JPH01299206A - Printing paste composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of keeping the antibacterial property and mildew-proofing property of a printed material such as textile fabric, paper or synthetic resin film over a long period and resistant to discoloration with time, by using a zeolite containing antibacterial metal ion as an active component. CONSTITUTION:The objective composition contains, as an active component, a zeolite having antibacterial metal ion, preferably a zeolite produced by substituting a part of the whole of ion-exchangeable ion in a zeolite with ammonium ion and an antibacterial metal ion. The antibacterial metal ion is, e.g., ion of silver. copper or zinc. A zeolite containing 0.1-15% of silver ion and 0.1-8% of copper or zinc ion is preferable from the viewpoint of antibacterial property. The amount of the ammonium ion is preferably 0.5-2%. The amount of the antibacterial zeolite in the composition is 0.01-50%, preferably 0.02-20%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a printing paste composition having antibacterial and antifungal properties, which is obtained by dispersing zeolite containing antibacterial metal ions.

[Conventional technology]

As is well known, printing pastes contain acrylic acid ester copolymer emulsion, surfactants, cellulose thickening agents, hydrophobic organic solvents, pigments, and other additives. There is. In addition, surfactants, warp sizing agents, oil agents, resin processing agents, etc. are also attached to textiles, knitted fabrics, non-woven fabrics, paper, synthetic resin films, etc. that are the objects of printing. All of these additives have the disadvantage that they are easily attacked by microorganisms such as bacteria and fungi.

[Problem to be solved by the invention]

In order to overcome these drawbacks, attempts have been made to add various antibacterial and antifungal agents to printing pastes. In other words, organic chlorine and organic sulfur compounds have been used, but their antibacterial properties, anti-fungal properties, and low toxicity are not always satisfied.In particular, printed products are used for clothing, bedding, etc. There are many things that can come into direct contact, so sufficient consideration must be given to low toxicity. In addition, durability is also an important point, as they are often washed repeatedly.

[Means to solve problems]

In order to prevent the occurrence of such bacteria and fungi, the inventors of the present invention have conducted intensive studies on antibacterial and antifungal agents for printed textile products, and have added zeolite that retains antibacterial metal ions. The resulting printing paste composition and its processed products have high antibacterial activity not only against fungi but also against -a bacteria, maintain antibacterial activity for a long period of time, and in particular retain antibacterial metal ions. By using a zeolite in which part or all of the ion-exchangeable ions in the zeolite are replaced with ammonium ions and antibacterial metal ions, a printing paste composition with less discoloration over time after printing can be obtained, We have found that this is particularly preferable and have completed the present invention.

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. The object of the present invention is to provide an antibacterial and antifungal printing paste composition containing an antibacterial zeolite substituted with zeolite.

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

Zeolites are generally aluminosilicates with a three-dimensional skeletal structure and have the general formula %. Here, M represents an ion that can be exchanged, and is usually an ion of l or a divalent metal. n is the valence of the (metal) ion. X and Y represent the respective metal oxide and silica coefficients, and Z represents the number of water of crystallization. Specific examples of zeolites include A-type zeolide, can be mentioned. However, the ion exchange capacities of these exemplary zeolites are not limited to these: 7 meq/g for A-type zeolide, 6.4 aeq/g for X-type zeolite, and 5s+ for Y-type zeolite.
eq/g, T-type zeolide 3.4 meq/g, sodalite 11.5 seq/g, mordenite 2.6+
*eq/g, Anna! Resyme 5seq/g - Clinoptilolite 2.6meq/g, Chabasite 5meq/g
- Erionite is 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 thallium, preferably ions of silver, copper or zinc.

From the point of view of antibacterial properties, the above antibacterial metal ions are contained in zeolite at a concentration of 0. It is appropriate that the content is 13% IN.

Antibacterial zeolites containing 0.1-15% silver ions and 0.1-8% copper or zinc ions are more preferred, while ammonium ions can be contained up to 20% in the zeolite, but The content of ammonium ions is 0.5 to 5%, preferably 0.5% to 5%.
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 dry basis at 110°C.

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 aqueous solution is 3 to 10, preferably 5 to 7.
It is appropriate to adjust the 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, ammonium thiosulfate, ammonium phosphate, etc. Silver ions include silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, diammine silver sulfate, etc. etc., copper ions are nitric acid M4 (II), perchlorate steel, acetic acid steel, potassium tetracyanocuprate, copper sulfate, etc., zinc ions are 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, and chromium nitrate. As the thallium ion, thallium perchlorate, thallium sulfate, thallium nitrate, thallium 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 the antibacterial zeolite contains ammonium ions and antibacterial ions, the ammonium ion concentration in the mixed aqueous solution is 0.2 M/1 to 2.5 M/J.

Silver ion concentration 0.002M/J -0.15M/
ffi, 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. In addition, when the antibacterial zeolite further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1 M/ml-0.
,85M/J, zinc ion concentration is 0.15M/t
By setting t~1.2M/1, copper ion content 0.1~89A and zinc ion content 0.1~8%.
antibacterial zeolite can be obtained.

In the present invention, in addition to the mixed aqueous solution as described above, ion exchange can also be performed by using an aqueous solution containing each ion individually and bringing each aqueous solution into contact with the zeolite sequentially. 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 70°C to 90°C under reduced pressure (1 to 30 torr).

Ion exchange of ions without suitable water-soluble salts such as lead and bismuth or organic ions can be carried out using an organic solvent solution such as alcohol or acetone so that hardly soluble basic salts are precipitated.

As the printing paste composition used in the present invention, both aqueous and oil-based printing paste compositions can be used, and although not particularly limited, an aqueous printing paste composition is usually used.

The aqueous printing paste composition 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%, preferably 0.5 to 20% of carboxyl group-containing polymerizable monomer and/or 0.2 to 5% of crosslinkable functional group-containing polymerizable monomer and other polymerizable monomers. body 99
．． Examples include aqueous printing paste compositions containing a copolymer of 8 to 75%.

Copolymerizing the carboxyl group-containing monomer 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, and vinylbenzoic acid, among which acrylic acid,
Methacrylic acid and itaconic acid are preferred.

Copolymerizing a crosslinkable functional group-containing polymerizable monomer results in intramolecular crosslinking with the carboxyl group-containing polymerizable monomer or itself, and improves water resistance by increasing the crosslinking density. I can do it. However, if the content of the crosslinkable functional group-containing polymerizable monomer exceeds 10%, the crosslinking reaction proceeds during polymerization to form a gelled product, making it impossible to obtain a normal aqueous emulsion.

Examples of crosslinkable functional group-containing polymerizable monomers include N-methylol (meth)acrylamide, glycidyl (meth)acrylate, (meth)acrylic M2-hydroxyethyl, maleic anhydride, (meth)acrylamide, (meth)acrylic Acid 2-hydroxypropyl, (meth)acrylic acid, N
, N-dimethylaminoethyl.

Other polymerizable monomers include alkyl (meth)acrylate (C: 1-12), acrylonitrile, styrene, vinyl acetate, vinyltoluene, butadiene, and the like.

The amount of copolymer contained in the printing paste composition is 40 to 1%, preferably 12 to 2% as resin solid content. When the resin solid content in the printing paste becomes high, the flexibility of the printed product is lost. Additionally, as the amount of copolymer in the printing paste increases, the number of antibacterial zeolites appearing on the surface of the printed product decreases, and the antibacterial and antifungal properties decrease when a certain amount of antibacterial zeolite is added. do. On the other hand, if it is less than 1%, the antibacterial zeolite loses its ability to adhere to the printing target.
Durability against washing and abrasion is lost.

The amount of antibacterial zeolite added in the printing paste composition is 0.01
-50%, preferably 0.02-20%. 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, the amount of antibacterial metal ions used for printing the printing paste composition on the printed product was 0.1 mg/cd -1 g/n.
In other words, when the amount of antibacterial zeolite added to the printing paste composition is small, it is necessary to increase the printing area on the object.

The pattern to be printed is of course printed on the entire surface with 100% of the printed area, but also for the purpose of softening the texture of the printed product.
Line patterns, dot patterns, checkered patterns, geometric patterns, etc. may also be used for the purpose of reducing the printing amount of printing paste.

The printing area is usually 2 to 100%, preferably 5 to 90%, and more preferably 10 to 60% of the processed area for antibacterial and antifungal purposes. However, the antibacterial and anti-mold effects are higher when the printing paste is printed as uniformly as possible.
Moreover, it is preferable that there is no non-printed part where the minimum distance to the printed part is greater than 30 cranes, and furthermore, the minimum distance is 5 fi.
Preferably, there are no larger printed areas.

The method and order of addition of the antibacterial zeolite into the printing paste composition are not particularly limited, and whether it is added into the copolymer, into the printing paste composition, or whether it is added into the aqueous Antibacterial zeolite may be added to colored printing paste containing processed pigments, etc. Antibacterial zeolite may be in the form of a powder, an aqueous paste prepared by grinding the powder with an activator, or a dried zeolite. It may be a wet cake of zeolite before the process, and there is no problem as long as it is uniformly dispersed in the printing paste.

The antibacterial zeolite-containing printing paste composition obtained in this manner not only has antibacterial and antifungal functions, but also allows the addition of an aqueous processing pigment in order to color the object to be processed. In addition, well-known resin emulsions such as acrylic, vinyl acetate, urethane, and rubber, latex, water-soluble resin, mineral turpentine, etc. for the purpose of improving various performances,
Hydrophobic organic solvents such as kerosene, water-soluble organic solvents such as alcohol and glycols, neutralizing agents such as ammonia and various amines, wetting agents, anti-drying agents-1 softeners,
Lubricants, thickeners, glues, surfactants, viscosity modifiers, antifoaming agents, matting agents, polishing agents, film thickening agents, dyes, body'ItI!
Various additives such as i-based dyes, tartaric acid used in resist dyeing, Rongalite used in side discharge printing, reducing agents such as dechlorin, optical brighteners, crosslinking agents such as melamine resin, dyeing aids, etc., as appropriate. can be used.

Processing machines include well-known textile printing machines such as auto screen printing machines, rotary screen printing machines, and roller printing machines; coating machines such as doctor coaters, roll coaters, and bar coaters; hand printing using screens; and brush coating. But it is possible.

The printing paste composition of the present invention can be used for all conventionally printed objects. In particular, it is used for antibacterial, anti-mold, and deodorizing purposes, such as socks, underwear, dress shirts, diapers, diaper covers, work clothes, uniforms, surgical gowns, rain jackets in the clothing field, and sheets, pillow cases, and pillowcases in the bedding field. Futon covers, bed covers, futons, seat covers, and daily necessities include carpent,
Slippers, shoe lining, shoe insoles, towels, napkins, hats, masks, bathroom mats, toilet seat covers, rental items,
In the apron and industrial materials field, products include wallpaper, wall cloth, book cloth, tents, chair upholstery, and filters.

〔Effect of the invention〕

As described above, since the present invention contains zeolite that retains antibacterial metal ions, it has the effect of maintaining high antibacterial and antifungal properties for a long period of time.

Moreover, it is possible to suppress the fading of color over time of the printed product, and it also has the effect of providing 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 A-type zeolide (NaxO-AIzO).

・1.9SiO1~x H@0: Average particle size 1.5 p+
), X-type zeolide (NazO・Altos・2
．． 3SiOz ・X HtO: average particle size 2.5, u
s), Y-type zeolide (1,1NaxO-A1.Ox
・4SiO□ ・x tl□0: Average particle size 0.7 μm
), natural clinoptilolite (150 to 250 mesh) were used. Salts to provide each ion for ion exchange: N Ha N Os, AgN0z
, Cu(NJ), and Zn(Nat)t were used.

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. 5, were obtained.

For each sample, water was added to 1 kg of zeolite powder that had been heat-dried at 110 tons to make a 1.31 slurry, which was then stirred and degassed, and an appropriate amount of 0.5N nitric acid solution and water were added to make a PO. 5 to 7, and the total volume was made into a slurry of 1.81. For zero-order ion exchange, 3i of a mixed aqueous solution of a specified salt with a predetermined concentration was added to make the total volume 4.81, and this slurry liquid was adjusted to 40 to 7. It was maintained at 60 t and stirred for 10 to 24 hours to reach an equilibrium state. After the ion exchange was completed, the zeolite powder was filtered and washed with room temperature water or warm water until the excess silver, copper, or zinc ions in the zeolite phase disappeared.Next, the samples were heated and dried at 110°C, and six types of samples were prepared. I got it. Obtained no.

Data regarding antibacterial zeolite samples Nos. 1 to 6 are shown in Table 1.

Reference Example 2 (Preparation method of aqueous emulsion resin for printing paste) 95 g of ion-exchanged water and 0.1 g of polyoxyethylene nonylphenol ether were added to a 4-tube flask equipped with a thermometer and a stirring bar, and after purging with nitrogen gas, 40-4
At 5° C., 25 g of a 1% aqueous solution of ammonium persulfate, 25 g of a 1% aqueous solution of sodium metabisulfite, and the following seven-mer mixtures (a)° to (d) were simultaneously dropped over a period of 3 hours. After the addition, stirring was continued for 30 minutes at 45 to 50°C, and then the pH was adjusted to 6 to B with 25% aqueous ammonia to obtain aqueous emulsion resins (A) to (D) with a resin content of 40%.

Monomer mixture (a) Butyl diacrylate 47.0g Ethyl acrylate 47.0g Acrylic acid 3.0g N-methylolacrylamide 3o0g Polyoxyethylene nonylphenol ether 5.0g Monomer mixture (a) 2-ethylhexyl diacrylate 30.0g Methyl methacrylate 30 .0g Ethyl acrylate 21.0g Methacrylic #I 18, Og Glycidyl methacrylate 1.0g Polyoxyethylene nonylphenol ether 5.08 Monomer mixture (C) Ethyl diacrylate 50.0g Butyl acrylate ao, og Styrene 12.0g Acrylic Acid 5.0g 2-Hydroxyethyl methacrylate 3.0g Polyoxyethylene nonylphenol ether 3.0g Monomer mixture (d) Ethyl nitacrylate 70.0g Acrylonitrile 24.0g Itacone @ 1.0g N-methylolacrylamide 5.0g Polyoxyethylene Nonylphenol ether 5.0g Reference Example 3 (Preparation of antibacterial zeolite paste) Reference Example 1
Samples N'o, 1 to 6 of antibacterial zeolite 15 obtained in
0g, monoethylene glycol 30g, polyoxyethylene nonylphenol ether 15g 1 ion exchange water 1
05g was kneaded in a sand grinder for 3 hours to obtain 50% aqueous antibacterial zeolite pastes (1) to (Vl).

Examples 1 to 6 and Comparative Examples (Manufacture of printing paste composition and printed fabric) A printing paste composition was prepared according to the recipe shown in Table 2, and printed on broad cotton #60 under the following printing conditions to produce a printed fabric. 1-6
and 1" were obtained.

(Printing conditions) Screen printing Niscreen mesh 90 process: Printing -
Drying (100℃, 1 minute) - Heat treatment (150℃, 1 minute) *1) Ryudai-W Blue RLC-H (Ryuud
ye-WBlue RLC-H) *2) Ryudye-W Left FBI (Ryudye
-WRed FBI) Both are water-based processed pigments manufactured by Dainippon Ink & Chemicals.

*3) Ryud-W Reducer-400 (Ryuud
ye-HR Reducer 400) Prescription *4) Ryudye-W Reducer-117 (Ryudye-W Re
ducer 117) Formulation 5) Pattern Dots: 25 dots/inch Plaid pattern: Checkered pattern width 0.5 fl Example 7 (Antibacterial activity test) Printed fabric 1 obtained in Examples 1 to 6 and Comparative Example 1 ~6 and 1' were sprinkled with Escherichia coli solution (10S cells/s1) for 15s+1 and A. black mold solution (10S cells/s1) for 15s+1, respectively, and cultured at 37°C for 18 hours.The bacterial solution was washed away with physiological saline, The number of Escherichia coli and Aspergillus niger present in this liquid was measured.The results are shown in Table 3.

Table 3 Example 8 (Lightfastness test) The printed fabric 1.6 obtained in Example 1.6 was tested using a fade-o-meter (^tlas Electric Devi).
A fading test was conducted for 50.100 hours using a CES company (manufactured by CES), and the color difference from the original fabric before the test was measured using a Minolta colorimeter CR-100.
It was measured using a mold (using Das light). The result is CIF
Table 4 shows the values of E values for L 11 to all 6 s color yarns according to 1976.

Table 4

Claims (1)

[Scope of Claims] 1. An antibacterial and antifungal printing paste composition comprising zeolite retaining antibacterial metal ions. 2. The printing paste 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 printing paste composition according to claim 2, wherein the zeolite retaining antibacterial metal ions contains 0.5 to 15% by weight of ammonium ions. 4. The printing paste 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 printing paste composition according to claim 1 or 2, wherein the content of zeolite retaining antibacterial metal ions is 0.01 to 30% by weight. 6. Printing paste contains carboxyl group-containing polymerizable monomer from 0.1 to
40% by weight and/or 0.0% crosslinkable functional polymerizable monomer.
1 to 10% by weight and 99.9 to 50% of other polymerizable monomers
The printing paste composition according to claim 1 or 2, comprising an aqueous emulsion of a copolymer consisting of % by weight.