JPH01263175A - Bactericidal and fungicidal tacky adhesive composition and tacky adhesive tape and sheet - Google Patents

Abstract

PURPOSE:To obtain a tacky adhesive composition having excellent bactericidal and fungicidal activity, by using solid particles of an aluminosilicate containing a metal ion having bactericidal activity. CONSTITUTION:Solid particles of an aluminosilicate (preferably powdery or granular zeolite, etc., having particle diameter of 0.1-3mum) are mixed with a solution of a water-soluble salt containing bacteriostatic metal ion (e.g., silver or copper) to effect the ion exchange and obtain solid particles of a bacteriostatic aluminosilicate (preferably containing 0.01-10% of the bacteriostatic metal) containing the bacteriostatic metal ion adsorbed to the ion exchange group of the aluminosilicate by ion-exchange. A bactericidal and fungicidal tacky adhesive composition is produced by adding preferably 0.02-5% of said bactericidal aluminosilicate solid particles to a tacky adhesive and a bactericidal and fungicidal tacky adhesive tape or sheet is produced by applying said composition to a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel adhesive composition having excellent antibacterial and antifungal properties and containing aluminosilicate solid particles that retain metal ions having a bactericidal effect. It is. Furthermore, the present invention provides adhesive tapes and sheets using such antibacterial and antifungal adhesives.

The proliferation of bacteria and mold from rubber-based, acrylic-based, vinyl-based, polyurethane-based adhesives, and from adhesive tapes and sheets using such adhesives has become a problem.

For this reason, organic antifungal agents have been added to adhesives as a measure to prevent the growth of bacteria and mold, but their toxicity, antibacterial, and antifungal properties are not necessarily satisfactory. The current situation is that it cannot be said that this is being done.

In order to overcome the current situation, the present inventors have made extensive studies on adhesive compositions and adhesive tapes that have antibacterial and antifungal properties. As a result, adhesive compositions containing aluminosilicate solid particles that retain bactericidal metal ions at °C, as well as adhesive tapes and sheets using the same, have extremely low toxicity and are highly effective in preventing We have completed the present invention by discovering that it exhibits antibacterial and antifungal properties.

That is, the present invention uses silver, copper, zinc, tin, lead, bismuth,
An aluminosilicate selected from the group of antibacterial metals consisting of iron and chromium retains two or more metal ions with an ion-exchangeable portion of an amorphous or crystalline aluminosilicate. The present invention provides an antibacterial and antifungal adhesive composition containing solid particles of the same type, and an adhesive tape and sheet using the same.

Examples of adhesives that can be used in the present invention include the following. Rubber adhesives include natural rubber, recycled rubber,
Synthetic rubber systems and mixtures of the above, as well as third components (e.g. tackifiers, adhesion and retention force regulators, fillers)
An example of this is a pressure-sensitive adhesive containing . Examples of the synthetic rubber include styrene-isoprene-styrene block copolymer, styrene-butadiene, polyisobutylene, polyisobutylene-based rubber, and silicone rubber. Examples of acrylic adhesives include copolymers of one or more acrylic monomers selected from acrylic esters and methacrylic esters and other unsaturated monomers. Furthermore, as a vinyl adhesive, vinyl chloride
Preferred examples include vinyl polymers such as vinyl acetate copolymers, vinyl acetate polymers, and polyvinyl butyral to which a plasticizer is added. Other adhesives that can be used in the present invention include polyurethane adhesives. Note that the adhesives mentioned in this application include all adhesives that are generally commercially available or described in patent publications, literature, etc.

Next, the pressure-sensitive adhesive composition of the present invention is prepared using the above-mentioned pressure-sensitive adhesive, and the shape (eg, tape or sheet) and support in which it is specifically used are not particularly limited in the present invention. For example, when the pressure-sensitive adhesive composition of the present invention is used in the form of a pressure-sensitive adhesive tape, various forms such as a single-sided tape, a double-sided tape, and a tape without a support can be made depending on the method of use. In addition, supports for single-sided tape and double-sided tape include paper such as Japanese paper, rayon paper, and high-quality paper;
Preferred examples include cloths such as vinylon and polyester fibers, nonwoven fabrics such as nylon, polypropylene, and polyester, and films such as polyethylene, polypropylene, polyester, and polyvinyl chloride. Furthermore, metal foils, various foams, and the like can also be used as supports for the pressure-sensitive adhesive composition of the present invention.

Next, the aluminosilicate solid particles used in the present invention to stably retain metal ions having a bactericidal effect will be described. The aluminosilicate used for the antibacterial metal support has the general formula %, where M is an ion-exchangeable monovalent to polyvalent metal (e.g., alkali metal, alkaline earth metal, etc.), However, silver,
Excludes the antimicrobial metal group consisting of copper, zinc, tin, bismuth, iron and chromium.

2 and ν represent the coefficients of metal oxide and silicon dioxide, respectively, and ν represents the number of water molecules in the aluminosilicate. When the aluminosilicate expressed by the above general formula is crystalline, it is a so-called zeolite, and when it is amorphous, it is called an amorphous aluminosilicate (hereinafter referred to as AMAPI).
).

Therefore, both crystalline aluminosilicate (zeolite) and AMAS can be used as the supporting matrix for the sterilizing metal ions of the present invention.

The natural or synthetic zeolite materials with a 5iO2/At*Os molar ratio of 10 or less, as exemplified below, have sufficient exchange to retain the required amount of one or more antibacterial metal ions required in the present invention. Retains capacity. specifically,
Natural zeolites suitable for the present invention include chabasite;
Examples include mordenite, erionite, and clinoptilolite. StO, which constitutes these zeolites, /
The molar ratio of At and O is 10 or less. On the other hand, examples of synthetic zeolides include A-type zeolite (840,/At
,0. : 2), X-type zeolite (St fake/At, 0
．． 2.5), Y-type zeolite (S ion/A403
``5) etc. are exemplified as preferable materials.The natural and synthetic zeolites mentioned above have a large specific surface area, are porous, and have sufficiently large theoretical ion exchange capacities, so they are suitable for this purpose. It is suitable as a material for use in the invention.

A J/ A S (zM40-A4Qs ・y 5if
t), the aluminosilicate material in the range of 2 = 0.6 to 1.8 and ν = 1.3 to 15 is porous and has a specific area of 9, and is also suitable for the present invention. It can be said to be a suitable material because it has sufficient ion exchange capacity to hold the required amount of one or more antibacterial metal ions required for the treatment.

The shape of the above-mentioned zeolite or AMAS is preferably powder to particulate. These aluminosilicates (non-antibacterial) are made antibacterial by the following method. Zeolite or AMAS is a water-soluble salt solution (e.g. silver nitrate) containing one or more antibacterial metal ions selected from the group of antibacterial metals consisting of silver, copper, zinc, tin, lead, bismuth, iron and chromium. A predetermined amount of antibacterial metal ions (e.g. A Q
The antibacterial silicate (crystalline or amorphous) is prepared by ion-exchange adsorption of ``:Ag+'';AlF+-Z%2+) onto the ion-exchange groups of the silicate matrix.

As mentioned above, antibacterial metal ions include single antibacterial metal ions (e.g. A, +, Ct2-)-,,2+) or combinations of two or more antibacterial metal ions fJ1 (e.g. Ag+).
-Cx2+;Ag+-Zs”;Ag2+-0%2+,
2-)-) is used. The antibacterial zeolite or AMAS prepared by the ion exchange method described above is filtered;
Excess metal ions are then removed from the solid phase by washing with water. The antibacterial silicate that has been washed with water is usually 1
The dried product is dried at a temperature of 00'-110°C, and if necessary, the dried product is pulverized and adjusted to have a predetermined particle size distribution.

The particle size of the antibacterial zeolite or AMAS powder added when preparing the antibacterial and antifungal adhesive composition is 1
It is preferably 0μ or less, and preferably in the range of 0.1 to 3μ. Further, the water content in the above antibacterial agent is desirably at least 1% or less.

Antibacterial Zeolite 17' (AMAS 200'-35
It is easy to prepare an activated powder with antibacterial activity by heating it to 0° C. (heating under reduced pressure if necessary) and keeping the water content in the powder at 1% or less. Next, antibacterial zeolite or A
The content of antibacterial metals in MAS is controlled by the type and combination of antibacterial metals and the type of adhesive used, but is usually adjusted to 0.01 to 10%.

antibacterial zeolite) or AM prepared by the method described above.
The activated powder of AS is added in a predetermined amount to the aforementioned rubber-based, acrylic-based, vinyl-based, polyurethane-based, etc. adhesive to prepare the antibacterial and antifungal adhesive composition of the present invention. For example, the adhesive composition of the present invention can be obtained by blending an acrylic adhesive, a curing agent, an antibacterial zeolite or AMAS, and a solvent in a fixed ratio. The content of antibacterial zeolite or AMAS in the adhesive composition is usually 10% or less,
Sufficient antibacterial and antifungal effects can be achieved at 5% or less. The preferred range of antimicrobial zeolite or AMAS in the above composition is 0.02-5%.

Next, by coating the above-mentioned adhesive composition on the above-mentioned support, antibacterial and antifungal adhesive tapes, sheets, etc. can be easily produced by MA.

Production Example 1 This example relates to a production example of the antibacterial aluminosilicate (crystalline; zeolite) used in the present invention.

Dry fine powder of A type synthetic acid zeolite [Nα2 type; 1.02
NalO=A110B ・1.985t02・zH10
] Approximately 50 (11ft collected, 0.30 M C%
(NO,)! -0,12AgN0j mixed solution was added about 2 times. The resulting mixture was stirred for about 3 hours and 30 minutes for ion exchange (at room temperature), and a portion of Na1 in the zeolite was partially replaced with Ag+-Cs2+ to prepare a NaAgC5Z type antibacterial zeolite. The solid phase is then filtered;
The zeolite solid phase was then washed with warm water to remove excess metal ions. The antibacterial zeolite that had been washed with water was dried at 105° to 110°C and then pulverized [Yield of dried NαAQC%Z = 493? ; Average particle diameter D
at = 2.3μ; Content of antibacterial metal: Ay = z,
7%, C5=4-9% (anhydrous basis)].

Next, the dried NaAgC Z powder (approximately 90?) is 24
It was heated under reduced pressure at a temperature of 0'-250°C, and the moisture content therein was maintained at 0.4%.

Production Example 2 This example relates to a production example of antibacterial aluminosilicate (amorphous; AMAS) used in the present invention.

Sodium type AMAS (1,10Na, 0-
AtzOs・2,51 SiO2; Da* = O1
3 μm) was used and converted to the antibacterial A g Cs - AM A S by partial replacement of some of the ion-exchangeable Na 0 in the 7 with AQ+-C%2+. That is, for the Na-AMAS material of about 5002, Q, 3 M C5 (NOs) t-.0. IMAgN
Approximately 1 t of O8 mixed solution was added, and ion exchange was performed in the same manner as in Production Example 1 described above.

In this production example, the AgCs-AMAS dry product is approximately 470
A fine powder of No. 2 was obtained [Content of antibacterial metal in AgCx-AM AS: Ag = 2.4%; C5 = 4.3% (
(anhydrous standard)].

Next, dried MinoAgCs-AM A S powder about 10O
f was heated at a temperature of 270° to 280°C, and the moisture content therein was kept at 0.2%.

This example relates to the preparation of the antibacterial and antifungal adhesive composition of the present invention. In this example, the acrylic adhesive composition was as shown in Table 1-2. ] A curing agent, antibacterial zeolite or antibacterial AMAS, and a solvent were mixed in a fixed ratio.

Daiichi Shishi Antibacterial and antifungal adhesive composition Acrylic adhesive 60 60 Insyanate hardener 0.3 0.3 Toluene solvent
2020 Tatami manufacturing example 1: NaAgC5Z (Ag = 2.7
%; C% = 4.9%; H, 0 = 0.4%) Compounding unit double placement part Table 2 Antibacterial and antifungal adhesive composition compounding components
Example 3 Acrylic adhesive 6° Isocyanate curing agent 0.3 Toluene solvent
20 tatami production example 2: AQC%-AMAS (A
g = 2.4%; C% = 4.3%; H, O = 0.2%) Blending unit: parts by weight In Examples 1 and 2, the antibacterial aluminosilicate (crystalline Quality: Antibacterial zeolite Na A g Cs
Z) and NaAgC5Z;
．． An antibacterial and antifungal adhesive composition containing 12 and 0.24 parts by weight (Table 1) was prepared. In Example 3, the antibacterial aluminosilicate (amorphous: antibacterial AgCs-AHAS) of Production Example 2 was used to produce AQC irises.
An antibacterial and antifungal adhesive composition containing 0.25 parts by weight of A and V A S (Table 2) was prepared.

This example relates to the antibacterial and antifungal adhesive tape of the present invention.

An acrylic adhesive tape was prepared by coating the antibacterial/antifungal adhesive composition of the present invention prototyped in Examples 1 to 3 on a polyester support, and an antibacterial activity test was conducted. When measuring changes in the number of bacteria over time, the above tape was cut into small test pieces of approximately 110 x 10, and 15 of these were used for each test using the shake flask method (Textile Sanitary Processing Council's antibacterial activity test). The test was conducted in accordance with the Act.

When using adhesive tapes made of the adhesive compositions of Examples 1 and 2, Staphylococcus aureus (Stαp)
srmsa) reduction rate was 90% at 6 hours of action.
% or more, and after 24 hours, it was 99.9% for the tape made of the adhesive composition of Example 1, and reached 100% for the tape made of the adhesive composition of Example 2 ( Table 3). On the other hand, it can be seen that the adhesive tape of Comparative Example 1 (no antibacterial agent added) has no effect on Staphylococcus aureus.

Table 4 shows Aspergillus niger (A
apgrgiLlsa sigar)
- This shows the antibacterial activity of acrylic adhesive tape containing AMAS. After 12 hours, the reduction rate of the above fungi had reached 96%, but on the other hand, the acrylic adhesive tape containing the adhesive of Comparative Example 1 (for blank test: no antibacterial agent added)
The antibacterial activity of is O. These tests showed that the pressure-sensitive adhesive composition of the present invention and the tape prototyped therefrom showed preferable antibacterial properties.
It is clear that it has an antifungal effect.

This example relates to the adhesive sheet having antibacterial and antifungal properties of the present invention. An acrylic adhesive sheet was prepared by applying the antibacterial and antifungal adhesive composition of the present invention prepared in Examples 1 and 2 to a polyester support. This was cut into test pieces of about 40 x 600, and a mold resistance test was conducted on the test pieces according to JIS Z2911.

Strain used - AspargiLlsa siger (IF
O4407), PmsiciL1smcsicslo
zsm (IFO6345), Chaatomistn
globossm (IFO6347), G11oaLt
Ldistn vtva*5 (IFO6355) and Asraobaztdtsmpsllslana (IF
5 types of spore suspension of O6353) - After culturing the above 5 types of strains on a potato dextrose agar slant until sufficient spores are formed,
The spores were suspended in a sterile 0.05% dioctyl sodium sulfoconophosphate solution to form a single spore suspension. Next, equal amounts of each single spore suspension are mixed to obtain a mixed spore suspension with v
I4! ! ! ! It was done.

Test procedure - The specimen was placed in a petri dish and the mixed spore suspension was sprinkled onto it until the surface was wet.

Next, these petri dishes were cultured for 30 days at a temperature of 29° C. and a humidity of 85% or more, and the growth state of mycelium produced on the surface of the test object was observed.

Table 5 Mold resistance test subject: Approximately 40 x 60 m (acrylic adhesive sheet) Adhesive sheet (Comparative example 1) 2 (Example 1) 1 (Example 2) 0 The results of the mold resistance test are shown in Table 5. . An evaluation value of O indicates no mold growth. Symbol 1 indicates mold growth on less than 10% of the surface area. Also, 2 is the surface area of 10 to 30
% indicates that mold growth is observed. Compared to the pressure-sensitive adhesive sheet prototyped using the adhesive composition of Example 1, the pressure-sensitive adhesive sheet prototyped using the pressure-sensitive adhesive composition of Example 2 exhibited superior mold resistance and inhibited mold growth. was found to be completely prevented. On the other hand, in the adhesive sheet of Comparative Example 1 (no antibacterial agent added; blank test), mold growth was observed over a considerable surface area.

In summary, the present invention provides a novel adhesive composition with excellent antibacterial and antifungal properties, which contains aluminosilicate (crystalline or amorphous) solid particles that retain metal ions having a bactericidal effect. It provides products as well as adhesive tapes and sheets, and is believed to have a wide range of uses.

Embodiments of the Invention (1) An antibacterial and antifungal adhesive composition comprising aluminosilicate solid particles retaining metal ions having a bactericidal effect.

(2) The content of the aluminosilicate solid particles mentioned in the previous section is 0.
The pressure-sensitive adhesive composition according to item 1 above, which has a content in the range of 0.02 to 5%.

(3) The pressure-sensitive adhesive composition according to item 1 above, wherein the albanosilicate solid particles are crystalline aluminosilicate (zeolite) solid particles.

(4) S i O with crystalline aluminosilicate (zeolite) solid particles of 10 or less! /At! The pressure-sensitive adhesive composition according to item 1 above, which has a molar ratio of Q1.

(5) The pressure-sensitive adhesive composition according to item 1 above, wherein the aluminosilicate solid particles are amorphous aluminosilicate solid particles.

(6) Amorphous aluminosilicate solid particles (AuAs:Z
A/IQ-A4Q3 ・y S tO2) z =
0.6-1.8, V-1.3-15, the adhesive composition according to item 1 above.

(7) Aluminosilicate containing one or more metal ions selected from the antibacterial metal group consisting of silver, copper, zinc, tin, lead, bismuth, iron, and chromium. The pressure-sensitive adhesive composition according to item 1 above, which contains salt-based solid particles (amorphous or crystalline).

(a) Adhesive tapes and sheets using antibacterial and antifungal adhesive compositions containing aluminosilicate solid particles (amorphous or crystalline) that retain metal ions with bactericidal activity. .

(9) The above item 8, which uses the antibacterial and antifungal adhesive composition containing 0.02 to 5% of the aluminosilicate solid particles (amorphous or crystalline) described in the previous item. The adhesive tape is a sheet.

Patent applicant: Hagiwara Giken Co., Ltd. Kanebo Co., Ltd. Representative Patent Attorney: Kyo Yu Asa Shimari (4 others)

Claims (2)

[Claims] (1) An antibacterial and antifungal adhesive composition containing aluminosilicate solid particles that retain metal ions having a bactericidal effect. (2) Adhesive tape or tape using an antibacterial and antifungal adhesive composition containing aluminosilicate solid particles (amorphous or crystalline) that retain metal ions that have a bactericidal effect. sheet.