JPH01158959A - Deodorant, deodorizing composite material, deodorizing resin composition, deodorizing resin molded product and deodorizing foam - Google Patents

Abstract

PURPOSE:To enhance a deodorizing property and heat stability, by compounding alpha,beta-unsaturated dicarboxylic anhydride polymer with a thermoplastic resin. CONSTITUTION:A deodorizing composite material wherein a deodorant containing an alpha,beta-unsatuurated dicarboxylic anhydride polymer as an effective component is contained in a base material is compounded with a thermoplastic resin. The alpha,beta-unsaturated dicarboxylic anhydride polymer to be used is a homopolymer of alpha,beta-unsaturated dicarboxylic anhydride and a copolymer of alpha,beta-unsaturated dicarboxylic anhydride and a monomer copolymerizable therewith. As alpha,beta-unsaturated dicarboxylic anhydride, maleic anhydride and citraconic anhydride are designated. As the monomer copolymerizable with alpha,beta-unsaturated dicarboxylic anhydride, there are styrene, isobutene or the like. The compounding amount of the deodorant containing the alpha,beta-unsaturated dicarboxylic anhydride as the effective component to the thermoplastic resin is usually 0.1-30%, pref., 1.0-20% by wt. of the resin component.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a deodorizing agent, a deodorizing composite material, a deodorizing resin composition, and a deodorizing resin molded article, and more particularly, to The present invention relates to a deodorizing agent, a deodorizing composite material derived therefrom, a deodorizing resin composition, a deodorizing resin molded article, and a deodorizing foam.

(Prior Art) Conventionally, aliphatic polycarbonates such as citric acid and oxalic acid have been used as basic odor removers such as ammonia and amines. It is known that acid or its salt is effective (Japanese Patent Publication No. 61-137565, Japanese Patent Publication No. 61-154673),
It has been reported that a deodorizing resin composition can be obtained by blending these compounds with a thermoplastic resin (Japanese Patent Laid-Open No. 61-209
662). However, these aliphatic polycarboxylic acids
Due to its poor thermal stability, when used at high temperatures, it tends to decompose with foaming and coloring, and its deodorizing properties are not sufficiently exhibited. In addition, deodorizing resin compositions obtained by blending these compounds with thermoplastic resins also suffer from poor dispersibility of these compounds in the resin and decomposition when exposed to high temperatures during the process of blending them into the resin. Therefore, there is a problem that deodorizing properties are not sufficiently exhibited.

(Problem to be solved by the invention) An object of the present invention is to solve the above problems.

As a result of intensive research to achieve this objective, the present inventors found that α
, a deodorizing agent with excellent thermal stability can be obtained by using a β-unsaturated unsaturated dinol anhydride polymer, and by blending this into a thermoplastic resin, a deodorizing agent with excellent deodorizing properties and thermal stability can be obtained. Based on this finding, the present invention was completed.

(Means for Solving the Problems) Thus, the present invention provides a deodorizing agent containing an α,β-unsaturated dicargonic acid anhydride polymer as an active ingredient, and a deodorizing composite material containing the deodorizing material. The present invention provides a deodorizing resin composition comprising a thermoplastic resin blended with the above deodorizing agent, and a deodorizing resin molded article formed by processing this composition.

The α,β-unsaturated nocarmenic anhydride-based polymer used in the present invention refers to a homopolymer of α,β-unsaturated zocarboxylic anhydride, α,β-unsaturated unsaturated dinormenic anhydride, and A copolymer with a copolymerizable monomer.

Moreover, α, β-unsaturated radicals used in the present invention? Examples of acid anhydride-based polymers include those obtained by introducing acid anhydride groups into polymer chains through known polymer reactions, such as those obtained by adding maleic anhydride to polybutatsuene. .

Furthermore, α and β contained in these polymers and copolymers
- Those having a structure in which part or all of the acid anhydride group of an unsaturated dicardic acid anhydride unit is converted into a cycargexyl group by a known reaction such as hydrolysis or alcoholysis are also α
, contained in β-unsaturated dicardic acid anhydride polymers.

At this time, the resulting polymers and copolymers may contain ester groups, amide groups, imide groups, etc. in addition to carboxyl groups.

Examples of α,β-unsaturated decarboxylic acid anhydrides include:
Examples include maleic anhydride, itacone anhydride, and citraconic anhydride. Among these, maleic anhydride is preferred from the viewpoint of reactivity, economy, etc.

Specific examples of monomers copolymerizable with α,β-unsaturated dicargonic acid anhydride include aromatic monoolefins such as styrene, α-methylstyrene, vinyltoluene, etc.; ethylene, propylene, isobutyne, butene-1, Butene-2, Penten-11 Inten-2,2-methylbutene-11,2-methylbutene-2, Hexene-1,2,2
, 4-)limethylpentene-1, 2.2.4-)limethylpentene-2, decene-1, octadecene-1, etc.; cyclic monoolefins such as cyclopentene, cyclohexene, cyclooctene, etc. Olefins; aliphatic diolefins such as butadiene, isogrene, piperylene, etc.; cyclic diolefins such as cyclopentadiene 7; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, etc.; ethyl acrylate, methacrylic acid Unsaturated caldenic acid esters such as methyl; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride; vinyl carboxylates such as vinyl acetate; Vinyl ethers; unsaturated sulfonic acids such as vinyl sulfonic acid, p-styrene sulfonic acid, etc. can be mentioned.

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

The occupancy of the α,β-unsaturated dicarbo/acid anhydride unit or the unit derived therefrom contained in the α,β-unsaturated dicargonic acid anhydride polymer used in the present invention is not particularly limited, but it is usually , 1 mole or more, preferably 5 mole or more of the edible units constituting the α,β-unsaturated dicargonic acid anhydride polymer. If this amount is too small, the amount of deodorizing agent added to the thermoplastic resin may be too large, which may cause problems in the moldability of the deodorizing resin composition.

The molecular weight of the α,β-unsaturated socalanhydride polymer used in the present invention is not particularly limited, but usually
500-soo, ooo, preferably 1,000-30
It is 0,000.

The deodorizer of the present invention may contain not only one type of α,β-unsaturated dicarbo/acid anhydride polymer, but also a combination of two or more types.

The deodorizer of the present invention may also contain existing deodorizers, bactericidal agents, antifungal agents, etc., as well as pigments, colorants, and stabilizers, if necessary, as long as they do not impair their effectiveness. Various additives such as antioxidants, antioxidants, etc. may also be included.

The deodorizing agent of the present invention can be used alone in various forms, for example, in the form of a solution, powder, tablet, etc., or can be incorporated into various base materials to form a deodorizing composite material.

The base material used in the deodorizing composite material of the present invention is not particularly limited as long as it can contain the deodorizing agent of the present invention by impregnation, coating, supporting, etc. Specific examples thereof include: Examples include paper, cloth, foam sheets, valves, fibers, activated carbon, alumina, silica gel, zeolite, clay, bentonite, diatomaceous earth, and acid clay. The shape of the base material is not particularly limited either, and examples thereof include powder, granule, fiber, sheet, and the like.

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

A deodorizing resin composition can be obtained by blending the deodorizing agent of the present invention with a thermoplastic resin, and this composition is useful as a raw material for deodorizing resin molded articles.

The thermoplastic resin used in the present invention may be any resin as long as it can be molded into films, sheets, fibers, foams, and other various molded products, and specific examples thereof include polyethylene, polypropylene, polybutadiene, etc. Polyolefins; such as polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, etc. Rivinyl compounds; aromatic vinyl compound-conjugated diene monomer block copolymers such as styrene-isoylene block copolymers, styrene/-butadiene block copolymers, etc.; cellulose esters such as cellulose diacetate, etc. ; i-semi-cellulose; polyesters; polyamide; fluorine-containing fat, and the like.

Furthermore, examples of the foamable thermoplastic resin described below include polyvinyl chloride, vinyl acetate-vinyl chloride copolymer, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene'dlHIW,
rJ! Examples include lipinyl alcohol, polyamide, cellulose, etc., but are not limited to these.

In the present invention, the blending amount of the deodorizer containing the α,β-unsaturated dicargonic acid pyrohydrate polymer as an effective fraction in the thermoplastic resin varies depending on the purpose, but is usually 0.1% of the resin component. ~30% by weight, preferably 1.0~20ffit
It is 96. If the amount used is too small, the deodorizing function may be insufficient.

In the present invention, the method of blending the thermoplastic resin and the deodorizing agent containing α,β-unsaturated socarbic acid anhydride polymer as the ringing component is not particularly limited. It may be blended into the OT plastic side fat, or the remaining 9 parts may be added after blending a part of the deodorizing agent with the thermoplastic resin. Alternatively, it is also possible to form the deodorizing resin composition of the present invention by blending a deodorizing agent into a part of the thermoplastic resin and blending the remainder of the thermoplastic resin therein. Furthermore, the deodorizing agent of the present invention supported on an inorganic base material such as activated carbon is suitable for blending because it has good dispersibility in thermoplastic resins.

In the present invention, the deodorizing resin molded product may be used in combination with existing deodorizing agents, stimulants, anti-mold agents, etc. as long as it does not impede its performance, and stabilizers, stabilizers, etc. Various additives may also be included, such as lubricants, antioxidants, UV absorbers, processing aids, blowing agents, pigments, fly burn, impact resistance aids, and the like.

The deodorizing resin composition of the present invention thus obtained can be molded by extrusion molding, compression molding, calendar molding, blow molding, injection paper molding,
It can be processed into various molded products including sheets, films, and sheets by conventional resin processing methods such as thermoforming, lamination molding, and rotational molding.

Further, the deodorizing resin composition of the present invention can be used alone or in combination with other fiber raw materials to form fibers. The obtained films and sheets can be made into breathable sheets, cloth, non-woven fabrics, etc. by punching fine holes with a punch or the like.
It is also possible to cover paper or the like or laminate it on other resin films. In addition, in the case of fibers, it can be made into cloth or net-like.

Furthermore, when a foamable thermoplastic resin is used as the thermoplastic resin, the resulting deodorizing resin composition can be foam-molded to form a deodorizing foam.

In the present invention, the method of molding the deodorizing foam (Fi%) is not particularly limited, and for example, a method may be mentioned in which the entire amount of the deodorizing agent is mixed in advance with a foamable thermoplastic resin, and then the foam is molded by a conventional method. However, it is also possible to mix a part of the deodorizer with a foamable thermoplastic resin in advance and foam mold it.
It is also possible to incorporate residual deodorizing agents into the foam by impregnation.

The production of foam from the deodorizing resin composition of the present invention has the advantage that it is possible to significantly reduce the bad odors of ammonia, amines, etc. generated during foaming of the resin, and that a foam with a high expansion ratio can be obtained. .

(Effects of the Invention) Thus, according to the present invention, it is possible to obtain a deodorizing agent that has superior deodorizing properties and thermal stability compared to the prior art. This deodorizing agent can be used alone or incorporated into various base materials to form a deodorizing composite material. By blending the deodorizing agent of the present invention with Atsumachi heavy fat-defining composition, a deodorizing resin composition having excellent deodorizing properties and thermal stability can be obtained. This deodorizing resin composition is useful as a raw material for films, sheets, fibers, foams, and other plastic shapes of oak that have functions such as deodorization and deodorization. It is useful as a material for a variety of products including bedding, furniture, wallpaper, food containers, packaging materials, and filters.

(Example) The present invention will be explained in more detail with reference to Examples below.

In addition, parts and weights in Examples and Comparative Examples are based on the weight of a hook without any particular break.

Example 1 Various deodorizing agent components (α,β-unsaturated dicargonic acid anhydride polymers) shown in Table 1 were ground in a mortar to prepare powder samples, which were subjected to the following tests.

(Thermal stability test) 1.9 of each sample was heated to 150℃ during open hot air circulation.
The heating loss rate (a) when the samples were allowed to stand for an hour, and the heating loss rate (middle) when each of these samples was further heated at 200° C. for 1 hour were measured. The results are shown in Table 1.

(Ammonia deodorization test and trimethylamine defruit test)
Put 1.9 of each sample into a glass angle with a crown with an internal capacity of 150 tJ, seal it tightly, and add 0.000 pp of ICl.
The inside of the ampoule was replaced with nitrogen gas containing m of ammonia or 10,000 ppm of trimethylamine, and the quality of the ammonia or trimethylamine in the ampoule was measured by gas chromatography after day and night, and the deodorization rate was calculated. The results are shown in Table 1.

Table 1 shows that the deodorizing agent of the present invention has excellent thermal stability and basic gas deodorizing performance.

Example 2 Styrene-maleic anhydride copolymer (copolymer composition ratio 50
150, manufactured by Arco Chemical Company, 5MA1
00OA) 256@henschelmie? A deodorizing resin composition was obtained by mixing ff. The obtained resin composition was extruded as a sheet from a T-shaped die using an extruder with a cylinder inner diameter of 65 mm and a screw compression ratio of 5.0, and this sheet was biaxially stretched to form a film with a thickness of 0 to 1 tm ( 1) was obtained. The obtained film (1) was clear, colorless, and odorless.

Example 3 In place of the styrene-maleic anhydride copolymer, a styrene-maleic anhydride monoester copolymer (copolymerization composition ratio 50150, manufactured by Arco Chemical Kanfu9ny, 5M
A film (2) having a thickness of 0.1 m was obtained in the same manner as in Example 2 except that Al 7352 A ) was used. The obtained film (2) was transparent, colorless, and odorless.

Example 4 Instead of styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer (copolymer composition ratio 50150
A film (3) with a thickness of 0.1 m was obtained in the same manner as in Example 2 except that DMA-21) was used. The obtained film (3) was transparent, colorless, and odorless.

Example 5 A film (4) having a thickness of 0.1 was obtained in the same manner as in Example 2, except that the amount of the styrene-maleic anhydride copolymer was changed to 10.2 parts. The obtained film (4) was clear, colorless, and odorless.

Example 6 Polyethylene resin (Tonen Petrochemical Co., Ltd., Polypro 8205) was used instead of polyethylene resin as thermoplastic resin.
A film (5) having a thickness of α1m+ was obtained in the same manner as in Example 2 except that a film (5) was used. The obtained film (5) was transparent, colorless, and odorless.

Comparative Example 1 A film (6) with a thickness of 0.1 m was obtained in the same manner as in Example 6, except that citric acid was used in place of the styrene-maleic anhydride copolymer. The obtained film (6) was odorless and transparent, but had a slightly yellow color and some bubbles were observed.

Example 7 (Deodorization test) Films IN obtained in Examples 2 to 6 and Comparative Example 1 were placed in a glass ampoule with a cap of 1150 m in content and sealed tightly, and then heated in an angle with air containing 25,000 ppm of ammonia. After replacing, the degree of ammonia content in the angle was measured over time using gas chromatography to determine the de-fruiting rate.

The results are shown in Table 2.

Table 2) It can be seen that the deodorizing resin molded product of the present invention has excellent deodorizing properties for basic odors.

Table 2 Example 8 Vinyl chloride resin (Nippon Zeon Co., Ltd., Zeon 43A)
Stabilizer (Ba-Zn manufactured by Asahi Denka Kogyo Co., Ltd.) per 100 parts
PVC stabilizer, MARK AC-173) 3 parts, α
4 parts of -olefin-maleic anhydride copolymer (manufactured by Mitsubishi Chemical Industries, Ltd., PA 208) and 60 parts of a plasticizer (dioctyl phthalate) were added and mixed for 10 minutes using a sieve machine to obtain a paste sol. After coating this sol on a glass plate with a percoater, it was treated at 190°C for 2 minutes while open.
A polyvinyl chloride film (7) with a thickness of 450 μm was obtained. The obtained film (7) was colorless and transparent.

Example 9 Instead of α-olefin-maleic anhydride copolymer, styrene-maleic anhydride copolymer (copolymerized Ni acid ratio 5
0150, Earth Chemical Bikan A? Made by knee, 5M
A3000A) was used in the same manner as in Example 8,
A film (8) with a thickness of 450 μm was obtained.

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 8, except that trimellitic acid was used instead of the α-olefin-maleic anhydride copolymer.

The obtained film (9) was colored brown and opaque.

Comparative Example 3 Example 8 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.
In the same manner as above, a film (io) having a thickness of 450 μm was obtained. The obtained film (lO) was colored brown, had many air bubbles, and was non-uniform.

Example 10 (Deodorization test) Example 7 except that the ammonia concentration was 5000 ppm.
A deodorization test similar to that was conducted on films (7) to (9). Regarding film (10), the test was omitted because the shape of the film was poor. The results are shown in Table 3.

Table 3 shows that the deodorizing resin molded product of the present invention has excellent deodorizing properties for basic odors.

Table 3 Example 11 95 parts of hard-density polyethylene (manufactured by Showa Denko K.K., Shorex F5012M), styrene-maleic anhydride copolymer (manufactured by Arp Chemical Company, SM)
A 3000A) 5 parts were mixed, and from an extruder equipped with a monofilament nozzle, 7 cylinders and a tip temperature of 2
It was extruded as an undrawn yarn at 20°C, passed through a cooling tank at 30°C, and then heated and drawn with boiling water at 100°C to obtain a fiber (1) of a particularly small 300 denier.

Example 12 α-olefin y-m water mamalic acid copolymer instead of stene-maleic anhydride copolymer Mitsubishi Chemical Industries, Ltd.
A 300 denier fiber (2) was obtained in the same manner as in Example 11 except that H1pA168) was used.

Example 13 A 300 denier fiber (3
) was obtained.

Comparative Example 4 A 300-denier fiber (4) was obtained in the same manner as in Example 11, except that no deodorizing agent was used.

Comparative Example 5 A 300-denier fiber (5) was obtained in the same manner as in Example 13, except that no deodorizing agent was used.

Example 14 (deodorization test) Fibers obtained in Examples 11 to 13 and Comparative Examples 4 and 5 (1
) to (5) were subjected to a deodorization test in the same manner as in Example 7. However, in this example, ammonia @ degree is 1
It was set as 0,000 ppm. The results are shown in Table 4.

From the results in Table 4, it can be seen that the fibers obtained from the deodorizing resin composition of the present invention have excellent deodorizing properties for basic odors.Table 4 Example 15 Polyvinyl chloride resin (Zeon Corporation ) to 100 parts of Zeon resin 33), add 3 parts of barium-zinc heat stabilizer, 6 parts of azodicarbonamide blowing agent, 15 parts of titanium oxide, 80 parts of calcium carbonate, 65 parts of dioctyl phthalate and 5 parts of mineral spirit. After making a slurry using a milling machine, styrene-maleic anhydride copolymer (copolymer composition ratio 50150), which accounts for 5% of the total solid content of the slurry, is
．． Arp Chemical Kannoya Knee W, SMA 100
OA>(D powder was added and mixed for another 5 minutes to obtain a paste sol. This sol was coated on paper with a percoater for 2 minutes.
After applying the coating to a thickness of 00 μm, it was treated at 210°C for 60 seconds in a hot air circulation system to form a foam sheet) (lb)
I got it.

Example 16 Instead of polyvinyl chloride resin, vinyl acetate-vinyl chloride copolymer resin (Zeon Resin 135J manufactured by Nippon Zeo Co., Ltd.) was used.
) was used in the same manner as in Example 15, except that a foam sheet (
2b) was obtained.

Comparative Example 6 Styrene - Anhydrous! Other than not adding leic acid copolymer,
A foamed sheet (3b) was obtained in the same manner as in Example 15.

Example 17 (Deodorization test) Foaming 7- obtained in Examples 15-16 and Comparative Example 6)
(lb) ~ (3b) each 0.5g content ii1501L
Pour into a glass angle with a crown and seal tightly, 380 ml.
After replacing the inside of the ampoule with air containing 0 ppm of ammonia, the quality of the ammonia inside the ampoule was measured by gas chromatography after a predetermined period of time, and the deodorization rate was calculated. Further foam sea) (lb) to (3b) each other II contents: fi3J? Place the silicone container in a 9mm odor bag with a stopper, then inject air 11 containing 10ppm of hydrogen sulfide, measure the amount of hydrogen sulfide in the angle with a kita type gas detection tube after a predetermined time, and deodorize it. The rate was calculated. These results are shown in Table 5.

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

Table 5 Example 18 1 g of the paste sol prepared in Example 15 and Comparative Example 6 was placed in an ampoule with an internal capacity of 150 mJ and sealed, and the ampoule was immersed in an oil bath at 220°C for 10 minutes to foam the paste sol. . When the angle was opened and the smell of the gas phase was examined, a strong ammonia odor was felt from the one of Comparative Example 6, but the one of Example 15 was odorless. Furthermore, when the strength of the foam in the ampoule was examined, it was found that the foam of Example 15 had no ammonia odor, whereas the foam of Comparative Example 60 had an ammonia odor.

In the method for producing a deodorizing foam in which the deodorizing agent of the present invention is mixed with a foamable thermoplastic resin and then foamed, the dispersion of ammonia odor that is often generated due to the decomposition of the foaming agent is significantly suppressed. I understand that.

Example 19 In Example 15 and Comparative Example 6, the heating immersion time was 30
Perform the same operation except for the foaming seams) (
1m) and (3a) were obtained. In addition, foamed sheets (le) and (3c) were obtained in the same manner, with the heat treatment time being 90 seconds. Table 6 shows the results of measuring the expansion ratios of these foam sheets (lb) and (3b).

The results in Table 6 show that the deodorizing agent of the present invention does not affect the shape of the deodorizing foam obtained from the deodorizing resin composition of the present invention.

Table 6 Patent applicant: Zeon Corporation

Claims (5)

[Claims] (1) A deodorizing agent containing an α,β-unsaturated dicarboxylic acid anhydride polymer as an active ingredient. (2) A deodorizing composite material comprising a base material containing the deodorizing agent according to claim (1). (3) A deodorizing resin composition comprising the deodorizing agent of claim (1) mixed with a thermoplastic resin. (4) A deodorizing resin molded article obtained by processing the deodorizing resin composition of claim (3). (5) A deodorizing foam obtained by foaming the deodorizing resin composition according to claim (3), which uses a foamable thermoplastic resin as the thermoplastic resin.