JPH0616866A - Resin composition excellent in antiseptic and antimildew properties - Google Patents

Abstract

PURPOSE:To obtain a resin composition which can inhibit microorganisms and mildews from growing and does not change in antiseptic and antimildew properties even when stored for a long time. CONSTITUTION:The composition is prepared by copolymerizing a monomer mixture comprising an acrylic ester (e.g. ethyl acrylate or butyl acrylate), a methacrylic ester (e.g. methyl methacrylate) and an alpha,beta-monoethylenically unsaturated carboxylic acid (e.g. acrylic acid or methacrylic acid) and optionally neutralizing the reaction mixture with ammonia. This composition is excellent in antiseptic and antimildew properties and is not so malodorous when it contains 0.0001-5wt.% (especially 3-5wt.%), based on the composition, alpha,beta- monoethylenically unsaturated carboxylic acid and/or its salt or ester.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition having excellent antiseptic and antifungal properties. INDUSTRIAL APPLICABILITY The present invention is used as a fiber treatment agent, a floor polish, a coating film protective agent, a paint, an adhesive, and the like.

[0002]

2. Description of the Related Art Generally, a resin composition containing a polymer latex is applied as an aqueous solution or a water diluting solution in a fiber treatment agent, a floor polish, a coating film protective agent, a paint, an adhesive agent and the like. , In storage, storage or use, microorganisms or mildew may be generated, putrefying and giving off a bad odor, or product viscosity may be increased, so that sufficient performance may not be exhibited. Here, one example thereof will be described with reference to a sizing agent for synthetic fibers.
Weaving machines for textile weaving include gripper rooms,
There are a rapier room, a normal weaving machine that sends a weft by striking with a weft sticking force, a water jet room that weaves a weft by flying water, and an air jet room that sends air by air pressure. Is being done. In this weaving process, an oil agent for imparting smoothness and antistatic properties to the fiber yarns to facilitate the process and improve the texture, and sizing for the fiber yarns is applied to converge to the fiber warp yarns. A so-called sizing agent is used for imparting water resistance and tying property and water resistance in a water jet loom to facilitate weaving and braiding.

The above-mentioned oil agent is used as an aqueous solution or emulsion comprising mineral oil, fats and oils, wax and the like, and many of the oil agent components are compounds serving as nutrient sources for microorganisms, and microorganisms around 20 to 35 ° C. Since it is placed under a temperature condition suitable for breeding, microorganisms easily propagate in the storage tank and the oil agent supply pipe. Thus, when a large amount of microorganisms propagate, destruction of the oil emulsion, deterioration of the oil components, accumulation of microorganisms and their excretion occur, so-called slime is generated in the tank or the circulation system, and the pipe is clogged and the surface of the refueling roller is soiled. It causes various troubles such as the generation of spots of adhesion of oil. As a measure for preventing such oil agents from being damaged by microorganisms, addition of formalin and other antiseptic / bactericidal agents has been attempted [for example, triazine-based compounds (JP-A-55-40822), fungicide-containing dioxane-based compounds ( JP-A-55-67073), an isothiazole compound and an ethylene glycol ester (JP-B-57).
No. 29580), a acetophenone compound having a halogen atom, a bromonitroalcohol compound (JP-A-2-175968), and the like].

On the other hand, as the above-mentioned sizing agents, conventionally, starch, polyvinyl alcohol, carboxymethyl cellulose, styrene-maleic acid copolymers, ethylene-vinyl acetate copolymers, polyacrylic acid ester resins and the like have high water solubility. Molecular substances are used. Among these,
Acrylic sizing agents are generally widely used due to their excellent performance balance such as refining properties and flexibility of coatings. Such a sizing agent was dissolved in water at an arbitrary ratio during sizing, was glued to the yarn, was dried at 100 to 120 ° C., was formed into a water-insoluble film on the yarn, was woven, and then adhered to the raw fabric. The glue is refined by removing the glue with an alkaline aqueous solution.

[0005]

However, if the drying in the weaving sizing process is insufficient, colored deposits such as warp threads, shavings, and healds adhere to the sizing process, which may affect the desizing and refining properties. May occur. This colored deposit is
Since the sizing agent component is easily assimilated, it occurs due to the generation of bacterial microorganisms or mold. Further, even when the sizing agent is stored for a long period of time, the sizing agent may rot due to the generation of microorganisms or mold and change in viscosity, which may cause a problem in the weaving operation. Therefore, there is a demand for a sizing agent for fibers that can prevent damages caused by microorganisms or mold and that does not change even after long-term storage. Further, the same applies to other polymer latexes used not only as the above-mentioned fiber sizing agent but also as a floor polish, an automobile coating film protective agent, a paint, an adhesive, etc. The fact is that resin compositions have not yet solved this problem.

[0006] The present invention solves the above problems and does not generate microorganisms and mold without adding an antiseptic or a bactericide, and maintains various performances even when stored for a long period of time. It is an object of the present invention to provide a copolymer resin composition having excellent antiseptic and antifungal properties.

[0007]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have earnestly studied the antiseptic and antifungal action of monomers in a resin composition containing a polymer latex, and as a result, the composition The present invention has been completed based on the finding that it is possible to prevent the generation of microorganisms and mold by containing a predetermined amount or more of a predetermined monomer therein. That is, the resin composition having excellent antiseptic and antifungal properties of the first aspect of the present invention (hereinafter referred to as "resin composition") comprises acrylic acid ester, methacrylic acid ester and α, β-monoethylenically unsaturated carboxylic acid. The amount of at least one monomer is 0.000 when the total resin composition is 100% by weight.
It is characterized by containing 1 to 5% by weight. The "resin composition" component is obtained by homopolymerizing or copolymerizing at least one monomer of acrylic acid ester, methacrylic acid ester and α, β-monoethylenically unsaturated carboxylic acid. Or other type of resin component may be used. Further, the “monomer” may be derived from the unreacted monomer constituting the resin composition or may be added separately. The content of this monomer is 0.0001
If it is less than 5% by weight, the antiseptic and antifungal effects are insufficient, while 5
This is because if it exceeds 5% by weight, the odor caused by the monomer becomes strong, which is a problem in work and the antiseptic / antifungal effect is saturated.

The resin composition of the second invention is obtained by copolymerizing a monomer mixture containing at least one of acrylic acid ester, methacrylic acid ester and α, β-monoethylenically unsaturated carboxylic acid. When at least one monomer selected from α, β-monoethylenically unsaturated carboxylic acids and salts thereof in the copolymer resin composition is 100% by weight of the entire copolymer resin composition. To 0.
It is characterized by containing 0001 to 5% by weight. Here, "at least one or more kinds of monomers selected from α, β-monoethylenically unsaturated carboxylic acids and salts thereof" may be derived from unreacted monomers or added separately. But it's okay. If the content of this monomer is less than 0.0001% by weight, the antiseptic and antifungal effects are not sufficient. On the other hand, if it exceeds 5% by weight, the odor caused by the monomer becomes too strong, which causes a problem in work, and This is because the antifungal effect is saturated.

Examples of the above-mentioned "acrylic acid ester" include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. Examples of the above-mentioned “methacrylic acid ester” include methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. In addition, the above "α, β-monoethylenically unsaturated carboxylic acid"
Examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and mixtures thereof. Examples of the above "salts" include ammonium salts such as acrylic acid and methacrylic acid, amine salts, alkali metal salts and the like.

[0010]

EXAMPLES The present invention will be specifically described below with reference to examples. (1) Preparation of Resin Composition First, a mixture of monomers having the compositions shown in Examples 1 to 8 and Comparative Examples 1 to 3 in Table 1 (hereinafter referred to as “mixture”).
Prepared.

[0011]

[Table 1]

The unit of numerical values showing the composition in the table is parts by weight. Then, 25 parts by weight of each of the above mixtures was added to an aqueous solution of sodium sulfate of polyoxyethylene (additional mol number: 9 mol) lauryl ether (concentration: 1% by weight).
Copolymerization was carried out in the presence of 0 parts by weight and 0.2 parts by weight of ammonium persulfate at a temperature of 75 ° C. for 5 hours. However, in the comparative example, the copolymer was copolymerized at a temperature of 75 ° C. for 25 hours, and then nitrogen was blown therein for 1 hour. Further, as Comparative Example 4, 1,2-benzisothiazoline-3 was added to the copolymer aqueous solution of Comparative Example 3 as a preservative.
The thing which added 0.001 weight% of -one was also prepared.

Further, in Examples 1 to 6 and Comparative Examples 1 and 2, after ammonia water was added for complete neutralization, water was added to obtain a 25% by weight aqueous solution of a copolymer ammonium salt. In addition, in Example 7 and Comparative Example 3, after copolymerization, water was added to prepare a 25 wt% aqueous solution of the copolymer.
In addition, except for Example 8, residual ester was removed by blowing nitrogen through the capillary for 1 hour and reducing the pressure for 1 hour (100 mmHg). The amount (% by weight) of acrylic acid or methacrylic acid (hereinafter referred to as "unsaturated carboxylic acid") or a salt thereof, and the unsaturated carboxylic acid ester in the copolymer aqueous solution thus obtained is shown in Table 1. Also described in. The content of the unsaturated carboxylic acid and the unsaturated carboxylic acid ester was measured by gas chromatography (GLC) using t-butanol as a standard substance. When neutralized with ammonia, both the unsaturated carboxylic acid and its salt were quantified.

(2) Performance Test and Performance Evaluation In order to clarify the performance of the resin composition of the present invention, a test for rot resistance was conducted on each of the above copolymer aqueous solutions.
That is, each of the above copolymer aqueous solutions was diluted 20 times with water, to which a septic solution of an oil agent collected from a fiber factory was added at a ratio of 0.1%, and the mixture was shake-cultured at 37 ° C. for 7 days. , "Presence or absence of putrid odor" was examined. In addition to this, the viable cell count was also measured by the plate counting method. The results of the above tests are shown in Table 2.

[0015]

[Table 2]

According to the above performance tests, the aqueous copolymer solutions of Comparative Examples 1 to 3 produce a strong putrid odor, have a large number of viable bacteria, and show poor performance as a resin composition. Further, in Comparative Example 4 in which a preservative is used in combination, although almost satisfactory spoilage resistance is exhibited, the use of the preservative causes a risk of deteriorating the health of the worker.

On the other hand, the copolymer aqueous solutions (Examples 1 to 8) of this embodiment show sufficient rot resistance. In particular, in Examples 3 to 6 containing 3 to 5% by weight of unsaturated carboxylic acid and its salt, the viable cell count after 7 days could be made zero. Further, also in Examples 1 and 2 containing the lower limit (0.0001% by weight) of the unsaturated carboxylic acid salt in the present invention, it is possible to secure almost the same degree of decay resistance as in Comparative Example 4 in which the preservative is used in combination. It was However, in this case, unlike Comparative Example 4, there is no fear of impairing the health of the worker. Further, in the case of containing methacrylic acid salt (Example 1)
In comparison with the case of containing acrylate (Example 2)
The result was excellent in rot resistance. Furthermore, in Example 7 containing the above-mentioned lower limit (0.0001% by weight) of unsaturated carboxylic acid, the viable cell count can be made zero, and in the case of this methacrylic acid, compared with methacrylic acid salt. Showed very good rot resistance. Similarly, for acrylic acid ester and methacrylic acid ester (Example 8),
It showed the same effect as α, β-monoethylenically unsaturated carboxylic acid.

Regarding the odor, in Examples 5 and 6 (unsaturated carboxylic acid amount; 5% by weight), Examples 1 and 2 (unsaturated carboxylic acid amount; 0.000) with almost no odor.
1% by weight), it was large, but not particularly unbearable. The present invention is not limited to the specific examples described above, and various modifications may be made within the scope of the present invention depending on the purpose and application.

[0019]

EFFECT OF THE INVENTION The copolymer resin composition of the present invention has excellent antiseptic and antifungal properties without adding a known antiseptic or bactericidal agent, does not generate microorganisms and mold, and has a long term It does not deteriorate even when stored, so that the required performance as a fiber treatment agent, a floor polish, a film protective agent, a paint, an adhesive, etc. can be maintained for a long time.

Claims (2)

[Claims] 1. An acrylic acid ester, a methacrylic acid ester and at least one monomer of an α, β-monoethylenically unsaturated carboxylic acid, and 100 parts of the entire resin composition.
A resin composition having excellent antiseptic and antifungal properties, characterized in that it is contained in an amount of 0.0001 to 5% by weight in terms of weight%. 2. A copolymer resin composition obtained by copolymerizing a monomer mixture containing at least one of acrylic acid ester, methacrylic acid ester and α, β-monoethylenically unsaturated carboxylic acid. , Α, β-monoethylenically unsaturated carboxylic acid and at least one monomer selected from salts thereof, and
A resin composition having excellent antiseptic and antifungal properties, which is characterized by containing 0.0001 to 5% by weight when the amount is 0% by weight.