JPH0622547B2 - Deodorant, deodorant composite material, deodorant resin composition, deodorant resin molding, and deodorant foam - Google Patents

Description

TECHNICAL FIELD The present invention relates to a deodorant, a deodorant composite material, a deodorant resin composition and a deodorant resin product, and more specifically, it is excellent in deodorant property and thermal stability. The present invention relates to a deodorant, a deodorant composite material derived therefrom, a deodorant resin composition, a deodorant resin molded article, and a deodorant foam.

(Prior Art) Conventionally, it has been known that an aliphatic polycarboxylic acid such as citric acid or oxalic acid or a salt thereof is effective as a removing agent for basic malodor such as ammonia or amine (JP-A-61-61 No. 137565, Japanese Patent Laid-Open No. 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 have poor thermal stability, there is a problem that decomposition at the time of use at a high temperature occurs due to foaming or coloring, and the deodorizing property is not sufficiently exhibited. Further, the deodorizing resin composition obtained by blending these compounds with a thermoplastic resin also has poor dispersibility in the resin of these compounds and decomposition when exposed to high temperature in the process of blending with the resin. Therefore, there is a problem that the deodorizing property is not sufficiently exhibited.

Further, a deodorant containing a low molecular weight dicarboxylic acid anhydride such as maleic anhydride (Japanese Patent Laid-Open No. 56-26542) has been proposed, and the acid anhydride should be supported on a porous plastic. Is proposed. However, when a dicarboxylic acid anhydride such as maleic anhydride is exposed to a high temperature, it is sublimated or decomposed, so that there is a problem that the deodorizing performance is not exhibited.

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

As a result of earnest research to achieve this object, the present inventors have
If an α, β-unsaturated dicarboxylic acid anhydride-based polymer (excluding a copolymer of ethylene and α, β-unsaturated dicarboxylic acid anhydride) is used, a deodorant having excellent thermal stability can be obtained. It was found that a deodorizing resin composition having excellent deodorizing property and thermal stability can be obtained by blending this with a thermoplastic resin, and based on this finding, the present invention has been completed.

(Means for Solving the Problem) Thus, according to the present invention, an α, β-unsaturated dicarboxylic acid anhydride polymer (a copolymer of ethylene and an α, β-unsaturated dicarboxylic acid anhydride is excluded. ) As an active ingredient, a deodorant composite material obtained by incorporating the deodorant into a base material, a deodorant resin composition obtained by blending the above deodorant with a thermoplastic resin, and a composition obtained by processing the composition. A deodorant resin molded article is provided.

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 A copolymer with a copolymerizable monomer (excluding ethylene).

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;
Propylene, isobutene, butene-1, butene-2, pentene-1, pentene-2, 2-methylbutene-1, 2
-Aliphatic monoolefins other than ethylene, such as methylbutene-2, hexene-1,2,2,4-trimethylpentene-1,2,2,4-trimethylpentene-2, decene-1, octadecene-1; Cyclic monomer olefins such as cyclopentene, cyclohexene, cyclooctene, etc .;
Aliphatic diolefins such as butadiene, isoprene and piperylene; cyclic diolefins such as cyclopentadiene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated carboxylic acids such as ethyl acrylate and methyl methacrylate Acid esters; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride; vinyl carboxylates such as vinyl acetate; vinyl ethers such as methyl vinyl ether; vinyl sulfonic acid, p And unsaturated sulfonic acids such as 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 compounded with respect to 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,
500 to 500,000, preferably 1,000 to 30
It is 10,000.

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

In addition, the deodorant of the present invention may optionally contain an existing deodorant, a bactericide, an antifungal agent, etc., as long as it does not impair the effect, and further, a pigment, a colorant, and a stabilizer. Various additives such as agents and antioxidants may also be included.

The deodorant of the present invention can be used alone in various forms, for example, in the form of a solution, powder, tablet or the like, or can be contained in various base materials to form a deodorant composite material.

The substrate used in the deodorant composite material of the present invention is not particularly limited as long as it can be contained by a method such as impregnation, coating and supporting of the deodorant of the present invention, and specific examples thereof 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 is not particularly limited, and examples thereof include powder, granules, fibers, and sheets.

In the deodorant composite material of the present invention, the amount of the deodorant contained in the base material is different depending on the purpose, but is usually 0.1 to 30% by weight, preferably 1 to 20% by weight based on the base material. is there. If the amount used is too small, the function may be insufficient, and if it is excessively large, the economy may be poor.

A deodorant resin composition is obtained by blending the deodorant of the present invention with a thermoplastic resin, which 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; styrene-isoprene Block copolymers of aromatic vinyl compound-conjugated diene monomers such as block copolymers and styrene-butadiene block copolymers; cellulose esters such as cellulose diacetate; 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.

The blending amount of the deodorant containing the α, β-unsaturated dicarboxylic acid anhydride polymer as an active ingredient in the present invention with respect to the thermoplastic resin varies depending on the purpose, but is usually 0.1 to 30 with respect to the resin component. %, Preferably 1.0 to 20% by weight. If the amount used is too small, the deodorizing function may be insufficient.

In the present invention, the blending method of the thermoplastic resin and the deodorant having an α, β-unsaturated dicarboxylic acid anhydride polymer as an active ingredient is not particularly limited, and for example, the deodorant can be heated at the same time for all of the deodorants. The deodorant may be added to the thermoplastic resin, or a part of the deodorant may be added to the thermoplastic resin and then the remaining portion may be added. Alternatively, it is possible to blend a deodorant into a part of the thermoplastic resin and blend the rest of the thermoplastic resin into the deodorant resin composition of the present invention. In addition, the deodorant of the present invention supported on an inorganic substrate such as activated carbon is
It is suitable for compounding because it has good dispersibility in thermoplastic resin.

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 deodorant resin composition of the present invention can 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.

Furthermore, 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.

In the present invention, the method for molding the deodorant foam is not limited to a particular time, and examples thereof include a method in which the entire amount of the deodorant is premixed with the foamable thermoplastic resin and then foam molding is carried out by a conventional method. However, it is also possible that a part of the deodorant is mixed with the expandable thermoplastic resin in advance and foam-molded, and then the remaining deodorant 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 having excellent deodorizing properties and thermal stability as compared with the prior art. This deodorant is used alone, or is contained in various base materials to be used as a deodorant composite material. By mixing the deodorizing material of the present invention with a thermoplastic resin, a deodorizing resin composition having excellent deodorizing properties 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 Various deodorant components (α, β-unsaturated dicarboxylic acid anhydride polymer) shown in Table 1 were crushed in a mortar to prepare powder samples, and the powder samples were subjected to the following tests.

(Thermal stability test) 1 g of each test 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 to 200 ° C for 1 hour. Heating loss rate
(B) was measured. The results are shown in Table 1.

(Ammonia deodorization test and trimethylamine deodorization test) 1 g of each sample was placed in a glass ampoule with a crown having an internal capacity of 150 ml, sealed, and then air containing 100,000 ppm ammonia or 10,000 ppm trimethylamine was introduced into the ampoule. After substitution, one day and night, the concentration of ammonia or trimethylamine in the ampoule was measured by gas chromatography to calculate the deodorization rate. The results are shown in Table 1.

From Table 1, it can be seen that the deodorant of the present invention is excellent in heat stability and basic odor deodorizing performance.

Example 2 100 parts of polyethylene resin (Showa Denko KK low-density polyethylene, Showlex 720FS) was added to styrene-
2.56 parts of maleic anhydride copolymer (copolymerization composition ratio 50/50, SMA1000A manufactured by Arco Chemical Company) was mixed with a Henschel mixer to obtain a deodorant resin composition.
The obtained 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 a thickness of 0.
A 1 mm film (1) was obtained. The obtained film (1) was colorless and transparent and had no odor.

Example 3 Instead of the styrene-maleic anhydride copolymer, a styrene-maleic anhydride monoester copolymer (copolymerization composition ratio
50/50, manufactured by Arco Chemical Company, SMA17352
The thickness is 0.1 m in the same manner as in Example 2 except that A) is used.
A film (2) of m was obtained. The obtained film (2) was colorless and transparent and had no odor.

Example 4 A film (4) having a thickness of 0.1 mm was obtained in the same manner as in Example 2 except that the amount of the styrene-maleic anhydride copolymer was 10.2 parts. The obtained film (4) was colorless and transparent and had no odor.

Example 5 Polypropylene resin (Polypro S205 manufactured by Tonen Petrochemical Co., Ltd.) instead of polyethylene resin as the thermoplastic resin
A film (5) having a thickness of 0.1 mm was obtained in the same manner as in Example 2 except that was used. The obtained film (5) was colorless and transparent and had no odor.

Comparative Example 1 A film (6) having a thickness of 0.1 mm was obtained in the same manner as in Example 5 except that citric acid was used instead of the styrene-maleic anhydride copolymer. The obtained film (6) was odorless and transparent, but was slightly yellowish and had bubbles.

Example 6 (Deodorization test) 1 g of the film obtained in each of Examples 2 to 5 and Comparative Example 1 was 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 determine the deodorization rate.

The results are shown in Table 2.

It can be seen from Table 2 that the deodorant resin molded product of the present invention is excellent in deodorizing basic odor.

Example 7 Vinyl chloride resin (Zeon 43A manufactured by Nippon Zeon Co., Ltd.)
Stabilizer (Ba-Zn-based vinyl chloride stabilizer (MARK AC-173) manufactured by Asahi Denka Kogyo Co., Ltd. 3 parts, α-olefin-maleic anhydride copolymer (manufactured by Mitsubishi Kasei Co., Ltd.) PA 20
8) 4 parts and 60 parts of a plasticizer (dioctyl phthalate) were added and mixed for 10 minutes with a raker machine to obtain a paste sol.
After applying this sol on a glass plate with a bar coater,
Treated in an oven at 190 ℃ for 2 minutes, thickness 450μ
m polyvinyl chloride film (7) was obtained. The obtained film (7) was colorless and transparent.

Example 8 Instead of the α-olefin-maleic anhydride copolymer, a styrene-maleic anhydride copolymer (copolymerization composition ratio 50/5
A film (8) having a thickness of 450 μm was obtained in the same manner as in Example 7 except that 0, SMA 3000A manufactured by Arco Chemical Company) was used. The obtained film (8) was colorless and transparent.

Comparative Example 2 A film (9) having a thickness of 450 μm was obtained in the same manner as in Example 7 except that trimellitic acid was used instead of the α-olefin-maleic anhydride copolymer. Film obtained
(9) was colored opaque and brown.

Comparative Example 3 Example 7 was repeated except that a mixture of ferrous sulfate, citric acid and sodium citrate (mixing ratio = 80: 15: 5) was used instead of the α-olefin-maleic anhydride copolymer.
A film (10) having a thickness of 450 μm was obtained in the same manner as in.
The obtained film (10) was colored brown and had a large number of bubbles and was non-uniform.

Example 9 (Deodorization test) Films (7) to (9) were subjected to the same deodorization test as in Example 6 except that the ammonia concentration was set to 5000 ppm. The test was omitted for the film (10) because the shape of the film was bad. The results are shown in Table 3.

It can be seen from Table 3 that the deodorant resin molded article of the present invention is excellent in deodorizing basic odor.

Example 10 95 parts of high-density polyethylene (Showa Denko KK, Shorex F5012M) and 5 parts of styrene-maleic anhydride copolymer (ARCO Chemical Company, SMA 3000A) were mixed to prepare a monofilament nozzle. From the attached extruder, extruded as unstretched yarn at a cylinder tip temperature of 220 ° C, passed through a 30 ° C cooling tank, and then 100 ° C.
A 300 denier fiber (1) was obtained by heating and drawing with boiling water.

Example 11 In place of the styrene-maleic anhydride copolymer, an α-olefin-maleic anhydride copolymer (Mitsubishi Chemical Industry Co., Ltd.)
Manufactured by PA 168) in the same manner as in Example 10, except that
A 0 denier fiber (2) was obtained.

Example 12 A 300 denier fiber (3) was obtained in the same manner as in Example 10 except that polypropylene (Showa Denko Co., Ltd., Show Allomer MA210) was used in place of the high-density polyethylene.

Comparative Example 4 A 300 denier fiber (4) was obtained in the same manner as in Example 10 except that the deodorant was not used.

Comparative Example 5 A 300 denier fiber (5) was obtained in the same manner as in Example 12 except that the deodorant was not used.

Example 13 (Deodorization test) Fibers (1) obtained in Examples 10 to 12 and Comparative Examples 4 and 5
For (5) to (5), the deodorization test was conducted in the same manner as in Example 6. However, in this embodiment, the ammonia concentration is 10,
It was 000 ppm. The results are shown in Table 4.

From the results shown in Table 4, it can be seen that the fiber obtained from the deodorizing resin composition of the present invention is excellent in deodorizing basic odor.

Example 14 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 65 parts of dioctyl acid and 5 parts of mineral spirit were added and made into a slurry by a raking machine, and then styrene-maleic anhydride copolymer (copolymerization composition ratio 50/50, arco. Powder of Chemical Company, SMA 1000A) was 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).

Example 15 Instead of polyvinyl chloride resin, vinyl acetate-vinyl chloride copolymer resin (Zeon Resin 135 manufactured by Nippon Zeon Co., Ltd.)
Foamed sheet in the same manner as in Example 14 except that J) is used.
(2b) was obtained.

Comparative Example 6 Except that a styrene-maleic anhydride copolymer was not added,
A foam sheet (3b) was obtained in the same manner as in Example 14.

Example 16 (Deodorization test) Foamed sheets (1) obtained in Examples 14 to 15 and Comparative Example 6
b) to (3b) 0.5 g of each was placed in a glass ampoule with a cap of 150 ml and sealed, and the inside of the ampoule was replaced with air containing 3800 ppm of ammonia, and after a predetermined time, the ampoule was gas chromatographed. The concentration of ammonia was measured and the deodorization rate was calculated. Furthermore, the foam sheets (1b) to (3
Put another 1 g of each of b) into a odor bag with a silicon rubber stopper having a capacity of 3, then inject air 1 containing 100 ppm of hydrogen sulfide, and after a predetermined time, change the amount of hydrogen sulfide in the ampoule to Kitagawa formula. The deodorization rate was calculated by measuring with a gas detector tube. The results are shown in Table 5.

From the results in Table 5, it can be seen that the deodorant foam obtained from the deodorant thermoplastic resin composition of the present invention is excellent in deodorizing ammonia and hydrogen sulfide.

Example 17 1 g of the paste sol prepared in Example 14 and Comparative Example 6 was placed in an ampoule having an inner volume of 150 ml and sealed tightly, 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 6, but Example 14 was odorless. Further, when the odor of the foam in the ampoule was examined, the foam of Example 15 had no ammonia odor, whereas the foam of Comparative Example 6 had an ammonia odor.

From this, the deodorant of the present invention is mixed with a foamable thermoplastic resin and then foamed. In the method for producing a deodorant foam, the emission of ammonia odor generated by the decomposition of the foaming agent to the surroundings can be significantly suppressed. I understand.

Example 18 In Example 14 and Comparative Example 6, the heat treatment time was 30.
Do the same operation except for setting each second and foam sheet (1a)
And (3a) were obtained. Similarly, the foaming sheets (1c) and (3c) were obtained by setting the heating time to 90 seconds. Table 6 shows the results of measuring the expansion ratio of these foamed sheets and the foamed sheets (1b) and (3b).

From the results in Table 6, it can be seen that the deodorant of the present invention does not affect the shape of the deodorant foam obtained from the deodorant resin composition of the present invention.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area (C08L 101/00 101: 08)

Claims (5)

[Claims] 1. A deodorant comprising an α, β-unsaturated dicarboxylic acid anhydride polymer (excluding a copolymer of ethylene and an α, β-unsaturated dicarboxylic acid anhydride) as an active ingredient. 2. A deodorant composite material comprising a base material containing the deodorant according to claim 1. 3. A deodorant resin composition obtained by blending the deodorant according to claim 1 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.