θ ~ 50%, solvent 5 ~ 70%,
Additives O~5%, other performance improvers θ~30%, and antibacterial zeolite 0.01~50%. here,
The amount of antibacterial zeolite added to the urethane resin composition is preferably 0.01 to 20%. If the amount of antibacterial zeolite added is less than 0.01%, the antibacterial and antifungal effects will decrease. On the other hand, even if the amount added exceeds 30%, the antibacterial and antifungal effects remain the same.

At the same time, when applying the urethane resin coating composition for synthetic leather to the synthetic leather substrate, the amount of antibacterial metal ions is O.1 mg.
/m+~Ig/% is preferable.

The method and order of addition of antibacterial zeolite into the urethane resin coating composition are not particularly limited, and whether it is added into the urethane resin or the coating 1-1 composition, It may also be added to colored urethane resin paints containing processed pigments and the like.

In addition, the form of antibacterial zeolite, even if it is a powder,
It may also be an oil-based paste prepared by kneading powder with a vehicle in advance.

Processing machines include coating machines such as doctor coat, roll coater, bar coater, gravure printing machine, screen printing, spray painting, dipping,
It is also possible to apply with a brush.

The urethane resin coating composition for synthetic leather of the present invention can be used for all purposes of synthetic leather, but especially for purposes such as antibacterial, anti-mildew, and deodorizing purposes, such as rain protection, rain protection, etc. in the clothing field.
Sportswear such as ski wear, shoes, sandals, and insoles in the daily necessities field, and tents, chair linings, etc. in the industrial materials field.

The water-based paint composition includes, for example, a resin for adhesion and coating film formation, titanium oxide, an extender, a dispersant, a viscosity modifier,
Coating aids, colorants, water and antibacterial zeolites and other additives may be mentioned.

Resins include water-soluble resins and emulsion resins, including acrylic resins, butadiene resins, vinyl chloride resins,
Examples include vinyl acetate resin, polyurethane resin, polyester resin, polyamide resin, and cellulose resin.

Titanium oxides include rutile-type titanium oxide and anatase-type titanium oxide; extender pigments include clay, talc, kaolin, calcium carbonate, etc.; dispersants include nonionic and anionic surfactants, sodium tripolyphosphate, sodium hexametaphosphate, and polycarbonate. Such as acid salts.

Colorants include dyes, organic pigments, inorganic pigments, and water-based processed dyes and pigments.

The composition of the water-based paint composition is such that the solid content of the resin is 5 to 50.
%, titanium oxide O~30%, extender pigment 0~30%, viscosity modifier 0~5% solids, dispersant 0.1~5%, colorant O-IO%, film forming aid agent 1-5%, water 50-9
0%, antibacterial zeolite from 0.01 to 50% and other additives θ to 5%.

In the present invention, in order to make an aqueous coating composition containing solid particles of antibacterial zeolite, the method and order of addition of antibacterial zeolite are not particularly limited, and the solid particles are added to the coating composition. It can also be a paste prepared by kneading solid particles with a dispersant in advance, or a wet cake of zeolite before the drying process in the production of antibacterial zeolite, and can be uniformly dispersed in an aqueous coating composition. If you do, there will be no problem.

The amount of solid particles of antibacterial zeolite added in the present invention is 0.01 to 50%, preferably 0.02 to 20%.

If the amount of antibacterial zeolite added is less than 0.01%, the antibacterial and antifungal effects will decrease. On the other hand, even if the amount added exceeds 30%, the antibacterial and antifungal effects do not change, and at the same time, the amount of antibacterial metal ions when applied to the object with the water-based paint composition is 0.
．． It is preferable to set it to 1 B/m to Ig/m.

Further, even when used in combination with conventionally used organic antibacterial and antifungal agents, the antibacterial and antifungal effects of the antibacterial zeolite-containing aqueous paint do not decrease, and there is no problem in using them in combination.

As a paint, it can be used, for example, as a water-based paint for building interiors and exteriors, a water-based paint for woodwork, and a water-based paint for metals. The objects to be coated with water-based paints for buildings include concrete, mortar, asbestos slate, cefcolla board, wood, etc. The water-based paint composition of the present invention is particularly used for water-based paints related to water areas (kitchens, bathrooms, exterior walls, interior walls). can.

The water-based paint composition containing antibacterial zeolite obtained in this way is resistant to bacteria and molds that are mixed in during the manufacturing process or that grow during storage, as well as bacteria and molds that grow in the coating solution, and has excellent preservative properties. It was confirmed that it has excellent anti-mildew properties.

〔Effect of the invention〕

Since the processing composition of the present invention contains antibacterial zeolite, it has the effect of maintaining high antibacterial and mold-proofing properties of processed materials for a long period of time.

Moreover, it is possible to suppress the discoloration of the processed product over time, resulting in high durability.

〔Example〕

The present invention will be explained in more detail below with reference to Examples.

Reference Example 1 (Preparation method of antibacterial zeolite) The zeolite was 8-type zeolide (NaxO-AIxOs・1.9S
iO1・x HIO: average particle size 1.5 μ11), X-
type zeolide (NazO・Altos・2.3Si
J ・X HtO: average particle size 2.5 #l11), Y
-type zeolide (1, INazOHat, o.

・4SiO1・x H2O: average particle size 0.7 μm),
Four types of natural clinoptilolite (150 to 250 mesh) were used. NH4NO3, AgNOs, Cu(
Four types were used: NJ)x and Zn(NO3)2.

Table 1 shows the type of zeolite used in preparing each sample and the type and concentration of salt contained in the mixed aqueous solution. N
Six types of antibacterial zeolite samples, No. 0, 1 to No. 6, were obtained.

For each sample, water was added to 1 kg of zeolite powder heated and dried at 110°C to make a slurry of 1.31, which was then stirred and degassed, and an appropriate amount of 0.5N nitric acid solution and water were added to adjust the pH. Adjust to 5-7, total 1.8 J
For ion exchange, a mixed aqueous solution 3j of a specified salt at a specified concentration is used as a slurry. was added to bring the total volume to 4.81, and this slurry liquid was maintained at 40 to 60°C and heated to 10 to 24°C.
The mixture was kept stirring for a period of time to reach an equilibrium state.

After the ion exchange was completed, the zeolite powder was filtered and washed with room temperature water or hot water until there were no excess silver ions, copper ions, or zinc ions in the zeolite phase.
Six types of samples were obtained by heating and drying at 0°C. Obtained no.

Examples 1 to 6 and comparative example 1 regarding antibacterial zeolite samples of No. 1 and No. 6 (Preparation of coating liquid for paper and antibacterial activity test of antibacterial coated paper) Acrylic aqueous emulsion (manufactured by Dainippon Ink & Chemicals) D?CNAL
E-8280) 300g, calcium carbonate aqueous paste (oispERsEF-1000 manufactured by the same company) 500
g, water-based processed pigment (DISPERSE BLU manufactured by the same company)
E 5D-6038) and 190 g of water were mixed and stirred for 10 minutes using a dispersion stirrer to prepare a paper coating liquid.

100 g of the above coating liquid was mixed with 3 g of each of the antibacterial zeolite samples No. 61 to No. 6 of Reference Example 1, but Comparative Example 1 was not mixed), and stirred and mixed with a dispersion stirrer for 30 minutes to mix the antibacterial zeolite. A paper coating liquid was obtained.

80 g of each of these coating compositions were applied onto commercially available high-quality paper using an automatic film applicator.
/ rrrwi: T2 cloth was applied and dried at 110° C. for 3 minutes to obtain an antibacterial zeolite surface coat.

Pseudomonas aeruginosa diluted to lXl0' cells/al
onasaeruginosa), Bacillus subtilis (Bacillus
llus 5ubtilis) was applied to 1 ml of a sterile Conlar Large coat prepared above, and heated at 37°C.
After culturing for 18 hours, the bacteria were washed out with physiological saline and the number of viable bacteria in the bacterial solution was measured.The number of viable bacteria in Examples 1 to 6 was 0 cells/mβ, and the number of viable bacteria in Comparative Example 1. is 8XIO @ 7ml
Met.

Examples 7 to 12 and Comparative Example 2 (Preparation of impregnating liquid for paper and anti-mold test of antibacterial impregnated paper) Acrylic water-based emulsion [Dainippon Ink & Chemicals ■
DICNAL E-8200] 600g, calcium carbonate aqueous paste [DICNAL E-8200 manufactured by the same company DISPER5E F-
1000] 100g, water-based processed pigment [DIS manufactured by the same company
PER5E RED 50-1011 ] 220 g and 280 g of water were mixed and stirred for 10 minutes using a dispersion stirrer to prepare an impregnating liquid for paper.

However, 3 g of each of the antibacterial zeolite samples No. 1 to No. 6 of Reference Example 1 were added to the impregnated eLloog.

Comparative Example 2 was not blended, and the mixture was stirred and mixed for 30 minutes to obtain an impregnated liquid containing antibacterial zeolite.

Each of these paper impregnating liquids was impregnated into commercially available filter paper using a band dryer (pick up 200%, drying 1
30° C. for 5 minutes) to obtain impregnated paper.

Aspergillus niger, Penicillium fu, diluted to lXl0"a/mj!
J[S
When the impregnated paper was tested for anti-mildew according to Z-2911, no mold was generated in Examples 7 to 12, and mold was generated on the entire surface in Comparative Example 2.

Examples 13 to 18 and Comparative Example 3 (Preparation of antibacterial zeolite-containing paper) Sample No. 1 obtained in Reference Example 1, 150 g of antibacterial zeolite 1 to 6, 30 g of monoethylene glycol, 45 g of naphthalene sulfonic acid formalin condensate, 1 ion exchange water 7
5 g was ground in a sand grinder for 3 hours to obtain 50% aqueous antibacterial zeolite pastes (1) to (■).

The wood pulp was beaten for 30 minutes using a beater, transferred to a beater, and the antibacterial zeolite pastes (I) to (
A papermaking raw material was prepared by adding 2% of Vl) to the wood pulp (but not in Comparative Example 3), 0.5% of a commercially available rosin sizing agent, and 2% of commercially available aluminum sulfate.

Wet paper was made using a hand-made papermaking machine using the above papermaking raw material, and after drying, paper containing 200 g/n of antibacterial zeolite was made.

Pseudomonas aeruginosa (Pseudomonas aeruginosa) diluted to 7 ml
onasaeruginosa), Bacillus subtilis (Bacillus
A mixed suspension of 5. When antibacterial properties were evaluated, the number of viable bacteria in Examples 13 to 18 was 0/111, and the number of viable bacteria in Comparative Example 3 was 4×10′/111.

Furthermore, the handmade papers obtained in Examples 13 and 18 were subjected to discoloration tests using a long-life fade-o-meter (manufactured by Suga Test Instruments Co., Ltd.) for 50 hours and 100 hours, and a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used to test the discoloration. The color difference ΔE from the base paper before the test was measured.

The results are shown in Table 2.

Table 2 Examples 19 to 24 and Comparative Example 4 (Preparation of heat-sensitive recording sheet) Liquid A (dye liquid) 3-(N-ethyl, P, toluidino)-6-methyl-7
-Anilitufluoran 1.0 parts Phenyl 1-hydroxy-2-naphthoate 2.0 lO% polyvinyl alcohol aqueous solution 3.0 Water
5.
0 total 11.0-
Solution B (acidic substance liquid) Bisphenol A 3.0 parts Calcium carbonate 3.0 Zinc stearate 0.5# Antibacterial zeolite No, 1 to No, 6 0.1 'lO%
Polyvinyl alcohol aqueous solution 7.0# water
10
．． 0 #total 23.
6. After separately blending the above A and B solutions and pulverizing and dispersing each with a paint conditioner, A solution 11.
0 part and 23.6 parts of liquid B were mixed to make a heat-sensitive coloring paint (However, in Comparative Example 4, no antibacterial zeolite was added.)
0 Then, this was applied on 64.5 g/nr high-quality paper with a coating amount of 8 g/n after drying. It was coated and dried to obtain a heat-sensitive recording sheet.

Using these heat-sensitive recording sheets, an antifungal test, an antibacterial test, and a light resistance test were conducted as follows.

The results are shown in Table 3.

(Mold-proof test) Aspergillus niger
JIS Z-291 using IFO4407
This was carried out in accordance with 1.

(Antibacterial test) A test piece was prepared by cutting each heat-sensitive recording sheet into sox and sowm pieces, and E. coli solution (10s/-
1) was poured onto the cells and cultured at 37°C for 18 hours. The bacterial solution was washed away with physiological saline, and the number of E. coli present in this solution was measured.

(Light resistance test) The heat-sensitive recording sheets obtained in Example 19 and Comparative Example 4 were tested using a fade-o-meter (^tras Electric).
(manufactured by Devices) for 50 hours and 1
The test was carried out for 00 hours, and the color difference from the sample before the test was measured using a Minolta colorimeter CR-100 model (using Dths light). The result is L*-a*-b* according to CIF 1976
It is expressed by the Teno color difference ΔE value.

Table 3 *Mold-proof evaluation 1: Mildew generated on the entire surface 3: Mildew-free Example 2
5 Liquid C (dye liquid) 3-(N-ethyl-P-toluidino)-6-methyl-7
-Anilitufluorane 1.0 parts Phenyl 1-hydroxy-2-naphthoate 2.0 parts Petroleum resin*-1
5% ligroin solution 6.0 parts ligroin
5.0 copies total
14.0 parts Liquor (acidic substance liquid) Bisphenol A 3.0 parts Calcium carbonate 3.0 parts Zinc stearate 0.5 parts No. 1 antibacterial zeolite 0.1 part Petroleum resin*
15% ligroin solution 14.0 parts ligroin
10.0 copies total
30.6 parts *Hyrenz C-110X manufactured by Nii Petrochemical Industry ■The above C liquid and D liquid were separately blended, and after each was pulverized and dispersed in a paint conditioner, 14.0 parts of C liquid and 30.6 parts of D liquid were mixed. A heat-sensitive color-forming paint was prepared by mixing the following parts. Thereafter, a heat-sensitive recording sheet was obtained in the same manner as in Example 19, and then the same test was conducted.

The results are shown in Table 4.

Examples 26 to 30 and Comparative Example 5 (Preparation of heat-sensitive recording sheet) Antibacterial zeolite NO12 to N006 in place of N011
are respectively 0.1.0.1.0.4.0.8 and 0.
3 parts or no antibacterial zeolite (
A heat-sensitive recording sheet was obtained in the same manner as in Example 25 except for Comparative Example 5), and then the same test as in Example 19 was carried out.
4 Examples 31 to 36 and Comparative Example 6 (Preparation of banking cloth) Ion exchange Ha
After adding 75 g of water and 0.1 g of polyoxyethylene nonylphenyl ether and replacing with nitrogen gas,
25 g of a 1% aqueous solution of ammonium perfaate and 1% water of sodium metabisulfite at ~45°C? 25 g of W solution and the following monomer mixtures (A) to (D) were simultaneously added dropwise over 3 hours.

After the dropwise addition was completed, stirring was continued for 30 minutes at 45-50°C, and then the pH was adjusted to 6-8 with 25% ammonia water, and the resin content was 4.
7% aqueous emulsion resins (A) to (D) were obtained.

Monomer mixture (^) Butyl acrylate 45.0g Ethyl acrylate 45.0g Acrylonitrile 10.0g Acrylic acid
3.0 g N-methylol acrylamide 3.0 g polyoxyethylene nonylphenyl ether 3.0 g Sodium dodecylbenzenesulfonate 0.5 g Monomer mixture (B) Butyl diacrylate 40.0 g Ethyl acrylate 40.0 g Styrene
20.0g acrylic acid
3.0 g N-methylol acrylamide 3.0 g Sodium dodesolbenzenesulfonate 18 g Sodium lauryl sulfate 0.5 g Monomer mixture (C) Ethyl diacrylate 95.0 g Acrylonitrile 5.0 g Itaconic acid
2.0 g N-methylol acrylamide 3.0 g Polyoxyethylene nonylphenyl ether 5.0 g Monomer mixture (D) Niacrylic acid 2-ethyl ester 20.0 g Ethyl acrylate 80.0 g Methacrylic acid 3.0 g Glycidyl methacrylate 3.0 g 3.5 g of polyoxyethylene nonylphenyl ether, 150 g of antibacterial zeolite of Sample No. 1 to 6 obtained in Reference Example 1, 30 g of monoethylene glycol, 1 polyoxyethylene nonylphenyl ether () ILB 13)
15 g and 105 g of ion-exchanged water were milled using a sand grinder for 3 hours to obtain 50% aqueous antibacterial zeolite pastes (1) to (Vl).

Buffing compositions were prepared according to the formulation shown in Table 5 and applied to the back side of the carpet under the following conditions to obtain banking fabrics 31 to 36 of Examples and banking fabric 6' of Comparative Example.

Foaming conditions: Hobart mixer (manufactured by Hobart) 3x foaming Coating conditions: Doctor knife coater Coating amount: 800g/rrr (WET) Table 5
Storage stability: 100 g of the above-mentioned backing composition was weighed into a tin can, and Bacillus 5ubtilis and Pseudomonas aeruginosa diluted to about 1X10' pieces/al were added as spoilage-causing bacteria.
) and a mixed suspension of Escherichia coli (Esherichia coli) were inoculated in 1111 volumes.

After sealing the container and culturing at 28°C for 7 days, the bactericidal effect was evaluated from the number of viable bacteria in the composition. The results are shown in Table 6.

Table 6 The backing composition of the present invention had a strong bactericidal effect and exhibited excellent antiseptic properties during the manufacturing process and storage. Incidentally, the properties as a backing agent of the backing composition to which the zeolite was added and the composition to which the zeolite was not added were compared, but no difference was observed.

Antibacterial property test for backing fabrics For backing fabrics 31 to 36 and 6'' obtained in Examples 31 to 36 and Comparative Example 6, Escherichia coli solution (10'' pieces/va
1) and black koji mold liquid (10S/ml) at 15mj each! It was sprinkled with water and cultured at 37°C for 18 hours. The bacterial solution was washed away with physiological saline, and the number of colon N and black mold present in this solution was measured. The results are shown in Table 7.

Table 7 It was shown that the backing composition of the present invention has a strong bactericidal effect and has excellent antifungal properties. Similar effects were also observed when used in combination with conventionally used antibacterial agents such as TBZ and carhendazine.

Light resistance test A fading test was conducted for backing fabrics 31 and 36 using a carbon arc type fade-o-meter (manufactured by Suga Test Instruments Co., Ltd.) for 50 and 100 hours, and the color difference from the original fabric before the test was measured using a Minolta color difference meter CR-100. Type (using Dis ray)
Measured using The result is L* according to CIF 1976
-a*-1)* The color difference is represented by the ΔE value in the color system, and is shown in Table 8.

Table 8 Examples 37 to 43 and Comparative Examples 7 to 9 (Preparation of resin composition for fiber adhesion) Activator aqueous solutions (al) to (dl) and catalyst shown in Table 9 were placed in a 214-hole flask equipped with a thermometer and a stirring bar. was added, and after one change of nitrogen gas, a 10% aqueous solution of ammonium persulfate and sodium metabisulfite and monomer emulsion mixtures (a2) to (d2) in Table 10 were added dropwise at 45 to 50°C over 3 hours to react. After the completion of the 0-drop addition, the temperature was 30°C at 45-50°C.
Stirring was continued for several minutes to obtain aqueous emulsion resins (A) to (D) with a solid content of 55%. Thereafter, the pH was adjusted to 5 to 7 with 25% ammonia water.

Table 9 (Unit: g) Table 10 8th place (g) Next, 150 g of antibacterial zeolite of samples N011-6 obtained in reference example full, 30 g of monoethylene glycol, ) ILB
13 polyoxyethylene nonylphenol ether 1
5g and 105g of ion-exchanged water using a sand grinder.
50% aqueous paste of time-dispersed antibacterial zeolite (+
) to (Vl) were obtained.

These were mixed in the composition shown in Table 11 to obtain a resin composition for fiber adhesion, and then cloth and cloth or cloth and paper were bonded together under the processing conditions shown in Table 11 to obtain a processed cloth.

*1) Luckstar 05-613EL: Styrene-butadiene copolymer emulsion manufactured by Dainippon Ink & Chemicals *2) DICNAL M-20: Foam stabilizer manufactured by Dainippon Ink & Chemicals *3)
Neocor SWC: Dioctylsulfosuccinate sodium manufactured by Daiichi Kogyo Seiyaku *4) DICNAL EX: Epoxy crosslinking agent manufactured by Dainippon Ink & Chemicals *5) Foaming machine: Hand mixer manufactured by Sanei Seisakusho Processed fabric obtained in this way About 15 m each of Escherichia coli solution (10' pieces/a1) and black koji mold (10' pieces/7 ml)
1 and cultured at 37°C for 18 hours. The bacterial solution was washed away with physiological saline, and the number of Escherichia coli and black mold present in this solution was measured. A light fastness test was conducted on the processed fabrics obtained in Examples 42 and 43 using a fade-o-meter (manufactured by Suga Test Instruments). 50
The time and the color difference between the sample and the original fabric after 100 hours were measured using a Minolta colorimeter CR-100 model (using 04% light). The result is L*- according to CIF 1976;
Table 13 shows the color difference ΔE value in the 1*-b* color system.

Table 13 Examples 44 to 47 and Comparative Example 10 (Preparation of resin processing liquid composition for nonwoven fabric) 150 g of antibacterial zeolite of Sample No. 1 to 6 obtained in Reference Example 1, 20 g of monoethylene glycol, polyoxyethylene nonylphenyl Ether (HLB approx. 13)
15 g of ion-exchanged water and 105 g of ion-exchanged water were milled for 3 hours using a sand grinder to obtain 50% aqueous pastes (1) to (Vl) of antibacterial zeolite. ), a resin processing liquid composition for nonwoven fabric was prepared according to the formulation shown in Table 15, and a spunpond nonwoven fabric (
loog/rd) after soaking, squeeze with two rolls,
After drying at 120°C for 5 minutes, it was heat-treated at 130°C for 5 minutes. The amount of processing fluid deposited was approximately 200 g/rrr.

Table 14 Unit (weight%) Table 15
Unit (wt%) Example 48 and Comparative Example 11
(Preparation of resin processing liquid composition for non-woven fabric) Using polyester short fibers (fiber length 31.4 mm, fineness 3 denier), a web with a weight of 40 g/rd was formed, and the web was sandwiched between two nylon nets. After being impregnated (immersed) in a resin processing liquid composition for nonwoven fabric having the formulation shown in No. 16, it was squeezed with a mangle. The net was removed, the web was dried at 110°C for 5 minutes, and then heat treated at 130°C for 3 minutes to obtain a nonwoven fabric. The amount of processing liquid attached to the web was adjusted to approximately 80,811 ml.

Table 16 The emulsion resin (D) was copolymerized according to the recipe shown in Table 17 below.

Table 17 Example 49 and Comparative Example 12 (Test of antibacterial nonwoven fabric) Resin processing liquid compositions for nonwoven fabrics according to the formulation shown in Table 18 were foamed to about 10 times (volume) using a foaming device (Hobart mixer manufactured by Hobart Co., Ltd.). After that, 200g/n? About 100 g/d of polyester spunbond nonwoven fabric was coated with a knife and impregnated using two rolls. Thereafter, it was dried at 120°C and heat treated at 145°C for 5 minutes.

Table 18 The emulsion resin (E) was copolymerized according to the recipe shown in Table 19 below.

Table 19 Large 11Jji liquid (10S piece/r
a I! ) and black koji mold solution (15 mj each at 10' pieces/mj) were applied and cultured at 37°C for 18 hours. The bacterial solution was washed away with physiological saline, and the number of Escherichia coli and black koji mold present in this solution was determined. The results are shown in Table 20.

Table 20 Next, discoloration tests were conducted for 50 hours and 100 hours on the resin-processed nonwoven fabrics obtained in Examples 44 and 49 using a carbon arc type fade-o-meter (manufactured by Suga Test Instruments Co., Ltd.), and the difference between the nonwoven fabrics and the original fabrics before the test was Minolta Color Difference Meter CR-100
It was measured using a mold (Dl, using light beam). The result is CIF
Color difference △E in L*-a*-b* color system according to 1976
It is expressed as a value and shown in Table 21.

Table 21 Examples 50 to 55 and Comparative Example 13 (Preparation of leather coating composition) 95 g of ion-exchanged water and 0.1 g of polyoxyethylene nonylphenol ether were added to a four-bottle flask equipped with a thermometer and a stirring bar. After nitrogen gas replacement, 40-45
25 g each of a 1% aqueous solution of ammonium persulfate and 1% aqueous solution of sodium metabisulfite and the following monomer mixtures (a) to +d+ were simultaneously added dropwise over 3 hours at °C. Stirring was continued for several minutes, and then the pH was adjusted to 6 to 8 with 25% aqueous ammonia for 8 times to obtain aqueous emulsion resins (A) to ([1]) with a resin content of 40%.

Monomer mixture (a) Ethyl diacrylate 97.0g Acrylic acid 3.0g Polyoxyethylene nonylphenol ether (HLB: 17)
2.0g seven-year mixture (bl
Butyl diacrylate 80.0g Acrylonitrile 15.0g Acrylic acid
5.0g polyoxyethylene nonylphenol ether (HLB: 17)
3.0g Monomer mixture (C) Butyl diacrylate 75.0g Acrylonitrile 20.0g Acrylic acid
4.0g N-methylolacrylamide 1. Og glycidyl memethacrylate 1.0g polyoxyethylene nonylphenol ether (HLB217) 2.0g seven-mer mixture (d) butyl diacrylate 51.0g methyl methacrylate 44.0g acrylic acid 2.0g polyoxyethylene nonylphenol ether (HLB :1
7) Next, 2.0 g of sample No. obtained in Reference Example 1, 150 g of antibacterial zeolites 1 to 6, 30 g of monoethylene glycol, 15 g of polyoxyethylene nonyl phenol ether JL, and 105 g of ion-exchanged water were kneaded in a sand grinder for 3 hours. 50% aqueous paste of antibacterial zeolite (1) ~ (Vl
A natural leather coating composition was prepared according to the formulation shown in Table 21, and coated on silver-finished and grained cowhide leather under the following coating conditions to obtain coated natural leather. However, Example 55
was spray-painted only on the back side of the silver glazed glass base.

(Coating conditions for Examples 50 to 52) Rooted cowhide leather: for clothing, thickness Q, 9 mm stroke, spray coating, drying at 50°C for 3 minutes, 3 cycles, coating amount per cycle: 120 g/rd゛ (implemented) Example 53
Coating conditions for ~55 and Comparative Example 13) Silver glazed glass base: For shoes, thickness 1,211 lines Process: Tight coat...
・−・−−−−−One hand painting 1 time – Drying at 50°C for 3 minutes on the back ・・・・・・・・・・・・−・−Spray painting location Same drying at 50°C for 3 minutes per coat M :Hand-painted 175g/rn' Table 21 * LCCCC Plaque 2 Water-based processed pigments manufactured by Nippon Ink Chemical Industry Co., Ltd. Examples 56 and 57 (Production of antibacterial leather)
LCC Clear L-3350 (Dainippon Ink Chemical Industry ■
After adding 150 g of glass beads with a diameter of 2 fi to 120 g of sample No. 1 (antibacterial zeolite) obtained in Reference Example 1 and kneading it with a paint conditioner for 3 hours, the antibacterial A 20% paste of natural zeolite was obtained. Add 1 g of this paste to 100 g of LCC Clear L-3350 using a dispersion stirrer.
After uniformly dispersing it in the liquid, add LCC thinner L-20 (
Example 51 and Comparative Example 1
On the leather coated with the coating composition No. 3, this Tompcoat agent was sprayed to give a coating weight of 100 g/nf to obtain coated natural leather.

Example 58 and Comparative Example 14 (Production of antibacterial leather) Wet blue of North American steer (thickness 1.5 to 2.0 mm)
After re-edging with chrome paste, further dyeing and fatliquing, 100g of wet blue was mixed with 100g of water at 40°C.
g, 50% aqueous paste of Reference Example 3 (11 g and LC
5 (acrylic resin emulsion manufactured by Dainippon Ink and Chemicals) was added to C-Penetenx and impregnated in a test drum. The pH of the bath at this time was approximately 4.5. After soaking in the bath for 30 minutes, the pH was adjusted to 3.3 with Ant #I (1:10), left for 10 minutes, washed with running water for 5 minutes, and dried at room temperature to obtain natural leather. As a comparative example, after dyeing and fatliquing, the product was adjusted to pH 3.3 with ant a (1:10) and left for 10 minutes, and then washed and dried in the same manner to obtain natural leather.

The natural leathers obtained in Examples 50 to 58 and Comparative Examples 13 to 14 were sprinkled with Escherichia coli solution (10 pieces/+j) and black koji bacteria (to' pieces/[0) and cultured at 37°C for 18 hours. The bacterial solution was washed away with physiological saline, and the number of E. coli and black mold present in this solution was measured. (manufactured by Suga Test Instruments) for 50 and 100 hours, and the color difference with the painted leather before the test was measured using a Minolta Color Difference Meter C.
It was measured using R-100 model (using Dis light beam). The results are expressed as color difference ΔE values in the L*-3*-b* color system according to CIF 1976, and are shown in Table 23.

Table 23 Examples 59 to 64 and Comparative Example 15 (Preparation of resin liquid for urethane leather) Resin solutions (A) to (D) for urethane leather having a resin content of 20% were obtained using the following formulations.

(A) - Most non-yellowing type Crisbon 3056 *1) 100 parts isopropyl alcohol 15 parts toluene
15 parts Dimethylformamide 20 parts (B) General non-yellowing type Krisbon 8166 *2) 100 parts Dimethylformamide 25 parts Methyl ethyl ketone 25 parts (C) Hydrolysis-resistant non-yellowing type Krisbon 1836P *3) 100
Part dimethylformamide 50 parts (D) Highly durable non-yellowing type Crysbon NY-331*4) 100 parts Isopropyl alcohol 15 parts Toluene
15 parts dimethylformamide 20 parts *1) to *4): Both are Dainippon Ink and Chemicals special oil solution for urethane, then 60 g of antibacterial zeolite of samples Nos. 011 to 6 obtained in Reference Example 1, 60 g of salted vinyl acetate resin, 180 g of cyclohexanone was kneaded in a paint shaker for 3 hours to obtain a 20% oil-based paste (+) to (Vl) of antibacterial zeolite. A urethane leather composition was prepared according to the formulation shown in Table 24. Approximately 150μ coating each on release paper, 100μ
A test film was obtained by drying at ℃ for 15 minutes.

Table U *5) In5tafine Black PV-53
38*6) Both Dilac Blue WT-1372 and oil-based d4 manufactured by Dainippon Ink & Chemicals ■ (antibacterial activity test) For the test films obtained in Examples 59 to 64 and Comparative Example 15, Escherichia coli solution (10 parts/m j! ) and Black Koji Kisei (10 parts/111) were sprinkled at 15o+1, respectively, and cultured at 37°C for 18 hours. The bacterial solution was washed away with physiological saline, and the number of Escherichia coli and black mold present in this solution was measured. The results are shown in Table 25.

Table 25 (Light resistance test) The sample films obtained in Examples 59 and 64 were subjected to a fading test using a fade-o-meter (manufactured by Suga Test Instruments Co., Ltd.) for 50
The test was carried out for 100 hours, and the color difference from the film before the test was measured using a Minolta colorimeter CR-100 model (using Das light). The result is L according to CIF 1976
Expressed as color difference ΔE value in *-a*-b* color system, Table 26
Shown below.

Table 26 Examples 65 to 70 and Comparative Example 16 76.9 g of water, Neugen EA-120 (polyoxyethylene nonylphenyl surfactant manufactured by Daiichi Kogyo Seiyaku ■)
2.7g, 25% Saikutan 731 (Rohm & Haas■
4.4 g of an aqueous solution (polycarboxylate dispersant), 17.7 g of ethylene glycol, and 199.6 g of Taibake R-550 (Titanium oxide manufactured by Ishihara Sangyo (Iil)) were mixed and stirred for 1 hour using a dispersion stirrer. and 199.6g of calcium carbonate.

Bestside FX (preservative manufactured by Dainippon Ink & Chemicals) 1.4g, Shichirosize QP-4400 (patch agent manufactured by Union Carbide ■) aqueous solution 174.2g, [1IS
PERSE YELLOW50-4002 (Dainippon Ink Chemical Industry ■ water-based processed pigment) 5g, Nopco ND
W (antifoaming agent manufactured by Sannopco ■) 2.7g.

Butylcarpitol acetate I 7.7g and DICN
348.1 g of ALε-621OA (acrylic emulsion manufactured by Dainippon Ink & Chemicals Co., Ltd.) was further blended and stirred for 30 minutes using a dispersion stirrer. Furthermore, gravestones (3 rin = 75 rin =
1/1) was blended and stirred for 30 minutes using a dispersion stirrer to prepare a ricin paint. To 100 g of this lysine paint, 1 g of each of Sample No. 1 to 6 of antibacterial zeolite of Reference Example 1 was added and stirred for 30 minutes using a dispersion stirrer to obtain an antibacterial zeolite-containing aqueous paint.

This water-based paint contains lXloh bacteria/m as rot-causing bacteria.
Bacillus subtilis (Bacillus 5ubLil) diluted in
is), Pseudomonas aereg
inosa) mixture/! ! Inoculate lll of 5 liquids,
After the can was sealed and cultured at 37°C for 18 days, the number of viable bacteria on the paint was measured using an agar medium. The results are shown in Table 27.

In addition, the above water-based paint was applied to a slate board that had been coated with a water-based sealer and dried, and after drying at room temperature for 7 days, lXl
Aspergillus niger (A
spergillus nigar), Penicillius funicu
JIS Z-29 using a mixed suspension of
The anti-mildew test of the coating film was carried out in accordance with No. 11. The results are shown in Table 27.

Furthermore, fading tests were conducted for 200 hours and 400 hours using a long-life carbon arc fade-o-meter (Suga Test Instruments Co., Ltd.) on the painted slates obtained in Examples 65 and 70, and the results were compared with the original painted boards before the test. Color difference (ΔE)
was measured using a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.). The results are shown in Table 27.

Table 27

Claims (1)

[Scope of Claims] 1. An antibacterial and antifungal processing composition comprising zeolite retaining antibacterial metal ions. 2. The processing composition according to claim 1, wherein the zeolite holding antibacterial metal ions is obtained by replacing some or all of the ion exchangeable ions in the zeolite with ammonium ions and antibacterial metal ions. thing. 3. The processing composition according to claim 2, wherein the zeolite retaining antibacterial metal ions contains 0.5 to 15% by weight of ammonium ions. 4. The processing composition according to claim 1 or 2, wherein the antibacterial metal ion is one or more metal ions selected from the group consisting of silver, copper, and zinc. 5. The processing composition according to claim 1 or 2, wherein the content of zeolite retaining antibacterial metal ions is 0.01 to 30% by weight. 6. Acrylic resin, vinylidene chloride resin, vinyl chloride resin, vinyl acetate resin, butadiene resin, urethane resin, polyester resin, polyamide resin,
3. The processing composition according to claim 1, which contains one or more resins selected from cellulose resins and protein resins.