JP2000136272A - Low malodorous polyolefin resin composition and low malodorous polyolefin resin molded product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a low malodorous polyolefin resin composition capable of suppressing the mechanical strength of a polyolefin resin from deteriorating due to irradiation of ionizing radiations for sterilizing treatment or curing of an ink coating agent, etc., and improved in the emitted malodor due to the decomposition and deterioration and a molded product using the same. SOLUTION: This low malodorous polyolefin resin composition is obtained by adding a phenolic compound, a hindered amine-based compound, phosphorus-based compound and a deodorizing compositions having deodorizing functions by at least one or more chemical neutralizing reactions to a polyolefin resin and comprises the phenolic compound in an amount of 0.005-0.3 pt.wt. based on 100 pts.wt. of the polyolefin resin, the hindered amine-based compound in an amount of 0.05-2.0 pts.wt. based on 100 pts.wt. of the polyolefin resin, the phosphorus-based compound in an amount of 0.01-2.0 pts.wt. based on 100 pts.wt. of the polyolefin resin and the deodorizing composition in an amount of 0.1-5 pts.wt. based on 100 pts.wt. of the polyolefin resin. The deodorizing composition is a mixture of one or more kinds consisting essentially of a fatty acid amide compound, an amine compound, a metal salt of a carboxylic acid, a betaine compound, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a low-odor polyolefin resin composition.
The present invention relates to reducing the unpleasant odor generated by the decomposition and degradation of polyolefin resin due to a sterilization treatment or a curing treatment of an adhesive or the like, and to provide a suitable package in the food packaging field and the medical and pharmaceutical field.

[0002]

2. Description of the Related Art Conventionally, polyolefin resins have been widely used as materials for medical devices and as materials for various packages such as food packaging, pharmaceutical packaging, cosmetic packaging in the field of printing and laminating. Ink, in the fields of sterilization of medical instruments, printing and laminating
The use of ionizing radiation is increasing as a means of instantly curing a coating agent or an adhesive to improve productivity.

However, when a polyolefin resin is irradiated with ionizing radiation, the energy of the ionizing radiation is extremely high, which significantly affects the polyolefin resin and is extremely brittle due to a decrease in mechanical strength due to decomposition and deterioration of the resin. It had many practical disadvantages such as discoloration, generation of decomposition odor and coloring.

Therefore, various proposals have been made as means for solving the decomposition and deterioration of the polyolefin resin due to the irradiation of ionizing radiation. For example, a radiation-resistant polyolefin resin composition in which a specific hindered amine-based compound, a phenol-based compound, or a phosphite-based compound is added to a polyolefin resin to prevent decomposition and deterioration of the resin due to irradiation is disclosed. Also disclosed is a radiation-resistant molded article in which the use of a random ethylene-propylene copolymer resin having a specific ethylene content suppresses deterioration of physical properties due to irradiation in the same manner as described above.

[0005] However, these polyolefin resins have been described as being improved with respect to mechanical properties such as elongation and impact strength, and problems of film coloring, but at present, odor is not studied at all. fact,
When a polyolefin resin is irradiated with ionizing radiation, a large amount of volatile oxides such as alcohols, aldehydes, ketones, and carboxylic acids are mainly generated by oxidative decomposition, causing an unpleasant odor. Among these substances, carboxylic acid has a particularly strong odor and has a low threshold value that humans perceive as an odor, and is therefore considered to be the main component of the offensive odor. So, what is conventionally known as a means of removing malodorous components is a plastic such as polyolefin resin, activated carbon, silica gel, alumina gel, silica sol, activated clay, acid clay, zeolite, etc. There is a method in which a substance is added and a malodorous component is physically adsorbed to these substances.

However, the above-mentioned method using an inorganic porous material does not have the ability to adsorb all kinds of odors, so that the deodorizing efficiency for the volatile oxides generated by the above-mentioned irradiation with ionizing radiation is low. Low and practically problematic. Therefore, even in such a method, the improvement of the odor of the polyolefin resin irradiated with ionizing radiation is insufficient, and in particular, when used for food packaging applications that dislike the adsorption of off-flavor components to the contents, it is not sufficient. Did not have satisfactory performance.

[0007] Further, since the above-mentioned inorganic porous material easily absorbs water, if the operation for removing water is not performed or is insufficient, plastic such as polyolefin resin is generally melted and heated. It is intended to be molded into a desired shape, and therefore, there may be a problem in processing suitability such that foaming of residual moisture occurs due to heat at the time of molding and molding cannot be performed.Furthermore, among the inorganic porous materials, Some of them have a problem of coloring after molding, and there are many obstacles in practical use other than odor.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and has as its object to sterilize and instantly cure inks, coating agents and adhesives. In addition to suppressing the decrease in the mechanical strength of the polyolefin resin by the irradiation of ionizing radiation, the degradation odor generated from the polyolefin resin is improved, and strict demands are made for off-flavors in the food packaging and medical fields. An object of the present invention is to provide a low-odor polyolefin resin composition useful for use in the field of medicine and a low-odor polyolefin resin molded article using the same.

[0009]

In order to achieve the above object, the present invention provides a polyolefin resin comprising at least one of a phenolic compound, a hindered amine compound, a phosphorus compound, A low-odor polyolefin resin composition characterized by adding a deodorizing composition having a deodorizing function by the above-described chemical neutralization reaction.

In the invention of claim 2, the mixing ratio of the polyolefin resin, the phenolic compound, the hindered amine compound, the phosphorus compound, and the deodorizing composition is such that the phenolic compound is added to 100 parts by weight of the polyolefin resin. 0.005 to 0.3 parts by weight, hindered amine compound 0.05 to 2.0 parts by weight, phosphorus compound 0.
The low-odor polyolefin resin composition according to claim 1, wherein the amount is 0.1 to 2.0 parts by weight and the deodorizing composition is 0.1 to 5 parts by weight.

[0011] In the invention according to claim 3, the deodorizing composition is one kind mainly composed of a fatty acid amide compound, an amine compound, a metal carboxylate, a betaine compound, an inorganic oxide, and an inorganic hydroxide. A low odor polyolefin resin composition according to claim 1 or 2, which is a mixture of two or more of these.

Further, in the invention of claim 4, the metal carboxylate, the betaine compound, the inorganic oxide, and the inorganic hydroxide are at least selected from Mg, Zn, Al, Si, K, Ca, and Ni. The low odor polyolefin resin composition according to any one of claims 1 to 3, comprising at least one kind.

Furthermore, in the invention of claim 5, the low-odor polyolefin resin composition according to any one of claims 1 to 4 is molded into a desired shape to produce a food, beverage or medicine. It is a low-odor polyolefin resin molded product characterized by being used as a package or a medical device to be packaged.

[0014]

Embodiments of the present invention will be described below. As the polyolefin resin used in the present invention,
Ethylene, propylene, 1-butene, 1-pentene, 1
-Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-
Tridecene, 1-pentadecene, 1-hexadecene, 1
-Heptadecene, 1-octadecene, 3-methyl-1-
Homopolymers of α-olefins such as butene, 4-methyl-1-pentene and 4,4-dimethyl-1-pentene, or copolymers using two or more thereof, or these α-olefins as main components Random, block, graft copolymers with other monomers such as vinyl esters such as vinyl acetate and unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters, and also polymers of these. Which have been subjected to a modification treatment such as chlorination, sulfonation, or oxidation, and a mixture of these polymers. These polymers are those polymerized by a multisite catalyst whose active sites are heterogeneous,
Alternatively, it may be polymerized by a single-site catalyst having a uniform active site.

Among the above-mentioned polymers, those showing particularly remarkable effects include polypropylene homopolymer, propylene-ethylene-random or block copolymer, ethylene-propylene-butene copolymer, and ethylene-butene copolymer. And propylene (co) polymers such as ethylene-4-methyl-pentene copolymer, propylene-hexene copolymer and propylene-hexene-butene copolymer.

The phenolic compound used in the present invention may be a hindered phenol compound mainly used as an antioxidant, for example, 2,6-di-t-
Butyl-4-methylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-t-
Butyl-4-methoxyphenol, 2,2′-methylene-bis- (6-t-butyl-4-methylphenol),
2,2′-methylene-bis- (6-t-butyl-4-ethylphenol), 2,2′-methylene-bis-[(4
-Methyl-6- (α-methylcyclohexyl) phenol], 1,1′-bis- (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,2′-bis-
(5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,2′-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 1,1 ′, 3
-Tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,2'-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-dodecylmercaptan, Ethylene glycol-bis-
[3,3-bis- (3'-t-butyl-4'-hydroxyphenyl) butyrate], 1,3,5-trimethyl-
2,4,6-tris- (3,5-di-t-butyl-4-
Hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester,
N, N'-hexamethylenebis- (3,5-di-t-butyl-4-hydroxy-hydroxynamamide), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis- [3- (3,5-di-t- Butyl-4-
Hydroxyphenyl) propionate].

The amount of the phenolic compound added is 0.005 to 100 parts by weight of the polyolefin compound.
0.3 parts by weight, preferably 0.01 to 0.15 parts by weight. If the addition amount is less than 0.005 parts by weight, the improvement of the odor generated from the polyolefin resin after the irradiation of ionizing radiation, which appears as a synergistic effect of each additive compound, becomes insufficient,
In addition, even if added in an amount exceeding 0.3 parts by weight, the odor improving effect reaches equilibrium, so that not only is it not economical, but also in some compounds, there is a problem of coloring of the polyolefin resin after irradiation with ionizing radiation. There are cases.

The hindered amine compound used in the resin composition of the present invention is a hindered amine compound having a 2,2,6,6-tetramethylpiperidine structure, for example, 4-benzoyloxy-2,2,2.
6,6-tetramethylpiperidine, 4-hydroxy-
2,2,6,6-tetramethylpiperidine, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine,
Bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (2,2,6,6-tetramethyl-4-N-methylpiberidyl) fumarate, di-
(1,2,2,6,6-pentamethyl-4-piperidyl) -2-n-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis- (2
2,6,6-tetramethyl-4-carbonyloxypiperidino) -p-dimethylbenzyl, poly-[{6-
(1,1,3,3, tetramethylbutyl) imino-1,
3,5-triazine-2,4-diyl) {(2,2
6,6-tetramethyl-4-piperidyl) imino} -hexamethylene-{(2,2,6,6-tetramethyl-4
-Piperidyl) imino}], poly-[{6-morpholino-1,3,5-triazine-2,4-diyl} 4-
(2,2,6,6-tetramethylpiperidyl) imino｝
-Hexamethylene- {4- (2,2,6,6-tetramethylpiperidyl) imino}], dimethyl succinate 1-
(2-hydroxyethyl) -4-hydroxy-2,2,
6,6-tetramethylpiperidine polycondensate, N, N'-
Bis (3-aminopropyl) ethylenediamine 2,4
-Bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-
1,3,5-triazine condensate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-
Triazaspiro [4,5] decane-2,4-dione, 1
-[2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4-
[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6, tetramethylpiperidine and the like can be exemplified.

The amount of the hindered amine compound added is 0.0 to 100 parts by weight of the polyolefin compound.
It is 5 to 2.0 parts by weight, preferably 0.1 to 0.5 parts by weight. When the addition amount is less than 0.05 parts by weight, the improvement of the odor generated from the polyolefin resin after the irradiation of ionizing radiation, which appears as a synergistic effect of each additive compound, becomes insufficient,
Further, even if it is added in excess of 2.0 parts by weight, the improvement effect reaches equilibrium, so that it is not economical.

The phosphorus compounds used in the present invention include phosphite compounds and phosphonite compounds mainly used as antioxidants or processing stabilizers. For example, distearyl-pentaerythritol-
Diphosphite, 2,2-methylenebis- (4,6-di-t-butylphenol) octyl phosphite, bis- (2,4,6-tri-t-butylphenyl) pentaerythritol-diphosphite, tris- (2,4 -Di-t-butylphenyl) phosphite, tris- (2,
5-di-t-butylphenyl) phosphite tris-
(2-t-butylphenyl) phosphite, tris-
[2- (1,1-dimethylpropyl) phenyl] phosphite, tris- (2,4-di-t-butyl-5-methylphenyl) phosphite, tris-phenyl phosphite, tris-nonyl phosphite, tris ( Mono-nonylphenyl) phosphite, tris- (mono-dinonylphenyl) phosphite, tris- (3,5-di-t
-Butyl-4-hydroxyphenyl) phosphite, bis- (2,6-di-t-butyl-4-methylphenyl)
Pentaerythritol-diphosphite, cyclic-neopentan-tetrayl-bis- (2,4-di-t
-Butylphenyl-phosphite), cyclic-neopentan-tetrayl-bis- (octadecyl-phosphite), cyclic-neopentan-tetrayl-bis- (2,6-di-t-butyl-4-methylphenyl-phospho). Fight), 4,4-butylidene-bis (3
-Methyl-6-t-butylphenyl-di-tridecyl)
Phosphite, 4,4-butylidene-bis- (3-methyl-4,6-t-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris- (2-methyl-4-
Di-tridecylphosphite-5-t-butylphenyl) butane, bis- (2,4-di-t-butylphenyl) -spiropentaerythritol-diphosphite,
Bis- (2,6-di-t-butyl-4-methylphenyl) -spiropentaerythritol-diphosphite,
Bis- (2,4,6-tri-t-butylphenyl) -spiropentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-diphosphonite, tetrakis (2,4 -Di-t-butyl-5-methylphenyl) -4,4-biphenylene-diphosphonite.

The amount of the phosphorus compound to be added is 0.01 to 2.0 parts by weight based on 100 parts by weight of the polyolefin compound.
4 parts by weight, preferably 0.02 to 1.2 parts by weight. When the addition amount is less than 0.01 parts by weight, not only is the improvement in the odor generated from the polyolefin resin after ionizing radiation irradiation appearing as a synergistic effect of each additive compound insufficient, but also the processing stability of the polyolefin resin is reduced. There is a possibility that it cannot be obtained. Further, even if added in excess of 2.0 parts by weight, the effect of improving odor and processing stability reaches equilibrium, so that it is not economical. Furthermore, since the phosphorus-based compound has an effect of suppressing the problem of coloring caused by the result of the phenol-based compound acting to prevent deterioration of the resin, when determining the amount of the phosphorus-based additive, the phosphorus-based compound and the phenol-based compound The weight ratio of the phosphorus compound is 1: 2 to 1: 8.
It is desirable to set so that If the weight ratio of the phenolic compound to the phosphorus compound is less than 1: 2, the polyolefin resin may have a problem of coloring, and the weight ratio of the phenolic compound to the phosphorus compound may be 1: 1:
If it exceeds 8, it is not economical and therefore not preferable.

Furthermore, the deodorizing composition used in the present invention is a composition having a deodorizing function by a chemical neutralization reaction, and alcohols, aldehydes, and the like, which are off-odor components generated from polyolefin resin by irradiation with ionizing radiation. It is used to deodorize volatile oxides such as ketones and carboxylic acids by a chemical reaction. In particular, among these components, those having the ability to deodorize carboxylic acids having a strong odor by a chemical reaction are desirable.

Examples of such deodorizing compositions include fatty acid amide compounds and amine compounds (eg, ROH-ROH-N
H), a carboxylic acid metal salt ^{(R-COO - M +)} , betaine compounds _{^{(eg: R 1,2,3 N + (··· X}} -) CH 2 CO
O ^- ··· M ^+), inorganic oxides, one or a mixture of two or more of these inorganic hydroxides. Further, it is desirable that the metal carboxylate, betaine compound, inorganic oxide, and inorganic hydroxide contain at least one or more selected from Mg, Zn, Al, Si, K, Ca, and Ni.

These deodorizing compositions have properties such as being free from coloring when melt-molded at a high temperature after being added to a polyolefin resin, and resistant to high temperatures of at least 150 ° C. or more. It is necessary. Furthermore, when these deodorizing compositions are added to a polyolefin resin, the deodorizing composition can be supported on a porous substance that does not impair the effects of the present invention.

The amount of the deodorizing composition to be added is 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the polyolefin compound. When the addition amount is less than 0.1 part by weight, the improvement of the odor generated from the polyolefin resin after ionizing radiation irradiation, which appears as a synergistic effect of each additive compound, becomes insufficient. In addition, the addition of more than 5 parts by weight can be expected to improve the deodorizing effect, but when the polyolefin resin composition is molded, there is a possibility that the transparency of the molded article may be reduced and there is no economic merit. There is a point.

The low odor polyolefin resin composition of the present invention may contain additional components, if necessary, in addition to the compounds described above, as long as the effects of the present invention are not impaired. Such additional components include, for example, benzophenone-based compounds, ultraviolet absorbers such as benzotriazole-based compounds, neutralizing agents such as calcium stearate, and further, antistatic agents, crosslinking agents, crosslinking assistants, antiblocking agents. , A lubricant, an inorganic filler, a nucleating agent, an anti-fogging agent, a pigment, a foaming agent and the like.

When the low-odor polyolefin resin composition is used for sanitary safety such as food packaging, the above-mentioned phenolic compound, hindered amine compound, phosphorus compound, deodorizing composition, etc. As a characteristic of the additional component, a compound whose safety has been confirmed by various toxicity tests may be used.

The low odor polyolefin resin composition of the present invention is generally prepared by adding the above-mentioned phenolic compound, hindered amine compound, phosphorus compound, deodorizing composition, and other additional components to a powdery or pelletized polyolefin resin. After blending with a mixer or the like, the mixture is melt-kneaded with a kneading machine such as an extruder, a kneading roll machine, or a Brabender plastograph. Thus, the melt-kneaded resin composition is pelletized and subjected to various molding processes.

The pelletized resin composition is formed into a film or sheet having a desired thickness by, for example, an extruder, or a container or the like having a desired shape is formed by an injection molding machine or a blow molding machine. By molding the device, it is possible to obtain a package using the low odor polyolefin resin composition of the present invention.

The low-odor polyolefin resin molded product formed into a film or a sheet is further processed into a bag-like package or a lid material for container packaging, and is put to practical use. Three- or four-sided seal bags, gasket seals (pillows)
Bags, gusset bags, standing bags, stick packages, strip packages, bag-in-boxes, laminate tubes, and the like. Examples of the lid material for container packaging include lid materials such as deep-drawing packaging containers and injection-molded cup containers. Examples of the polyolefin resin molded product molded into a container or an instrument include a deep-drawing packaging container and an injection molded cup container as a container package, and examples of an instrument include a medical syringe, tweezers, and a clamp. And the like.

In order to obtain the low-odor polyolefin resin molded product of the present invention, each component may be added to the polyolefin resin, blended, and then directly molded.

When the low-odor polyolefin resin molded product of the present invention obtained as described above is subjected to irradiation with ionizing radiation for sterilization and curing of inks, coating agents and adhesives, mainly electron beams, γ rays and ultraviolet rays are emitted. Although it is used, it has a characteristic that it has an extremely high effect even when irradiated with an electron beam or γ-ray, which has a relatively high energy among such ionizing radiations and is likely to cause degradation of the resin by irradiation. ing. The energy dose of the electron beam or γ-ray used in the above applications is generally 10 to 300 kGy,
The resin molded article made of the low-odor polyolefin resin composition of the present invention has an extremely high effect in suppressing generation of an unusual odor due to irradiation of ionizing radiation within such an energy range.

As described above, the low-odor polyolefin resin composition of the present invention can be sterilized or coated by blending a specific deodorizing composition in addition to a phenolic compound, a hindered amine compound, and a phosphorus compound. When ionizing radiation is applied to instantaneously cure the chemical, the phenolic compound, hindered amine compound, and phosphorus compound suppress the decomposition and deterioration of the resin, which is not enough. The effect can be greatly improved by adding a specific deodorizing composition. Furthermore, a molded product obtained by molding the low-odor polyolefin resin composition into a desired shape is irradiated with ionizing radiation even when used in a food packaging field or a medical / pharmaceutical field in which strict demands are made particularly for off-flavors. Since practically no odor is generated from the polyolefin resin, it becomes extremely practical. This greatly contributes to the expansion of the application field of the technology using ionizing radiation.

[0034]

Next, the present invention will be described in detail with reference to examples. <Example 1> Powder-like propylene-ethylene random copolymer (ethylene content 3.0 wt%, MFR = 6
g / 10 min) 100 parts by weight of the phenolic compound Yoshinok 2246G in an amount as shown in Table 1.
0.03 parts by weight (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), 0.3 parts by weight of hindered amine compound, CHIMASSORB-944LD (manufactured by Ciba Specialty Chemicals), 0.1 part by weight of phosphorus compound, IRGAFOS-168 (manufactured by Ciba Specialty Chemicals) Parts and 0.25 parts by weight of a deodorizing composition, Dime Shoe 6000P (manufactured by Dainichi Seika Kogyo Co., Ltd.), and 0.05 parts by weight of calcium stearate and 0.02 parts by weight of a lubricant were further added as neutralizing agents. After that, dry blending was performed by a mixer. Then
Using a 30 mmφ twin screw extruder, the mixture was kneaded into a bellet at a temperature of 220 ° C. Next, a 40 mmφ extruder was used to perform melt extrusion at an extrusion temperature of 240 ° C.
A 0 μm film specimen was prepared.

Example 2 A film test piece was obtained in the same manner as in Example 1 except that the deodorizing composition was 2.0 parts by weight of Dime Shoe 6000P (manufactured by Dainichi Seika Kogyo Co., Ltd.).

Example 3 A phenolic compound represented by I
0.04 parts by weight of RGANOX-1076 (manufactured by Ciba Specialty Chemicals), 0.5 parts by weight of TINUVIN-783 (manufactured by Ciba Specialty Chemicals) as a hindered amine compound, phosphorus compound / IRGAF
OS-168 (manufactured by Ciba Specialty Chemicals)
0.2 parts by weight, and a deodorizing composition / dimme shoe 60
A film test piece was obtained in the same manner as in Example 1, except that 0.5 parts by weight of 00P (manufactured by Dainichi Seika Kogyo KK) was used.

Example 4 The pelletized polyolefin resin composition obtained by the same formulation as in Example 1 was injected with an injection molding machine at an injection temperature of 230 ° C. and an injection pressure of 700.
kg / cm ² , thickness 1.0mm, size 10c
An mx 10 cm sheet test piece was obtained.

Example 5 The pelletized polyolefin resin composition obtained by the same formulation as in Example 2 was injected with an injection molding machine at an injection temperature of 230 ° C. and an injection pressure of 700.
kg / cm ² , thickness 1.0mm, size 10c
An mx 10 cm sheet test piece was obtained.

Example 6 The pelletized polyolefin resin composition obtained in the same manner as in Example 2 was injected with an injection molding machine at an injection temperature of 230 ° C. and an injection pressure of 700.
kg / cm ² , thickness 1.0mm, size 10c
An mx 10 cm sheet test piece was obtained.

Comparative Example 1 A film test piece was obtained in the same manner as in Example 1 except that the deodorizing composition was not added.

Comparative Example 2 A sheet test piece was obtained in the same manner as in Example 4, except that the deodorizing composition was not added.

Obtained in Examples 1 to 3 and Comparative Example 1
The film test piece was subjected to an acceleration voltage of 200 in a nitrogen atmosphere.
irradiate with an electron beam under the conditions of kV and an absorbed dose of 30 kGy,
The off-flavor generated from the test specimen after electron beam irradiation is as follows
The evaluation was performed according to the evaluation method shown below. Table 1 shows the results.
did. [Evaluation method] 1) Evaluation of odor The film test pieces obtained in Examples 1 to 3 and Comparative Example 1 were:
After irradiation with electron beam, the surface area is 2000cm^TwoCut to be
Removed, packed in a mayonnaise bottle and stored at room temperature for 3 days
Thereafter, it was used for sensory evaluation of odor. In addition, as a comparative sample
Commercial propylene-ethylene that does not irradiate ionizing radiation
30 μm thick film made of random copolymer
With a surface area of 2000 cm ^TwoCut so that
After filling in a yonais bottle and storing it at room temperature for 3 days,
It was used for performance evaluation. The sensory evaluation, by a pairwise comparison method,
The film test pieces of Examples 1 to 3 are films of Comparative Example 1.
Three types of test pieces and commercially available films not irradiated with electron beam
The test was carried out by comparing odors. Furthermore, the systems of Examples 4 to 6
The test piece was a mayonnaise bottle of the sheet test piece of Comparative Example 2.
It was carried out in a form to be compared with the odor inside. The number of panelists is 1
Performed by 5 people, ○: good with little off-flavor (1% superior level),
×: Many off-flavors were poor (1% superior level),-: No difference in off-flavors
(1% superior level). 2) Evaluation of coloring property Judgment was made by visual observation, ：: good (no coloring), △: little
Good (slightly yellowing), x: poor (yellowing).

Further, the sheet test pieces obtained in Examples 4 to 6 and Comparative Example 2 were irradiated with γ-rays from a cobalt 60 radiation source so as to have an absorbed dose of 30 kGy. The off-flavor generated was evaluated in the same manner as described above. The results are also shown in Table 1. In addition,
After the electron beam irradiation, the sheet test pieces of Examples 4 to 6 and Comparative Example 2 were packed in a mayonnaise bottle in their original shape, stored at room temperature for 3 days, and then used for sensory evaluation of odor.

[0044]

[Table 1]

From the results of the sensory tests shown in Table 1, it was confirmed that all the examples had a lower level of off-flavor than the comparative example at a significance level of 1%. In addition, when the test piece according to the present example was compared with a commercially available film that was not irradiated with ionizing radiation, no significant difference was observed at a significant level of 1%. The molded film was found to have an odor level approximately equal to that of a commercial film that was not irradiated with ionizing radiation. Furthermore, in all examples of the present invention, occurrence of other practical problems such as coloring of the test piece and reduction in mechanical strength were not observed,
It was confirmed that the composition also had excellent performance in balance.

[0046]

As described above, the present invention has the following effects. That is, a phenolic compound, a hindered amine compound, a phosphorus compound, and a deodorizing composition having a deodorizing function by at least one chemical neutralization reaction are added to a polyolefin resin. The compounding ratio of the compound, the hindered amine compound, the phosphorus compound, and the deodorizing composition is such that the phenolic compound is 0.005 to 0.3 parts by weight, the hindered amine compound is 0.05 to 2 parts with respect to 100 parts by weight of the polyolefin resin. 0.0 parts by weight, 0.01 to 2.0 parts by weight of a phosphorus compound, 0.1 of a deodorant composition
In an amount of from 5 to 5 parts by weight, the deodorizing composition contains one or more of a fatty acid amide compound, an amine compound, a metal carboxylate, a betaine compound, an inorganic oxide, and an inorganic hydroxide as main components. Since the mixture is a low-odor polyolefin resin composition, not only the decomposition and deterioration of the resin due to ionizing radiation can be suppressed, but also the off-odor generated after irradiation with ionizing radiation can be extremely reduced.

[0047] Therefore, by using the polyolefin resin composition of the present invention to prepare molded instruments, containers and packaging bags in the field of medical medicine and food packaging which are subjected to sterilization treatment by electron beam or γ-ray, even after sterilization treatment. It is possible to extremely reduce the unpleasant odor, and to differentiate the product from other products.

Further, by using the low-odor polyolefin resin composition of the present invention, films and sheets used in the field of curing inks, coating agents and adhesives by using an electron beam are produced. In particular, the food packaging field which is difficult to use due to the generation of off-flavors at present, such as snacks, hygroscopic foods, processed oils and fats, chilled / frozen foods, standing bags, bags-in-boxes, laminate tubes, and packaging for boiling It can be used for a body, a liquid paper container, various trays to be deep drawn, a lid material, and the like.

As described above, according to the present invention, not only the generation of an unpleasant odor from the polyolefin resin by irradiation with ionizing radiation is improved, but also the use of ionizing radiation is expected to significantly improve productivity and quality. On the other hand, the range of application can be expanded to fields where the use has not progressed slowly, and it is possible to make an extremely large contribution to the industry.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/13 C08K 5/17 5/17 5/20 5/20 5/49 5/49 A61J 1/00 331A F-term (reference) 4F100 AA04A AA17A AA17H AA18A AA18H AA19A AA19H AA20A AA20H AA24A AA24H AA25A AA25H AH02A AH02H AH03A AH03H AH08A AH08H AK03A AK64 AL05A BA01 CA30A GB17 GB23 GB66 JB20 JD14A JD14H YY00A YY00H 4J002 BB001 BB031 BB121 BB161 DE059 DE079 DE089 DE099 DE109 DE149 EG009 EJ016 EJ026 EJ036 EJ046 EN009 EP009 EU077 EU087 EU187 EU237 EW068 EW128 FD076 FD078 GB01 GG02

Claims (5)

[Claims] 1. A polyolefin resin comprising a phenolic compound, a hindered amine compound, a phosphorus compound, and a deodorizing composition having a deodorizing function by at least one chemical neutralization reaction. Low odor polyolefin resin composition. 2. The compounding ratio of the polyolefin resin, the phenolic compound, the hindered amine compound, the phosphorus compound, and the deodorizing composition is 100 parts by weight of the polyolefin resin.
Phenolic compound 0.005 to 0.3 part by weight
2 parts by weight, 0.05 to 2.0 parts by weight of a hindered amine compound, 0.01 to 2.0 parts by weight of a phosphorus compound, and 0.1 to 5 parts by weight of a deodorizable composition.
The low odor polyolefin resin composition according to the above. 3. The deodorizing composition comprises one or more of a fatty acid amide compound, an amine compound, a metal carboxylate, a betaine compound, an inorganic oxide and an inorganic hydroxide as a main component, or a mixture of two or more thereof. The low odor polyolefin resin composition according to claim 1 or 2, wherein 4. The metal salt of a carboxylic acid, a betaine compound,
Inorganic oxides and hydroxides are Mg, Zn, Al, S
4. The method according to claim 1, wherein at least one selected from i, K, Ca, and Ni is contained.
Item 6. The low-odor polyolefin resin composition according to item 1. 5. A package, a medical device, or the like, which is formed into a desired shape by using the low-odor polyolefin resin composition according to any one of claims 1 to 4, and is used to package food, beverages, pharmaceuticals, and the like. A molded article of a low-odor polyolefin resin, characterized in that: