JPS5817765B2 - Chlorinated polyethylene resin composition with excellent microbial adhesion prevention properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chlorinated polyethylene soft resin composition that prevents the adhesion of microorganisms such as mold, bacteria, and algae.

Polyvinyl chloride soft compositions, which are representative of conventional soft resin compositions, often have mold, bacteria, or microorganisms such as algae attached to them in water because of the large amount of plasticizers they contain. There were many inconveniences when using the plasticizer, as the contained plasticizer oozed out to the surface and polluted the environment, and the properties of the plasticizer itself deteriorated due to the deplasticizer.

The present invention provides a soft resin composition that does not have the above-mentioned drawbacks and has excellent antimicrobial adhesion properties, and has a chlorine content of 2.
It is characterized in that it is made of a chlorinated polyethylene resin mainly composed of rubber-like chlorinated polyethylene having a weight of 5 to 45% by weight, and a specific compound described later as an agent having a microbial adhesion prevention effect.

The chlorinated polyethylene resin used in the present invention refers to chlorinated polyethylene alone, or polymers with a low degree of polymerization that are compatible with chlorinated polyethylene, such as polyvinyl chloride, ethylene-vinyl chloride copolymer, etc., which flow during molding. A mixture with a polymer having good properties is prepared.

The chlorinated polyethylene used in the present invention is preferably rubber-like chlorinated polyethylene with a chlorine content of 25 to 45% by weight, which is chlorinated at the melting temperature of the raw material polyethylene crystals or a temperature lower than that.

The raw material polyethylene preferably has a molecular weight of 10,000 to 130,000; anything less than this range will result in chlorinated polyethylene with poor mechanical strength, and one with a molecular weight exceeding the above range will have poor processability and will result in 9-chlorinated polyethylene. , both are unfavorable.

To chlorinate polyethylene, a preferred method is to disperse polyethylene powder in water or other non-solvent and introduce chlorine.

As mentioned above, the chlorination temperature is preferably the melting temperature of the crystals of the raw polyethylene, or a temperature lower than that. Favorable wrinkles to prevent coagulation.

The agents to be incorporated into the composition of the present invention include antifungal agents,
Algaecides and other substances that have a microbial adhesion prevention function have a certain degree of affinity with the base material, chlorinated polyethylene resin, and the base material is used to maintain the microbial adhesion prevention function over a long period of time after mixing with the agent. A compound that satisfies the requirements that a drug mixed into the material can be gradually leached and transferred to the surface is preferable, and is selected from the compounds listed below.

Namely, 2(4-thiazolyl)penzimitasole, bis(P-chlorophenyl)diguanide, N-(fluorodichloromethylthio)phthalimidohexandinohydrochloride, N-lauryl-β-alanine, 10.10'
-Oquinisphenoquine, dodecylguanidine hydrochloride, 2,4,5,6-titrachloroisophthalonitrile, dibutyltin oxide, etc.

Although the drug may be directly blended into the base resin, the amount of the drug can be reduced if it is blended with a carrier prepared with an additive that has good compatibility with the base resin, such as a small amount of plasticizer or stabilizer. However, it is preferable because the effect becomes noticeable and the effect of keeping the microbial prevention function for a long time increases.

Additives with good compatibility with such base resins include:
Examples of plasticizers include diisooctyl phthalate, chlorinated paraffin, tricresyl phosphate, and epochene type plasticizers, and as stabilizers, organic tin type, organic lead type, etc. are preferably used.

In this case, the additive serving as the carrier' is preferably liquid at room temperature.

The amount of these additives added is chlorinated polyethylene resin io
20 parts by weight or less is suitable for 0 parts by weight.

Addition of more than 20 parts by weight is not preferred because the drug will be significantly eluted as the additive migrates to the surface, long-term effects cannot be expected, and the adhesion of microorganisms due to the additive will increase.

The amount of the drug to be added is selected to be an appropriate amount that has good affinity with the base resin, does not cause environmental pollution due to significant migration and elution of the drug to the surface, and maintains its effect for a long period of time. The range of 0.05 to 5% by weight is selected.

The composition of the present invention may contain various commonly used additives depending on the purpose of use, such as fillers, reinforcing agents, processing aids,
Anti-aging agents, heat retardants, etc. can be added as desired.

Mixing of the compositions is accomplished by dosing and mixing the entire formulation using commonly available mixers.

In this case, it is preferable to add a small amount of the drug by mixing other ingredients and then finally adding the drug to increase the effect of the drug after molding.

The temperature of the blend during mixing is suitably between 40 and 50°C.

If the temperature exceeds 50°C, the chlorinated polyethylene resin tends to become plasticized and becomes difficult to handle, so it must be avoided.

The composition of the present invention can be advantageously used as a molded article having antimicrobial adhesion properties in various applications such as films, trunks, pipes, and laminates, similar to the applications of conventionally known flexible polyvinyl chloride resin compositions.

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

Example 1 70 tons of water and 70 tons of suspension stabilizer (polyacrylic acid amide) were added to 7 pieces of powdered polyethylene with a density of 0.945, a melt index of 6.9, a crystal melting temperature of 127 to 130°C, and an average molecular weight of 40,000. While stirring, raise the temperature to 110℃.
Chlorine gas was introduced at (reaction pressure 3 to 4 to 9/L, L2)
.

When the chlorine content reached 13 parts, the temperature was raised and chlorination was further carried out at 115°C with a chlorine content of 133 parts by weight.

The temperature was further raised to 127°C to chlorinate the final chlorine content to 35 parts by weight.

After the reaction, the solution was neutralized, and the polymer was thoroughly washed with water and dried.

To 100 parts by weight of the above chlorinated polyethylene, 10 parts by weight of talc, 3 parts by weight of a stabilizer (tin laurate) and 0.1 parts by weight of 2(4-thianyl)benzene imidazole to the resin.
Add weight, 200 Orpm in Hennel mixer
Mixing was carried out at high speed rotation until the powder temperature reached 50°C.

The above blend was made into pellets using an extruder at a temperature of 150°C,
Threading was carried out by extrusion molding under the following conditions.

Extrusion molding extruder Pressure = 22 Diameter 40vx Screw rotation speed 3 Orpm Mold temperature C3C2C1 160℃ 150 100℃ 100℃ mold
T-die, width 400cm, sheet thickness u Formability A drug dissolution extraction test was conducted using the molded piece with good appearance.
The dissolution test was conducted according to the WA (Japan Water Works Association Standards) dissolution test.

The test method is to use a sample immediately after manufacture (size 200 x 70 x 2
sm) in 2 tons of water at 20°C and 50°C, respectively.
The amount of drug dissolved in water after 24 hours was measured.

In the next step, we would like to immerse this sample in 2 tons of fresh water and measure it after 1 week at each temperature. The amount dissolved was measured.

Table 1 shows the measurement results.

As is clear from the results in Table 1, it was found that the amount of drug dissolved in water at room temperature (20°C) was within the detection limit, and there was almost no contamination of reed water.

Example 2 Density 0.955. Powdered polyethylene 7 malt having a melt index of 0.04, a crystal melting temperature of 127 to 132°C, and an average molecular weight of 120,000 and 70 tons of ion-exchanged water.

Add 70 t of suspension stabilizer (acrylic acid amide), raise the temperature while stirring, and introduce chlorine gas at 115°C to make 20% by weight.
Until the chlorine was loosened.

Next, the temperature was raised to 125°C, chlorination was carried out to 30% by weight, and further 1
The temperature was raised to 28°C and chlorination was carried out to 37% by weight.

The reaction soaking liquid was neutralized, and the polymer was thoroughly washed with water and dried.

80 parts by weight of the above chlorinated polyethylene, 20 parts by weight of ethylene-vinyl chloride copolymer (rE-430 manufactured by Nichikagaku Kogyo Co., Ltd., degree of polymerization 430), 3 parts by weight of a stabilizer (tin laurate), and epokinized soybean oil as a carrier. And so.

10. Add a 2-weight solution of 10'-okinbisphenoquine arsine to the resin to give a concentration of 0.05% by weight of the raw material, and reduce the powder temperature to 50% at a high speed of 200 rpm using a Hennel mixer. Mixing was carried out until the temperature reached ℃ to obtain a homogeneous blend.

The above blend was pelletized at 150° C. using an extruder, and sheet molded in the same manner as in Example 1.

The appearance of the molded sheet was relatively good.

The obtained molded sheet was subjected to a drug dissolution and extraction test in water at 20°C in the same manner as in Example 1, and the results are shown in Table 2.

Example, 3, Comparative Example 1 In the formulation of Example 2, 2 of 10.10'-okineviscoenoxyarsine with epochinated soybean oil as a carrier.
A formulation in which 0.055% by weight of the weight-related solution is added to the resin based on the base material, and 0.1% by weight of 2,4,5.6-titrachloroisophthalonitrile alone is added to the resin as a drug. A molded sheet was obtained in the same manner as in Example 2 except that the material was used.

As a comparative example, polyvinyl chloride (degree of polymerization 1030) 100
parts by weight, stabilizer (tin laurate) 3 parts by weight, 2.4,5
．． 6-titrachloroisophthalonitrile was added in an amount of 0.1% by weight based on the resin, and a plasticizer (diisooctyl 7-talate) was added to give the same degree of softness as the formulation of Example 3.
A molded sheet was produced in the same manner as in Example 3 by processing 60 parts by weight of the following.

The molded sheets of Example 3 and Comparative Example 1 were subjected to drug dissolution and extraction tests in water at 20°C in the same manner as in Example 1, and the results are shown in Table 3.

The molded sheets of Mildew Resistance Test Example 3 and Comparative Example 1 were placed in a 50 x 50 x 2 m
Cut into pieces, add 25 tons of glucose, 13 tons of agar,
It was placed in a culture medium in a petri dish containing 500 ml of tap water and left indoors (about 20°C) for one week to culture the bacteria falling indoors.

Oral observation was then conducted to examine the state of mold growth on the sheet.

The results are shown in Table 4. In addition, as a blank, the progress of using only the above medium without using molded media is also shown.

Claims (1)

[Scope of Claims] 1. A compound selected from the following is added to a chlorinated polyethylene resin mainly composed of rubber-like chlorinated polyethylene with a chlorine content of 25 to 45% by weight based on the weight of the chlorinated polyethylene resin. A chlorinated polyethylene resin composition having excellent antimicrobial adhesion properties, characterized in that it contains 5 parts by weight. 22(4-thiazolyl)benzimidazole, bis(parachlorophenyl)diguanide, N-C fluorodichloromethylthio)phthalimidohexane dihydrochloride, N-lauryl-β-alanine, 10.10'-oquinbiphenoquine arsine, Dodecylguanidine hydrochloride, 2.4,5.6-titrachloroisophthalonitrile, dibutyltin oxide.