JPH0647003B2 - 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, a deodorant resin molded article and a deodorant foam, and more specifically, a deodorant composition. The present invention relates to a deodorant composition having excellent properties, a deodorant composite material, a deodorant resin composition, a deodorant resin molded article and a deodorant foam which are derived therefrom.

(Prior Art) 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 (Japanese Patent Publication No. 61-1).
37565, JP-B-61-154673), and it has been reported that these compounds are blended with a thermoplastic resin to obtain a deodorant resin composition (JP-A-61-209662). However, these aliphatic polycarboxylic acids do not have sufficient deodorizing properties for malodorous components other than the basic malodorous component, and therefore a deodorant resin composition containing the same has the same drawbacks, and improvement is desired. It was

(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,
By using (A) a carboxylic acid anhydride and (B) a copper compound in combination, a deodorizing composition having excellent deodorizing property is obtained, and by adding this to a thermoplastic resin, a basic odor and a sulfur-based odor can be obtained. It was found that a deodorant resin composition excellent in deodorizing property can be obtained, and based on this finding, the present invention has been completed.

(Means for Solving the Problems) Thus, according to the present invention, (A) a carboxylic acid anhydride and (B)
Deodorizing composition comprising a copper compound, (A) carboxylic acid anhydride and (B) a deodorizing composite material containing a copper compound contained in a substrate, (A) a carboxylic acid anhydride and (B) a copper compound Provided are a deodorant resin composition formed by blending with a plastic resin, a deodorant resin molded article and a deodorant foam formed by processing the deodorant resin composition.

The carboxylic acid anhydride used in the present invention is not particularly limited, and specific examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and other aromatic polycarboxylic acid anhydrides. An anhydride of an aromatic monocarboxylic acid such as benzoic anhydride; an anhydride of a chain monocarboxylic acid such as butyric anhydride, propionic anhydride, or lauric anhydride; an succinic anhydride, a methylsuccinic anhydride, a glutaric anhydride; Anhydrides of chain polycarboxylic acids such as acrylic acid-based polymers having acid anhydride cross-linking such as acid anhydride, maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, and polyacrylic acid anhydride; for example, cyclohexanecarboxylic acid anhydride and cyclopentane anhydride. An alicyclic monocarboxylic acid anhydride such as a carboxylic acid; for example, 1,2-cyclohexanedicarboxylic acid Things, 3-methyl - △ ⁴ - tetrahydrophthalic anhydride of a cycloaliphatic polycarboxylic acid such as phthalic anhydride can be exemplified.

Furthermore, the Diels-Alder reaction type addition reaction product of an α, β-unsaturated dicarboxylic acid anhydride and an olefin and its derivative are also included in the carboxylic acid anhydride used in the present invention.

The acrylic acid-based polymer having an acid anhydride cross-link used in the present invention may be one having an acid anhydride group structure formed in the same molecule or different molecules of the acrylic acid-based polymer, for example, two It can be obtained by carrying out a heat dehydration reaction between the carboxyl groups, but is not limited by the synthetic method.

In the present invention, the acrylic acid-based polymer means an α, β-unsaturated monocarboxylic acid homopolymer or an α, β-unsaturated monocarboxylic acid and an α, β-unsaturated carboxyl group copolymerizable therewith. It means a copolymer with a monomer not containing.
Specific examples of the α, β-unsaturated monocarboxylic acid include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid and the like. The α, β-unsaturated monocarboxylic acid-copolymerizable monomer that does not contain an α, β-unsaturated carboxyl group is not particularly limited, but specific examples include, for example, methyl methacrylate, ethyl acrylate, and butyl methacrylate. , (Meth) acrylic acid esters such as 2-ethylhexyl acrylate; aromatic monoolefins such as styrene and α-methylstyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; for example vinyl acetate and caproic acid Examples thereof include vinyl carboxylates such as vinyl; aliphatic diolefins such as butadiene and isoprene; and unsaturated acid amides such as acrylamide and N-methylol acrylamide.

The method for obtaining the acrylic acid-based polymer is not particularly limited, and known polymerization methods such as emulsion polymerization and solution polymerization can be applied.

The amount of the acid anhydride group contained in the acrylic acid-based polymer having the acid anhydride cross-linking used in the present invention is not particularly limited, but usually 1 mol% of all monomer units constituting the acrylic acid-based polymer. Or more, preferably 5 mol% or more. If this amount is excessively small, the amount of the deodorant component mixed with the thermoplastic resin becomes too large, which causes a problem in the shape of the thermoplastic resin molded product.

The molecular weight of the acrylic acid-based polymer is not particularly limited, but is usually 500 to 500,000, preferably 1.00.
It is 0 to 300,000.

Examples of the Diels-Alder reaction type addition reaction product of α, β-unsaturated dicarboxylic acid anhydride and olefin used in the present invention include α, β-unsaturated dicarboxylic acid anhydride and diolefin. Products of Diels-Alder reaction, products of ene reaction of α, β-unsaturated dicarboxylic acid anhydrides with olefins (for this ene reaction, edited by Minoru Imoto, "Lecture Organic Reaction Mechanism", Volume 5, "Addition Reaction") (Written by Minoru Imoto and Niichiro Tokura) and published on pages 308 to 316 of Tokyo Kagaku Dojinsha Co., Ltd.), but the invention is not limited thereto.

Specific examples of the α, β-unsaturated dicarboxylic acid anhydride used in the Diels-Alder reaction type addition reaction include maleic anhydride, itaconic anhydride, and citraconic anhydride. Of these, maleic anhydride is preferred from the viewpoints of reactivity and economy.

The diolefin used in the Diels-Alder reaction type addition reaction for the Diels-Alder reaction with the α, β-unsaturated dicarboxylic acid anhydride is not particularly limited, and specific examples thereof include butadiene. , Chain-conjugated diolefins such as isoprene and piperylene, aliphatic trienes such as 1,3,5-hexatriene, cyclic conjugated polyolefins such as cyclopentadiene, 1,3-cyclohexadiene and cyclooctatetraene. Unsaturated olefins, for example, aromatic compounds such as styrene, indene and naphthalene can be mentioned. Other diolefins include MC
Creschel et al., "Organic Reactions" No. 4
The compounds described in Volumes 1 to 60 (John Willie and Sons) can be mentioned.

The olefin which is used in the Diels-Alder reaction type addition reaction and undergoes an ene reaction with the α, β-unsaturated dicarboxylic acid anhydride is not particularly limited,
For example, propylene, isobutene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 1-hexene, 2,
Various types of 2,4-trimethyl-1-pentene, 2,2,4-trimethyl-2-pentene, 1-decene, 1-octadecene, various monoolefins obtained by polymerizing lower monoolefins such as ethylene and propylene with a Ziegler catalyst or the like. α
-Chain monoolefins such as olefins; cyclic monoolefins such as cyclopentene, cyclohexene and cyclooctene; chain or cyclic non-conjugated diolefins such as 1,4-pentadiene and 1,4-cyclohexadiene Examples thereof include higher unsaturated fatty acids such as oleic acid.

The derivative of the Diels-Alder reaction type addition reaction product of the α, β-unsaturated dicarboxylic acid anhydride and the olefin used in the present invention does not define the synthesis method thereof, and the α, β-unsaturated derivative is not defined. Any compound having a structure derived from a Diels-Alder reaction type addition reaction product of a saturated dicarboxylic acid anhydride and an olefin by a known reaction may be used. Specific examples thereof include a hydrogenated product of a Diels-Alder reaction type addition reaction product of an α, β-unsaturated dicarboxylic acid anhydride and an olefin.

In the present invention, the carboxylic acid anhydride is only one kind,
Alternatively, two or more kinds can be used in combination.

The copper compound used in the present invention may be any of an inorganic acid salt, an organic acid salt, a complex and an oxide, and specific examples thereof include copper sulfate, copper nitrate, cuprous chloride, cupric chloride and bromide. Cuprous, cupric bromide, cuprous bromide, copper carbonate, cupric hydroxide, cupric sulfide, copper cyanide, copper acetate, cupric citrate, copper gluconate, copper malate , Copper glyoxylate, 2
-Copper ketoglutarate, copper pyruvate, copper oxaloacetate,
Acid copper phosphate, copper pyrophosphate, copper chlorophyll, copper chlorophyllin sodium, copper chlorophyllin potassium, phthalocyanine copper, copper porphyrin, ethylenediaminetetraacetic acid copper, copper acetylacetonate, cuprous oxide, cupric oxide, copper oleate, Copper naphthenate and the like are shown. or,
The polymer chain may contain copper in the form of, for example, a carboxylic acid copper salt. 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.

In the present invention, the copper compound may be used alone or in combination of two or more.

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 with respect to 100 parts by weight of the component (A).
The amount is preferably in the range of 0.02 to 50 parts by weight, more preferably 0.05 to 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. Various additives such as an inhibitor can be contained.

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 for obtaining a solid material and a method for uniformly mixing the components 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.

The deodorizing composite material of the present invention can be obtained by incorporating (A) a carboxylic acid anhydride and (B) a copper compound into various base materials.

The substrate used in the deodorant composite material of the present invention is
(A) carboxylic acid anhydride and (B) a copper compound is impregnated, coated, as long as it can be contained by a method such as carrying, is not particularly limited, as a specific example, paper, cloth, foamed sheet, Pulp, fiber, activated carbon, alumina, silica gel,
Zeolite, clay, bentonite, diatomaceous earth, acid clay and the like can be mentioned. The shape of the base material is not particularly limited, and may be powder, powder, fiber, sheet, or the like.

In the deodorant composite material of the present invention, the amounts of (A) carboxylic acid anhydride and (B) copper compound differ depending on the purpose, but usually (A) and (B) are the total amount of both components of the base material. It is 0.1 to 30% by weight, preferably 1 to 20% 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, the ratio of the (A) carboxylic acid anhydride and the (B) copper compound in the deodorant composite material of the present invention can be appropriately selected according to the purpose, but usually, relative to 100 parts by weight of the (A) component, ( 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 order of containing the (A) carboxylic acid anhydride and (B) copper compound in the substrate is not particularly limited, the (A) component,
The component (B) may be contained separately or simultaneously.

(A) A carboxylic acid anhydride and (B) a copper compound can be mixed with a thermoplastic resin to obtain a deodorant resin composition of the present invention, which is useful as a raw material for a deodorant resin molded article. is there.

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 Block copolymers of aromatic vinyl compound-conjugated diene monomers such as styrene-isoprene block copolymers, styrene-butadiene block copolymers, etc .; regenerated cellulose; polyesters; polyamides; 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 deodorant resin composition of the present invention, the compounding amounts of (A) carboxylic acid anhydride and (B) copper compound are different depending on the purpose, but usually (A), (B) the total of both components 0. of the plastic resin.
It is 1 to 30% by weight, preferably 1 to 20% by weight. If the amount used is too small, the function may be insufficient,
On the other hand, if the amount is too large, the economy may be poor. Further, the ratio of the (A) carboxylic acid anhydride and (B) copper compound in the deodorant resin composition of the present invention can be appropriately selected according to the purpose, but usually, relative to 100 parts by weight of the (A) component, (B) component is 0.
It is in the range of 01 to 200 parts by weight, preferably 0.02 to 50 parts by weight, and more preferably 0.05 to 20 parts by weight.

In the present invention, the blending method of the (A) carboxylic acid anhydride and (B) copper compound to the thermoplastic resin is not particularly limited, for example, (A) component and (B) component were premixed After that, it may be blended with the thermoplastic resin, or the thermoplastic resin may be blended with a part of the component (A) and / or a part of the component (B) and then with the rest of the deodorant component added. Good. Alternatively,
It is also possible to blend the component (A) into a part of the thermoplastic resin, blend the component (B) into the rest of the thermoplastic resin, and mix both formulations to obtain the deodorant resin composition of the present invention. It is 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, etc., and contains various additives such as stabilizers, lubricants, antioxidants, UV absorbers, processing aids, foaming agents, pigments, flame retardants, impact resistance aids, etc. Can be made.

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) carboxylic acid anhydride and
(B) After mixing the entire amount of the copper compound with the expandable thermoplastic resin in advance, it is possible to cite a method of foam-molding by a conventional method, and, for example, the above-mentioned (A) component with the expandable thermoplastic resin in advance. It is also possible to adopt a method in which after the components are mixed and foam-molded, the component (B) is impregnated into the foam.

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 deodorant composition which is superior in deodorizing property to the prior art. This deodorant composition is used alone, or is contained in various base materials to be used as a deodorant composite material.

In addition, it is possible to obtain a deodorizing composite material having excellent deodorizing properties by incorporating (A) carboxylic acid anhydride and (B) copper compound into various base materials. Furthermore, by blending the thermoplastic resin with (A) carboxylic acid anhydride and (B) copper compound, a deodorizing resin composition having excellent deodorizing properties 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.
The parts and% in the examples and reference examples are based on weight unless otherwise specified.

In this example, the deodorization test was performed as follows unless otherwise specified.

(Ammonia deodorization test and methyl mercaptan deodorization test) A predetermined amount of each sample is put in a glass ampoule with a crown having an inner volume of 150 ml and sealed. Next, after replacing the inside of the ampoule with air containing a predetermined concentration of ammonia or methyl mercaptan, after a predetermined time, the amount of ammonia or methyl mercaptan in the ampoule is measured by gas chromatography.

(Hydrogen sulfide deodorization test) A predetermined amount of each sample was placed in an odor bag with a silicone rubber stopper having an internal capacity of 3, and air 1 containing a predetermined concentration of hydrogen sulfide was injected. The amount of hydrogen is measured with a Kitagawa gas detector tube.

Reference Example 1 100 g of acrylic acid in a 500 ml separable flask,
300 g of water was charged, 0.1 g of ammonium persulfate was added under a nitrogen atmosphere, and polymerization was carried out at 30 ° C. for 10 hours to obtain polyacrylic acid having a molecular weight of about 6,000. This polyacrylic acid was placed in a hot air circulation oven under a nitrogen atmosphere at 120 ° C. for 4 hours.
After heating for an hour, polyacrylic anhydride (1) was obtained. In addition,
In the infrared absorption spectrum of this product, it was found from the intensity of absorption at 1780 cm ^-1 characteristic of the acid anhydride group that about 40% of the carboxyl group was changed to the acid anhydride group.

Example 1 (Deodorization test) Various components (A) (carboxylic acid anhydride) 10 shown in Table 1
Various parts (B) component (copper compound) with 0 part and the number shown in Table 1
Are uniformly mixed in a mortar and pulverized to prepare a deodorizing composition, and 1 g of each deodorizing composition is subjected to an ammonia deodorizing test (concentration 50,000 ppm) and a hydrogen sulfide deodorizing test (concentration 1
00ppm) and methyl mercaptan deodorization test (concentration 5,
000 ppm). The results are shown in Table 1.

From these results, it was found that the deodorizing composition of the present invention containing (A) carboxylic acid anhydride and (B) copper compound is excellent not only in basic malodor but also in deodorizing performance of sulfur malodor. It

Reference Example 2 Various α-olefins shown in Table 2 and an equimolar amount of maleic anhydride were charged in an autoclave, and addition reaction was carried out at 200 ° C. for 15 hours in the presence of a polymerization inhibitor. The unreacted α-olefin is removed under reduced pressure, and the ene reaction products I to V shown in the table are removed from the deodorant composition.
Obtained as the component (A).

Reference Example 3 A pressure-resistant autoclave was charged with 68.6 parts of maleic anhydride and 70 parts of toluene, and after melting at 55 ° C., 0.162 parts of hydroquinone was added, followed by trans-1,
130.9 parts of crude trans-1,3-pentadiene consisting of 40% of 3-pentadiene, 20% of cis-1,3-pentadiene and 40% of pentanes in total (trans-1,3-pentadiene per mol of maleic anhydride) (Corresponding to 1.1 mol) was continuously added at 50 ° C. for 6 hours, then the temperature was raised to 60 ° C. and the reaction was performed for 3 hours. After the reaction,
Volatile components are removed by atmospheric distillation at 90 ° C.
As a Diels-Alder reaction product, 3-methyltetrahydrophthalic anhydride (melting point: 61 ° C.) was obtained with a yield of 99%.

Example 2 (Deodorization test) A deodorant composition was prepared in the same manner as in Example 1 from 100 parts of each component (A) shown in Table 3 and the amount of each component (B) shown in Table 3. Then, the same deodorization test as in Example 1 was performed. The results are shown in Table 3.

From this result, it can be seen that the deodorant composition of the present invention is excellent not only in basic malodor but also in deodorizing performance for sulfur malodor.

Example 3 (Deodorization test) Predetermined amounts of the components (A) and (B) shown in Table 4 were weighed and added with a solvent to dissolve them so that the total amount became 20 g to obtain a deodorant composition solution. It was 1 g of this solution was placed in a 100 ml Erlenmeyer flask and 1 ml of nitrogen gas containing 20 mg of methyl mercaptan or 70 mg of ammonia in 1 was added.
After adding, stopper tightly. After standing for 1 hour, the amount of methyl mercaptan or ammonia in the gas phase was measured by gas chromatography to evaluate the mercaptan deodorizing performance or ammonia deodorizing performance. The results are shown in Table 4.

From these results, it can be seen that the deodorizing composition of the present invention is excellent in deodorizing performance of methyl mercaptan and ammonia even in a solution state.

Example 4 (Storage stability test) The solutions of the various deodorant compositions prepared in Example 3 were collected in ampoules, sealed, and allowed to stand for 1 week. Ferrous sulfate / L-ascorbic acid / copper sulfate. For the deodorant composition containing pentahydrate, the aqueous solution turned brown, and the deodorization rate of methyl mercaptan was reduced to 35%, but for the other deodorant compositions, almost the same results as in Example 3 were obtained. .

From this, it can be seen that the deodorant composition of the present invention has excellent storage stability.

Reference Example 4 100 parts of the thermoplastic resin shown in Table 5 and the components (A) and (B) shown in the same table were mixed with a Henschel mixer to obtain a deodorant resin composition. The obtained deodorant resin composition was extruded as a sheet from a T-type die using an extruder having a cylinder inner diameter of 65 mm and a screw compression ratio of 5.0, and the sheet was biaxially stretched to give a film having a thickness of 0.1 mm ( 1) ~ (20)
Got The obtained films (1) to (20) were odorless.

Example 5 (Deodorization test) A sample was prepared from the films (1) to (20) shown in Table 5,
Table 6 shows the results of the same ammonia deodorization test, hydrogen sulfide deodorization test, and methyl mercaptan deodorization test as in Example 1. In this test, the ammonia concentration was 20,000 ppm and the methyl mercaptan concentration was 300 p.
It was pm.

From the results in Table 6, it can be seen that the deodorant resin molded product of the present invention is excellent in deodorizing properties of basic malodor and sulfur malodor.

Reference Example 5 100 parts of the thermoplastic resin shown in Table 7 and (A) component and (B) component shown in the same table were used to prepare a film (2
1) to (29) were obtained. The resulting film was odorless.

Example 6 (Deodorization test) Samples were prepared from the films (21) to (29) shown in Table 7,
The results of the ammonia deodorizing test and the methyl mercaptan deodorizing test performed in the same manner as in Example 5 are shown in Table 8.

From the results in Table 8, it can be seen that the deodorant resin molded product of the present invention is excellent in deodorizing properties of basic malodor and sulfur malodor.

Reference Example 6 Vinyl chloride resin (Zeon 43A, manufactured by Nippon Zeon Co., Ltd.) 1
3 parts of stabilizer (Ba-Zn vinyl chloride stabilizer manufactured by Asahi Denka Co., Ltd., MARK AC-173), 4 parts of dodecenyl succinic anhydride, 0.1 part of copper naphthenate, and plasticizer (dioctyl). 60 parts of phthalate) was added and mixed for 10 minutes with a raker machine to obtain a paste 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 obtain a polyvinyl chloride film (30) having a thickness of 450 μm. The obtained film (30) was slightly blue and transparent.

Reference Example 7 A film (31) having a thickness of 450 μm was obtained in the same manner as in Reference Example 6 except that the amount of copper naphthenate was 0.2 part. The film (31) was light blue and transparent.

Reference Example 8 A film (32) having a thickness of 450 μm was obtained in the same manner as in Reference Example 6 except that copper oleate was used instead of copper naphthenate. The film (31) was light green and transparent.

Reference Example 9 A film (33) having a thickness of 450 μm was obtained in the same manner as in Reference Example 6 except that copper naphthenate was not used. The film (33) was colorless and transparent.

Reference Example 10 A film (34) having a thickness of 450 μm was obtained in the same manner as in Reference Example 9 except that trimellitic acid was used instead of dodecenyl succinic anhydride. The obtained film (34) was brown and opaque.

Example 7 (Deodorization test) A deodorization test similar to that of Example 1 was performed with an ammonia concentration of 5,000 ppm and a methylmercaptan concentration of 150 ppm.
Performed on films (30)-(34). The results are shown in Table 9.

It can be seen from Table 9 that the deodorant resin molded article of the present invention is excellent in deodorizing basic odor and sulfur odor.

Reference Example 11 High-density polyethylene (Showa Denko KK, Sholex
F5012M) 94.8 parts, 5 parts of the ene reaction product II of α-olefin and maleic anhydride, and 0.2 parts of copper naphthenate were mixed, and the temperature at the cylinder tip was 220 ° C. from an extruder equipped with a nozzle for monofilament. An unstretched yarn is extruded, passed through a 30 ° C. cooling tank, and then heat-stretched with boiling water at 100 ° C. to give a fiber having 300 denier.
I got (1).

Reference Example 12 A 300 denier fiber (2) was obtained in the same manner as in Reference Example 11 except that the amount of copper naphthenate was 0.4 part.

Reference Example 13 A 300 denier fiber (3) was obtained in the same manner as in Reference Example 11 except that copper oleate was used instead of copper naphthenate.

Reference Example 14 300 denier fiber as in Reference Example 11 except that the ene reaction product III was used in place of the ene reaction product II.
I got (4).

Reference Example 15 Instead of high-density polyethylene, polypropylene (Showa Denko
A fiber (5) having 300 denier was obtained in the same manner as in Reference Example 11 except for using Show Allomer MA210 manufactured by Co., Ltd.

Reference Example 16 A 300 denier fiber (6) was obtained in the same manner as in Reference Example 11 except that the amount of high-density polyethylene was 95 parts and copper naphthenate was not used.

Reference Example 17 In the same manner as in Reference Example 11 except that the deodorizing component was not used, 30
A 0 denier fiber (7) was obtained.

Reference Example 18 In the same manner as in Reference Example 11 except that the deodorizing component was not used, 30
A 0 denier fiber (8) was obtained.

Example 8 (Deodorization test) The fibers (1) to (8) obtained in Reference Examples 11 to 18 were subjected to the same deodorization test as in Example 7. In this example, the ammonia concentration was 10,000 ppm. The results are shown in Table 10.

From the results shown in Table 10, it can be seen that the deodorant resin molded article (fiber obtained from the deodorant resin composition) of the present invention is excellent in deodorizing properties of basic odor and sulfur odor.

Reference Example 19 Polyvinyl chloride resin (Zeon Resin 3 manufactured by Nippon Zeon Co., Ltd.)
3) To 100 parts, add 3 parts of barium-zinc heat stabilizer, 6 parts of azodicarbonamide foaming agent, 15 parts of titanium oxide, 80 parts of calcium carbonate, 65 parts of dioctyl phthalate and 5 parts of mineral spirit After the slurry was formed by a machine, 5% of the total solid content of the slurry, the ene reaction product IV and 10% of copper naphthenate were added and mixed for 5 minutes to obtain a paste sol. This sol was applied on paper with a bar coater to a thickness of 200 μm, and then treated at 210 ° C. for 60 seconds in a hot air circulation type oven to obtain a foamed sheet (1b).

Reference Example 20 A foamed sheet (2b) was obtained in the same manner as in Reference Example 19 except that the ene reaction product II was used in place of the ene reaction product IV.

Reference Example 21 A foamed sheet (3b) was obtained in the same manner as in Reference Example 20 except that the amount of copper naphthenate was 20% of the ene reaction product II.

Reference Example 22 A foamed sheet (4b) was obtained in the same manner as in Reference Example 20 except that cupric chloride was used instead of copper naphthenate.

Reference Example 23 Instead of polyvinyl chloride resin, vinyl acetate-vinyl chloride copolymer resin (ZEON Resin 135J manufactured by Nippon Zeon Co., Ltd.)
Foam sheet (5b) in the same manner as in Reference Example 20 except that
Got

Reference Example 24 A foamed sheet (6b) was obtained in the same manner as in Reference Example 19 except that the ene reaction product V was used in place of the ene reaction product IV.

Reference Example 25 Except that succinic anhydride is used instead of the ene reaction product IV,
A foamed sheet (7b) was obtained in the same manner as in Reference Example 19.

Reference Example 26 A foamed sheet (8b) was obtained in the same manner as in Reference Example 19 except that 3-methyl-Δ ⁴ -tetrahydrophthalic anhydride was used instead of the ene reaction product IV.

Reference Example 27 A foamed sheet (9b) was obtained in the same manner as in Reference Example 19 except that lauric anhydride was used instead of the ene reaction product IV.

Reference Example 28 A foamed sheet (10b) was obtained in the same manner as in Reference Example 19 except that the polyacrylic anhydride (1) obtained in Reference Example 1 was used instead of the ene reaction product IV.

Reference Example 29 Except that phthalic anhydride is used instead of the ene reaction product IV,
A foamed sheet (11b) was obtained in the same manner as in Reference Example 19.

Reference Example 30 A foamed sheet (12b) was obtained in the same manner as in Reference Example 19 except that trimellitic anhydride was used instead of the ene reaction product IV.

Reference Example 31 A foamed sheet (13b) was obtained in the same manner as in Reference Example 19 except that pyromellitic dianhydride was used instead of the ene reaction product IV.

Reference Example 32 Except that the ene reaction product IV and copper naphthenate were not added,
A foam sheet (14b) was obtained in the same manner as in Reference Example 19.

Reference Example 33 The ene reaction product IV and its 10% copper naphthenate were dissolved in toluene to prepare a 5% toluene solution. This was impregnated with the foamed sheet (14b) obtained in Reference Example 32 and dried, and then the foamed sheet (15b) having a deodorant composition adhesion amount of 5%
Got

Example 9 (Deodorization test) The foamed sheets (1b) to (15b) obtained in Reference Examples 19 to 33 were subjected to an ammonia deodorization test and a methyl mercaptan deodorization test. The results are shown in Table 11.

In this example, the deodorization test was conducted as follows.

(Ammonia deodorization test) 0.5 g of each sample is placed in a glass ampoule with a crown having an inner volume of 150 ml and the bottle is tightly sealed. Next, after replacing the inside of the ampoule with nitrogen gas containing 3,800 ppm of ammonia, 24
After a lapse of time, the amount of ammonia in the ampoule is quantified by gas chromatography and the deodorization rate is calculated.

(Mercaptan Deodorization Test) The deodorization rate is calculated for nitrogen gas containing 100 ppm of methyl mercaptan by the same method as the ammonia deodorization test.

From this result, it can be seen that the deodorant foam of the present invention is excellent in the deodorizing performance of ammonia and methyl mercaptan.

Example 10 1 g of the bastosol prepared in Reference Examples 19 and 32 was placed in an ampoule having an inner volume of 150 ml and sealed tightly.
The paste sol was foamed by immersing it in an oil bath at 0 ° C. for 10 minutes. When the ampoule was opened and the odor of the gas phase was examined, a strong ammonia odor was felt from Reference Example 32, but Reference Example 19 was odorless. When the odor of the foam in the ampoule was examined, the foam of Reference Example 19 had no ammonia odor, whereas the foam pair of Reference Example 32 had an ammonia odor.

From this, the components (A) and (B) are mixed with the expandable thermoplastic resin, and then the expandable thermoplastic resin is foamed. In the case of the method for producing a deodorant foam, ammonia generated by decomposition of the foaming agent. It can be seen that the emission of odor to the surroundings is significantly suppressed.

Example 11 (foaming test) In Reference Examples 19, 21, 26 and 32, the same operation was performed except that the heat treatment time was 30 seconds, and the foamed sheets (1a), (3a), (8a) and ( 14a) was obtained. Similarly, the heat treatment time was set to 90 seconds, and the foam sheets (1c), (3
c), (8c) and (14c) were obtained. Table 12 shows the results of measuring the expansion ratio of these foamed sheets and the foamed sheets (1a), (3a), (8a) and (14c).

From this, it can be seen that the (A) carboxylic acid anhydride and (B) copper compound used in the deodorant thermoplastic resin foam do not affect the shape of the foam.

Claims (5)

[Claims] 1. A deodorizing composition containing (A) a carboxylic acid anhydride and (B) a copper compound. 2. A deodorant composite material comprising (A) a carboxylic acid anhydride and (B) a copper compound contained in a base material. 3. A deodorant resin composition obtained by blending (A) a carboxylic acid anhydride 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.