JPH064767B2 - Deodorant composition, deodorant composite material, deodorant resin composition, deodorant resin molded product and deodorant foam - Google Patents

Description

TECHNICAL FIELD The present invention relates to a deodorant composition, a deodorant composite material, a deodorant resin composition and a deodorant resin molded article, and more specifically to deodorant and heat stability. The present invention relates to an excellent deodorant composition, a deodorant composite material, a deodorant resin composition, a deodorant resin molded article and a deodorant foam which are derived therefrom.

(Prior art) In recent years, along with the improvement of living standards, not only the malodor generated industrially but also various malodors in daily life (odor of toilet and sewage, smell of garbage and waste, cooking of fish and garlic, etc.) The smell of time is a problem. The main components of these malodors are ammonia, amines, hydrogen sulfide and mercarcaptans.

As a method of removing various malodors in these daily lives, a method of masking the malodor by spraying or volatilizing a compound having an aroma, a method of adsorbing the malodor to activated carbon, etc. have been carried out. It cannot be said that satisfactory results have been obtained.

Conventionally, it has been known that aliphatic polycarboxylic acids such as citric acid and oxalic acid or salts thereof are effective as agents for removing basic malodors such as ammonia and amines (JP-A-61-137565, JP-A-61-137565). 61-154673), it has been reported that these compounds are blended with a thermoplastic resin to obtain a deodorant resin composition (Japanese Patent Laid-Open No. 61-2096).
62). However, since these aliphatic polycarboxylic acids are poorly dispersed in the resin and have poor thermal stability when exposed to high temperatures during the process of compounding with the resin, decomposition with foaming or coloring occurs. However, the deodorizing property is not sufficiently exhibited, and therefore, the deodorizing resin composition containing the same has the same drawbacks, and improvement has been desired.

(Problems to be Solved by the Invention) An object of the present invention is to solve the above problems.

The present inventors, as a result of earnest research to achieve this object,
(A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B)
By using a copper compound in combination, a deodorant composition excellent in deodorizing property and thermal stability is obtained, and by mixing this with a thermoplastic resin, deodorizing property of basic odor and sulfur-based odor,
It was found that a deodorant resin composition having excellent thermal stability can be obtained, and the present invention has been completed based on this finding.

(Means for Solving the Problems) Thus, according to the present invention, a deodorant composition comprising (A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B) copper compound, (A) α, β-unsaturated dicarboxylic anhydride polymer and (B) deodorant composite material containing a copper compound as a base, (A) α, β-unsaturated dicarboxylic anhydride polymer and (B) Provided are a deodorant resin composition obtained by mixing a copper compound with a thermoplastic resin, a deodorant resin molded article obtained by processing the resin composition, and a deodorant foam.

The α, β-unsaturated dicarboxylic acid anhydride polymer used in the present invention is a homopolymer of α, β-unsaturated dicarboxylic acid anhydride, α, β-unsaturated dicarboxylic acid anhydride and It refers to a copolymer with a copolymerizable monomer.

Further, the α, β-unsaturated dicarboxylic acid anhydride-based polymer used in the present invention may be formed into a polymer chain by a known polymer reaction such as obtained by adding maleic anhydride to polybutadiene. Those obtained by introducing an acid anhydride group are also included.

Furthermore, α, β contained in these polymers and copolymers
An α, β-unsaturated dicarboxylic acid having a structure in which a part or all of the acid anhydride group of the unsaturated dicarboxylic acid anhydride unit is converted into a carboxyl group by a known reaction such as hydrolysis or alcoholysis. Included in anhydride polymers. At this time, the obtained polymer or copolymer may contain an ester group, an amide group, an imide group or the like in addition to the carboxyl group.

Specific examples of the α, β-unsaturated dicarboxylic acid anhydride include:
Maleic anhydride, itaconic anhydride, citraconic anhydride, etc. are mentioned. Of these, maleic anhydride is preferred from the viewpoints of reactivity, economy and the like.

Specific examples of the monomer copolymerizable with the α, β-unsaturated dicarboxylic acid anhydride include aromatic monoolefins such as styrene, α-methylstyrene and vinyltoluene;
Ethylene, propylene, isobutene, butene-1, butene-2, pentene-1, pentene-2, 2-methylbutene-1,2-methylbutene-2, hexene-1,2,2,4-
Trimethylpentene-1,2,2,4-trimethylpentene-
2, aliphatic monoolefins such as decene-1, octadecene-1 and the like; cyclic monoolefins such as cyclopentene, cyclohexene, cyclooctene and the like; aliphatic diolefins such as butadiene, isoprene and piperylene; cyclopentadiene and the like Such as cyclic diolefins; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated carboxylic acid esters such as ethyl acrylate and methyl methacrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; Examples thereof include vinyl halides such as vinyl; vinyl carboxylates such as vinyl acetate; vinyl ethers such as methyl vinyl ether; unsaturated sulfonic acids such as vinyl sulfonic acid and p-styrene sulfonic acid.

The method for obtaining the α, β-unsaturated dicarboxylic acid anhydride polymer used in the present invention is not particularly limited, and known polymerization methods such as emulsion polymerization and solution polymerization can be applied.

The amount of α, β-unsaturated dicarboxylic acid anhydride units or units derived therefrom contained in the α, β-unsaturated dicarboxylic acid anhydride polymer used in the present invention is not particularly limited, but is usually It is 1 mol% or more, preferably 5 mol% or more, of all the monomer units constituting the α, β-unsaturated dicarboxylic acid anhydride polymer. If this amount is too small, the amount of the deodorant composition to be blended with the thermoplastic resin becomes too large, which may cause a problem in moldability of the deodorant resin composition.

The molecular weight of the α, β-unsaturated dicarboxylic acid anhydride polymer used in the present invention is not particularly limited, but usually,
It is 500 to 500,000, preferably 1,000 to 300,000.

The deodorant composition of the present invention may contain not only one kind of α, β-unsaturated dicarboxylic acid anhydride polymer but also two or more kinds thereof in combination.

The (B) copper compound used in the present invention is an inorganic acid salt,
It may be an organic acid salt, hydroxide, sulfide, complex or oxide. As specific examples thereof, for example, copper sulfate, copper nitrate,
Cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, copper carbonate, cupric hydroxide, cupric sulfide, copper cyanide, copper acetate, citric acid Cupric acid, copper gluconate, copper malate, copper glyoxylate, copper 2-ketoglutarate, copper pyruvate, copper oxaloacetate, copper acid phosphate, copper pyrophosphate, copper chlorophyll, sodium copper chlorophyllin, potassium copper chlorophyllin Examples include copper phthalocyanine, copper porphyrin, copper ethylenediaminetetraacetate, acetylacetonate, cuprous oxide, cupric oxide, copper oleate, and copper naphthenate. Further, the polymer chain may contain copper in the form of, for example, a carboxylic acid copper salt. It may contain copper in the form of these copper compounds. Among these copper compounds, an inorganic acid salt is preferable in terms of cost and availability, and a complex is preferable in terms of safety.

The deodorant composition of the present invention may contain not only one kind of copper compound but also two or more kinds thereof in combination.

The ratio of the component (A) and the component (B) in the deodorant composition of the present invention can be appropriately selected depending on the required performance of the target object, but is usually
The component (B) is 0.01 to 200 parts by weight, preferably 0.02 to 50 parts by weight, and more preferably 0.05, relative to 100 parts by weight of the component (A).
-20 parts by weight. If the amount of the component (B) is excessively small, the deodorizing performance for the malodorous sulfur may be inferior, and if it is excessively large, it may be unfavorable in terms of toxicity.

The deodorant composition of the present invention may be used in combination with an existing deodorant, bactericide, antifungal agent, etc., if necessary, within a range not impairing its effect, pigment, colorant, stabilizer, oxidation agent, etc. It may also contain various electrifying agents such as inhibitors.

The method for preparing the deodorant composition in the present invention is not particularly limited, and for example, a method of forming a solution with a solvent capable of uniformly dissolving each component, drying the solution by vacuum drying, atomization drying, etc. Examples thereof include a method of forming a solid material and a method of uniformly mixing each component by a method such as crushing.

The deodorant composition of the present invention is in various forms, such as a solution,
It can be used alone in the form of powder, tablets, etc.
It may be contained in various base materials to form a deodorant composite material.

(A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B)
The deodorant composite material of the present invention can be obtained by incorporating a copper compound into various base materials.

The substrate used in the deodorant composite material of the present invention is
(A) α, β-unsaturated dicarboxylic acid anhydride-based polymer and (B) copper compound is not particularly limited as long as it can be contained by a method such as impregnation, coating, and supporting, and its specific Examples include paper, cloth, foamed sheet, pulp, fiber, activated carbon, alumina, silica gel, zeolite, clay, bentonite, diatomaceous earth, acid clay and the like. The shape of the base material is not particularly limited, and examples thereof include powder, granules, fibers, and sheets.

In the deodorant composite material of the present invention, the amounts of (A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B) copper compound are
Although it depends on the purpose, it is usually 0.1 to 30% by weight, preferably 1 to 20% by weight of the base material in total of both components (A) and (B). If the amount used is too small, the function may be insufficient, and if it is excessively large, the economy may be poor. The ratio of the (A) α, β-unsaturated dicarboxylic acid anhydride polymer and the (B) copper compound in the deodorant composite material of the present invention can be appropriately selected depending on the purpose, but is usually (A ) Ingredient 10
The amount of the component (B) is 0.01 to 200 parts by weight, preferably 0.02 to 50 parts by weight, and more preferably 0.05 to 20 parts by weight, based on 0 parts by weight.

In the present invention, the order in which the base material contains (A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B) copper compound is:
There is no particular limitation, and the component (A) and the component (B) may be contained separately or simultaneously.

(A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B)
The deodorant resin composition of the present invention can be obtained by blending a copper compound with a thermoplastic resin, and this is useful as a raw material for a deodorant resin molded article.

The thermoplastic resin used in the present invention may be any as long as it can be formed into a film, a sheet, a fiber, a foam, other various molded articles, and the like, and specific examples thereof include polyethylene, polypropylene, polybutadiene and the like. Polyolefins; polyvinyl compounds such as polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-butadiene-styrene copolymers, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers; cellulose diacetate Such as cellulose ester; block copolymer of aromatic vinyl compound-conjugated diene monomer such as styrene-isoprene block copolymer, styrene-butadiene block copolymer; regenerated cellulose; polyesters; polyamide; Fluororesin And the like.

Further, as the foamable thermoplastic resin described below, for example, polyvinyl chloride, vinyl acetate-vinyl chloride copolymer, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene resin, polyvinyl alcohol, polyamide, cellulose and the like. However, the present invention is not limited to these.

In the thermoplastic resin composition, the blending amount of (A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B) copper compound is
Depending on the purpose, it is usually 0.1 to 30% by weight, preferably 1 to 20% by weight of the total amount of the components (A) and (B) of the thermoplastic resin.
% By weight. If the amount used is too small, the function may be insufficient, and if it is excessively large, the economy may be poor. Further, in the deodorant resin composition of the present invention (A)
The ratio of the α, β-unsaturated dicarboxylic acid anhydride polymer to the (B) copper compound can be appropriately selected according to the purpose, but is usually
With respect to 100 parts by weight of the component (A), the component (B) is 0.01 to 200 parts by weight, preferably 0.02 to 50 parts by weight, more preferably 0.
It is in the range of 05 to 20 parts by weight.

In the present invention, the blending method of the (A) α, β-unsaturated dicarboxylic acid anhydride polymer and the (B) copper compound to the thermoplastic resin is not particularly limited, and, for example, (A) component and (B)
After blending with the components in advance, it may be blended with the thermoplastic resin, or the thermoplastic resin (A) part of the component and / or (B)
After mixing a part of the components, the remaining part of the deodorant component may be added. Alternatively, the component (A) is blended with a part of the thermoplastic resin, the component (B) is blended with the rest of the thermoplastic resin, and both the blends are mixed to obtain the deodorant resin composition of the present invention. It is also possible. In addition, the deodorizing composition of the present invention supported on an inorganic substrate such as activated carbon has a good dispersibility in a thermoplastic resin and is suitable for blending.

In the present invention, the deodorant resin composition, as long as it does not hinder the function, existing deodorant, if necessary,
Used in combination with germicides, fungicides, and various additives such as stabilizers, lubricants, antioxidants, UV absorbers, processing aids, foaming agents, pigments, flame retardants, impact resistance aids, etc. Can be included.

The deodorant resin composition of the present invention thus obtained, extrusion molding, compression molding, calender molding, hollow molding, injection molding,
It can be processed into various molded products such as films and sheets by ordinary resin processing methods such as thermoforming, laminated molding, and rotational molding. Further, the deodorizing resin composition of the present invention may be used alone or in combination with other fiber raw materials to form fibers. The obtained film or sheet may be finely punched with a needle punch or the like so as to have air permeability, coated with cloth, nonwoven fabric, paper or the like, or laminated with another resin film. In the case of fibers, it can be woven into a cloth or a net.

Further, when a foamable thermoplastic resin is used as the thermoplastic resin, the resulting deodorant resin composition can be foam-molded to obtain a deodorant foam.

Molding method of the deodorant foam in the present invention is not particularly limited, for example, (A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B) the total amount of the copper compound foamable heat. Examples of the method include pre-mixing with a plastic resin, followed by foam molding by a conventional method.
It is also possible to employ a method in which the component (A) is mixed with the expandable thermoplastic resin in advance and foam-molded, and then the component (B) is contained in the foam by impregnation.

The production of a foam from the deodorant resin composition of the present invention has an advantage that a bad odor of ammonia, amine, etc. generated during foaming of the resin can be remarkably reduced and a foam having a high expansion ratio can be obtained.

(Effect of the Invention) Thus, according to the present invention, it is possible to obtain a deodorizing composition having excellent deodorizing properties and thermal stability as compared with the prior art.
This deodorant composition is used alone, or is contained in various base materials to be used as a deodorant composite material.

(A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B)
By incorporating a copper compound into various base materials, a deodorant composite material having excellent deodorizing properties can be obtained. Also, for thermoplastic resins
(A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B)
By adding a copper compound, a deodorizing resin composition having excellent deodorizing property and thermal stability can be obtained. This deodorant resin composition is useful as a raw material for films, sheets, fibers, foams and other various plastic molded products having functions such as deodorization and deodorization, and various molded products obtained are clothing, bedding, It is useful as a material for various products such as furniture, wallpaper, food containers, packaging materials, and filters.

(Example) Hereinafter, the present invention will be described more specifically with reference to Examples.
Parts and% in the examples and comparative examples are based on weight unless otherwise specified.

Example 1 100 parts of each component (A) (α, β-unsaturated dicarboxylic acid anhydride-based polymer) shown in Table 1 and the number of each component (B) component (copper compound) shown in Table 1 Were uniformly mixed and crushed in a mortar to prepare a powder sample.

(Thermal stability test) 1 g of each sample was left in a hot air circulation type oven at 150 ° C for 1 hour to reduce the heating loss (a), and each of these samples was further heated at 200 ° C for 1 hour. Heating loss rate
(B) was measured. The results are shown in Table 1.

(Methyl mercaptan deodorization test) 100 mg of each sample was placed in a glass ampoule with a crown and having an internal capacity of 150 ml, and the bottle was tightly sealed. After replacing the inside of the ampoule with air containing 500 ppm of methyl mercaptan, 24
After a lapse of time, the amount of methyl mercaptan in the ampoule was quantified by gas chromatography and the deodorization rate was calculated. The results are shown in Table 1.

(Ammonia deodorization test) 5000pp by the same method as the methyl mercaptan deodorization test
Deodorization rates were calculated for air containing m ammonia.
The results are shown in Table 1.

It can be seen from Table 1 that the deodorant composition of the present invention is excellent in heat stability and deodorizing performance of basic odor and sulfur odor.

Example 2 Styrene-maleic anhydride copolymer (copolymerization composition ratio 50/5
(0, manufactured by Arco Chemical Company, SMA 1000A) 2.46
0.1 part of copper oleate was added to the part and mixed well in a mortar.
This mixture was mixed with 100 parts of polyethylene resin (Showa Denko KK-made low-density polyethylene, Shorex 720FS) with a Henschel mixer to obtain a deodorant resin composition. The obtained deodorizing resin composition is used to measure the cylinder inner diameter of 65 m.
A sheet (1) having a thickness of 0.1 mm was obtained by extruding the sheet as a sheet from a T-type die using an extrusion base having a m and a screw compression ratio of 5.0, and biaxially stretching the sheet. The obtained film (1) was light yellow-green transparent and odorless.

Example 3 A film (2) having a thickness of 0.1 mm was obtained in the same manner as in Example 2 except that the amount of copper oleate was 0.2 part. The obtained film (2) was slightly yellowish green, but transparent and odorless.

Example 4 Example 2 except that cupric chloride is used instead of copper oleate.
A film (3) having a thickness of 0.1 mm was obtained in the same manner as in (1). The obtained film (3) was light brown, transparent and odorless.

Example 5 Styrene-instead of styrene-maleic anhydride copolymer
Maleic anhydride monoester copolymer (copolymerization composition ratio 50
A film (4) having a thickness of 0.1 mm was obtained in the same manner as in Example 2 except that the SMA17352A manufactured by Arco Chemical Company, Inc./50 was used. The obtained film (4) was slightly yellowish green, but transparent and odorless.

Example 6 A film (5) having a thickness of 0.1 mm was obtained in the same manner as in Example 2 except that polypropylene resin (Polypro S205 manufactured by Tonen Petrochemical Co., Ltd.) was used as the thermoplastic resin instead of polyethylene resin. . The obtained film (5) was slightly yellowish green, but transparent and odorless.

Comparative Example 1 A film (6) having a thickness of 0.1 mm was obtained in the same manner as in Example 3 except that citric acid was used instead of the styrene-maleic anhydride copolymer. The obtained film (6) was slightly yellow and transparent, but had bubbles and was odorless.

Comparative Example 2 A film (7) having a thickness of 0.1 mm was obtained in the same manner as in Example 6 except that copper oleate was not used. The obtained film (7) was colorless and transparent and had no odor.

Comparative Example 3 A film having a thickness of 0.1 mm (7-2) was prepared in the same manner as in Example 3 except that aluminum sulphate was used instead of copper oleate.
Got The film (7-2) was colorless and transparent and had no odor.

Example 7 (Deodorization test) 1 g of the films (1) to (7) obtained in Examples 2 to 6 and Comparative Examples 1 to 3 were placed in a glass ampoule with a crown and having an inner volume of 150 ml and tightly stoppered. Next, after replacing the inside of the ampoule with air containing 25,000 ppm of ammonia, the concentration of ammonia in the ampoule was measured over time by gas chromatography to obtain the deodorization rate.

The results are shown in Table 2.

From Table 2, it can be seen that the film obtained from the deodorant resin composition of the present invention is more useful as a basic odor deodorant than the film obtained from the conventional deodorant resin composition.

It is considered that this is because the α, β-unsaturated dicarboxylic acid anhydride-based polymer of the present invention is superior in thermal stability to the aliphatic polycarboxylic acid and excellent in compatibility with the thermoplastic resin.

Example 8 (Deodorization test) Films (1) obtained in Examples 2-6 and Comparative Examples 1-3
For (7) to (7), a deodorization test of 300 ppm of methyl mercaptan mixed in air was conducted by the same method as in Example 7.

The results are shown in Table 3.

It can be seen from Table 3 that the molded article of the deodorant resin composition of the present invention is also useful as a deodorant for sulfur odors.

Example 9 Vinyl chloride resin (Zeon 43A, manufactured by Nippon Zeon Co., Ltd.)
Stabilizer (Ba-Zn stabilizer for PVC, MARK AC-173 manufactured by Asahi Denka Co., Ltd.) 3 parts to 100 parts, α-olefin-
Maleic anhydride copolymer (Mitsubishi Chemical Co., Ltd., PA2)
08) 4 parts and copper naphthenate 0.1 part plasticizer (dioctyl phthalate) 60 parts were added and mixed for 10 minutes by a raker machine to obtain a pate sol. This sol was coated on a glass plate with a bar coater and then treated in an oven at 190 ° C. for 2 minutes to give a polyvinyl chloride film (8) having a thickness of 450 μm.
Got The obtained film (8) was slightly blue and transparent.

Example 10 A film (9) having a thickness of 450 μm was obtained in the same manner as in Example 9 except that the amount of copper naphthenate was 0.2 part. The film (9) was light blue and transparent.

Example 11 Instead of the α-olefin-maleic anhydride copolymer, a styrene-maleic anhydride copolymer (copolymerization composition ratio 50/5
0, ARC 3000 Chemical Company, SMA 3000A)
Except that copper oleate is used instead of copper naphthenate,
A film (10) having a thickness of 450 μm was obtained in the same manner as in Example 9. The film (10) was light green and transparent.

Comparative Example 4 A film (11) having a thickness of 450 μm was obtained in the same manner as in Example 9 except that copper naphthenate was not used. The film (11) was colorless and transparent.

Comparative Example 5 A 450 μm-thick film (12) was obtained in the same manner as in Example 9 except that trimellitic acid was used in place of the α-olefin-maleic anhydride copolymer and copper naphthenate was not used. . The obtained film (12) was brown and opaque.

Example 12 (Deodorization test) The same ammonia deodorization test as in Example 7 was performed except that the ammonia concentration was 5,000 ppm, and the methyl mercaptan concentration was 2
Films (8) to (12) were subjected to the same mercaptan deodorization test as in Example 8 except that the amount was 50 ppm. The results are shown in Table 4.

From Table 4, it can be seen that the deodorant resin molded article of the present invention is excellent in deodorizing properties of basic odor and sulfur odor.

Example 13 High density polyethylene (Showa Denko KK, Showlex F5012M) 94.8 parts, α-olefin-maleic anhydride copolymer (Mitsubishi Kasei Kogyo KK, PA168) 5 parts, copper naphthenate 0.2 parts Was mixed and extruded as an undrawn yarn at a cylinder tip temperature of 220 ° C. from an extruder equipped with a monofilament nozzle, passed through a 30 ° C. cooling tank, and then heated and drawn with boiling water of 100 ° C. to give 300
A denier fiber (1) was obtained.

Example 14 A 300 denier fiber (2) was obtained in the same manner as in Example 13 except that the amount of copper naphthenate was 0.4 part.

Example 15 A 300 denier fiber (3) was obtained in the same manner as in Example 13 except that copper oleate was used instead of copper naphthenate.

Example 16 In the same manner as in Example 13, except that a styrene-maleic anhydride copolymer (SMA 3000A, manufactured by Arco Chemical Company) was used instead of the α-olefin-maleic anhydride copolymer, 300 denier was prepared. Fiber (4) was obtained.

Example 17 A 300 denier fiber (5) was obtained in the same manner as in Example 13 except that polypropylene (Showa Denko Co., Ltd., Show Allomer MA 210) was used in place of the high-density polyethylene.

Comparative Example 6 A 300 denier fiber (6) was obtained in the same manner as in Example 13 except that the amount of high-density polyethylene was 95 parts and copper naphthenate was not used.

Comparative Example 7 30 was carried out in the same manner as in Example 13 except that the deodorizing component was not used.
A 0 denier fiber (7) was obtained.

Comparative Example 8 30 was carried out in the same manner as in Example 17 except that the deodorizing component was not used.
A 0 denier fiber (8) was obtained.

Example 18 (Deodorization test) The fibers (1) to (8) obtained in Examples 13 to 17 and Comparative Examples 6 to 8 were subjected to the same deodorization test as in Example 12. In this example, the ammonia concentration was 10,000 ppm. The results are shown in Table 5.

From the results in Table 5, it can be seen that the deodorant resin molded article of the present invention (fiber obtained from the deodorant resin composition) is excellent in deodorizing properties of basic odor and sulfur odor.

Example 19 Polyvinyl chloride resin (Zeon Resin 33 manufactured by Nippon Zeon Co., Ltd.) 100 parts, barium-zinc heat stabilizer 3 parts, azodicarbonamide foaming agent 6 parts, titanium oxide 15 parts, calcium carbonate 80 parts, phthalate Dioctyl acid (65 parts) and mineral spirits (5 parts) were added to make a slurry with a rafting machine, and a styrene-maleic anhydride copolymer (copolymerization composition ratio 50/50, Arco Chemical. Company's SMA 1000A) powder and 10% copper naphthenate of the above polymer were added, and a further 5
After mixing for minutes, a paste sol was obtained. After coating this sol on paper with a bar coater to a thickness of 200 μm,
In a hot air circulation oven, treat at 210 ° C for 60 seconds,
A foamed sheet (1b) was obtained.

Example 20 A foamed sheet (2b) was obtained in the same manner as in Example 19 except that the amount of copper naphthenate was 20% of the styrene-maleic anhydride copolymer.

Example 21 Instead of the styrene-maleic anhydride copolymer, a 1-octadecene-maleic anhydride copolymer (copolymer composition ratio 5
A foam sheet (3b) was prepared in the same manner as in Example 19 except that 0/50, PA-18) manufactured by Gulf Oil Chemicals Company, was used, and cupric chloride was used instead of copper naphthenate. Obtained.

Example 22 Instead of the polyvinyl chloride resin, a vinyl acetate-vinyl chloride copolymer resin (Zeon Resin 135 manufactured by Nippon Zeon Co., Ltd.)
A foamed sheet (4b) was obtained in the same manner as in Example 19 except that J) was used.

Comparative Example 9 A foamed sheet (5b) was obtained in the same manner as in Example 19 except that the styrene-maleic anhydride copolymer and copper naphthenate were not added.

Example 23 1-octadecene-maleic anhydride copolymer (copolymerization composition ratio 50/50, manufactured by Gulf Oil Chemicals Company, PA-18) and its 10% copper naphthenate,
It was dissolved in toluene to prepare a 5% toluene solution. This was impregnated with the foamed sheet (5b) obtained in Comparative Example 9 and dried, and then the foamed sheet (6
b) was obtained.

Example 24 0.5 g of each of the foamed sheets (1b) to (6b) obtained in Examples 19 to 23 and Comparative Example 9 was placed in a glass ampoule with a crown having an inner volume of 150 ml and sealed, and 3800 ppm of ammonia or 100 ppm of 100 ppm was added. After replacing the inside of the ampoule with air containing methyl mercaptan, after a predetermined time, the concentration of ammonia or methyl mercaptan in the ampoule was measured by gas chromatography to calculate the deodorization rate. The results are shown in Table 6.

From these results, it can be seen that the deodorant foam obtained by foaming the deodorant composite material and the deodorant resin composition of the present invention is excellent in the deodorizing performance of ammonia and methyl mercaptan.

Example 25 1 g of the paste sol prepared in Example 19 and Comparative Example 9 was placed in an ampoule having an inner volume of 150 ml and sealed, and the ampoule was immersed in an oil bath at 220 ° C. for 10 minutes to foam the paste sol. When the ampoule was opened and the odor of the gas phase was examined, a strong ammonia odor was felt from Comparative Example 9, but no odor was obtained from Example 19. When the odor of the foam in the ampoule was examined, the foam of Example 19 had no ammonia odor, whereas the foam of Comparative Example 9 had an ammonia odor.

From this (A) α, β-unsaturated dicarboxylic acid anhydride polymer and (B) copper compound after mixing with a foamable thermoplastic resin, to foam the foamable thermoplastic resin, deodorant thermoplastic resin It can be seen that in the method for producing a foam, the emission of ammonia odor generated by the decomposition of the foaming agent to the surroundings is significantly suppressed.

Example 26 In Examples 19 to 21 and Comparative Example 9, the foamed sheets (1a), (2a), (3a) and (5a) were respectively subjected to the same operations except that the heat treatment time was 30 seconds. Obtained. Similarly, the heat treatment time was set to 90 seconds to obtain foamed sheets (1c), (2c), (3c) and (5c). These foam sheets and foam sheets (1b),
The results of measuring the expansion ratios of (2b), (3b) and (5b) are shown in Table 7.

From this, (A) α, β-unsaturated dicarboxylic acid anhydride-based polymer used in the deodorant thermoplastic resin foam of the present invention and (B)
It can be seen that the copper compound does not affect the shape of the foam.

Claims (5)

[Claims] 1. A deodorizing composition containing (A) an α, β-unsaturated dicarboxylic acid anhydride polymer and (B) a copper compound. 2. A deodorant composite material comprising (A) an α, β-unsaturated dicarboxylic acid anhydride polymer and (B) a copper compound in a base material. 3. A deodorant resin composition obtained by blending (A) an α, β-unsaturated dicarboxylic acid anhydride polymer and (B) a copper compound with a thermoplastic resin. 4. A deodorant resin molded product obtained by processing the deodorant resin composition according to claim 3. 5. A deodorant foam obtained by foaming the deodorant resin composition according to claim 3, wherein a foamable thermoplastic resin is used as the thermoplastic resin.