JPH111624A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition exhibiting a high CO2 gas/O2 gas permeability ratio, having good antibacterial and antifungal properties and good appearance, being odorless and improved in gas barrier properties, etc., by mixing a thermoplastic resin with a hinokithiol compound, an inorganic filler and a polyglycerol fatty acid ester in a specified ratio. SOLUTION: The thermoplastic resin (A) is at least one member selected among polyvinyl chloride, ethylene/vinyl acetate copolymer saponificate resins, polyolefin resins, etc. The hinokithiol compound (B) used is at least one member selected from among hinokithiol itself, its salt or a cyclodextrin inclusion compound containing it. The inorganic filler (C) is desirably silicic acid, a silicate or a carbonate. The polyglycerol fatty acid ester (D) is desirably diglycerol monosterate or the like. This compositoin is prepared by mixing 100 pts.wt. component A with 0.1-1.0 pt.wt. component B, 0.05-2.0 pts.wt. component C and 0.05-1.5 pts.wt. compoennt D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition useful as a packaging material for foods and medical use which excels in selective permeability of carbon dioxide gas to oxygen gas, antibacterial and antifungal properties, appearance and odor. About. The thermoplastic resin composition of the present invention is particularly useful as a packaging material for fresh foods such as fruits and vegetables, fresh fish and meat.

[0002]

2. Description of the Related Art Conventionally, polyolefin resins are lightweight,
Due to its excellent transparency, mechanical strength, heat resistance, chemical resistance, oil resistance, etc., it is widely used in various fields. In recent years, with the enhancement of functions and cost reduction, there has been a demand for improved characteristics of materials. For example, a polyolefin resin is a hydrophobic resin and thus has an excellent steam barrier property, and is used in various packaging fields utilizing the same.

In general, vegetables, root vegetables, fruits, flowers, flowers and trees,
Mushrooms (hereinafter abbreviated as "vegetables") have shifted from conventional open-field cultivation to planned diversified cultivation through horticultural facility cultivation, employing means for producing, packaging, and transporting large quantities of fruits and vegetables. The problem in the distribution process of such fruits and vegetables before reaching the consumers is how to maintain the freshness of the fruits and vegetables when they are harvested.

[0004] Generally, fruits and vegetables continue the ripening process even after harvesting, causing changes such as changes in the aroma and color of the fruits and vegetables and softening of the flesh. Among the fruits and vegetables, the fruits, depending on the type,
If it grows to a certain stage, it does not wait for maturity, even when harvested when it is quite immature, the maturation effect is performed after harvesting,
Some are edible and can be served. The ripening phenomenon after harvesting such fruits and vegetables is called ripening, and this phenomenon is used to transport and store fruits and vegetables.
Or, on the contrary, they promote it.

[0005] Generally, the respiratory volume of fruits and vegetables differs depending on the type of fruits and vegetables. Therefore, the suitable gas permeation amount required for the freshness-keeping packaging material differs depending on the kind of fruits and vegetables. For example, Hiromi Sato, Yutaka Ishikawa, Takashi Hirata; Journal of the Packaging Society of Japan, Vol. 1, p1123-1128 (19
The CO ₂ gas / O ₂ gas transmission ratio required for packaging films of various fruits and vegetables based on the simulation disclosed in 93) is in the range of 6.0 to 8.5. A material having a transmission ratio can be said to be an ideal freshness preserving packaging material. Regarding the permeation ratio, Tadahiko Kuzu, Heiwao: New packaging material, p. 87, Kyoritsu Shuppan (1988) and Yutaka Ishikawa, Hiromi Sato, Kosuke Ishitani, Takashi Hirata: Journal of the Packaging Society of Japan, Vol. 2, p. 143-153 (1992).

[0006] Polyolefin resins are also used in the field of freshness-keeping packaging because of their relatively high gas permeability. However, the polyolefin resin has a low CO2 content.
₂ Gas / O ₂ gas permeability ratio is usually 5 or less, for the O ₂ gas permeation amount and the CO ₂ gas permeation amount, although it is possible by adjusting the thickness of the film, increasing the CO ₂ gas / O ₂ gas transmission ratio It was difficult to do.

As a method for increasing the selective transmission ratio,
There has been known a method in which an additive which easily dissolves carbon dioxide gas is blended to selectively enhance the permeability of carbon dioxide gas. For example, Takeda, Yamaguchi: Journal of the Industrial Chemistry, Vol. 62, p1897 (19
59) describes that the addition of a plasticizer such as a phthalic ester to polyvinyl chloride increases the permeability of carbon dioxide gas. However, in such a method, there is a potential problem that the plasticizer bleeds over time, and there is a limitation on use.

On the other hand, the water vapor transmission amount is an important factor for maintaining the freshness together with the gas transmission amount.
It is said that it only has to be in the range of g / m ² · day.
That is, when the amount is less than 5 g / m ² · day, mold is generated, and when the amount exceeds 80 g / m ² · day, the fruits and vegetables are liable to wither due to evaporation of moisture.

Therefore, as a conventional technique for preventing the ripening action of fruits and vegetables and extending the transportation and storage period, there is known a method of adsorbing ethylene which causes an increase in respiratory action accompanying ripening of fruits and vegetables ( For example, JP-A-56
JP-878752, JP-A-63-110186, JP-A-63-277249, etc.). In addition, a method using a film in which a number of fine holes are opened (for example, Japanese Patent Publication No. 8-11036, Japanese Patent Publication No.
7, JP-A-62-235086, JP-A-4-3
Many methods have been proposed.

[0010] Further, as a method of preventing decay due to the growth of microorganisms (for example, mold) after harvesting, fruits and vegetables are washed with saline or chlorine water, or an alcohol preparation or other antibacterial substance is added to a synthetic resin film or nonwoven fabric. Blending,
There have been proposed methods of storing the coated product together with fruits and vegetables in a cardboard box or a synthetic resin film package, or spraying the antibacterial agent directly into a mist.

[0011] However, these prior arts are still insufficient in their effect on keeping freshness. Further, after harvesting, washing the fruits and vegetables and putting the fruits and vegetables in a cardboard box or a synthetic resin package together with alcohol and other antibacterial substances were complicated. The method of surface coating has a large loss of antibacterial substances, has a low effect of maintaining freshness, and is difficult to control. The method of opening many fine holes in the film not only has an insufficient freshness retention effect, but also leads to impact resistance and tear resistance. There is a problem that the bag is easily broken at the time of distribution or at the distribution stage.

Further, JP-A-4-359028 discloses a food having a layer in which hinokitiol, a salt thereof or a conjugate of cyclodextrin is added to linear low-density polyethylene or ethylene-vinyl acetate copolymer. A packaging film is described and further teaches the addition of glycerin fatty acid esters or polyglycerin fatty acid esters to impart self-adhesion, anti-fog properties and the like to the film.

However, as described in JP-A-4-359028, a film of a polyethylene or an ethylene-vinyl acetate copolymer containing a hinokitiol compound and a (poly) glycerol fatty acid ester has good self-adhesiveness and anti-adhesion properties. Shows cloudiness and water vapor permeability, but with CO2
_{The 2} gas / O ₂ gas permeation ratio was low, the antibacterial and antifungal properties could not be said to be sufficient, and the film was yellowish, its appearance was poor, and in addition, it had an unpleasant odor.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high CO ₂ gas / O ₂ gas permeation ratio, good antibacterial and antifungal properties and appearance, no odor, and a better gas barrier. It is an object of the present invention to provide a thermoplastic resin composition having properties, water vapor barrier properties, and rigidity, and particularly suitable as a packaging material useful for maintaining the freshness of fresh foods such as fruits and vegetables, fresh fish and meat.

[0015]

The object of the present invention is to provide at least one kind selected from (B) hinokitiol and a salt thereof and a cyclodextrin clathrate containing them per 100 parts by weight of a thermoplastic resin. 0.1 to 1.0 parts by weight of a hinokitiol compound, 0.05 to 2.0 parts by weight of (C) an inorganic filler, and 0.05 to 1.5 parts by weight of (D) a polyglycerol fatty acid ester. The problem is solved by a thermoplastic resin composition characterized in that:

Hereinafter, the thermoplastic resin composition of the present invention will be specifically described. The thermoplastic resin as the component (A) of the thermoplastic resin composition of the present invention is not particularly limited,
Generally, a thermoplastic resin having a film or sheet forming property is widely used. Specific examples thereof include polyvinyl chloride, polyvinyldene chloride, saponified ethylene vinyl acetate copolymer resin, polyamide, polyester, polystyrene, polycarbonate, and polybutylene and polymethylpentene, low-density polyethylene, linear low-density polyethylene, Copolymer of ethylene and α-olefin having 3 to 12 carbon atoms, polypropylene, ethylene-vinyl acetate copolymer resin, ethylene-alkyl ester-maleic anhydride terpolymer, ethylene-alkyl ester-glycidyl ternary Examples include polyolefin resins such as copolymers and ionomer resins. These may be used alone or as a mixture of two or more.

Among thermoplastic resins, polyolefin resins are particularly preferable because they have excellent steam barrier properties, gas barrier properties, transparency and a CO ₂ gas / O ₂ gas transmission ratio.
Polyolefin-based resins include ethylene, propylene, 1-
A homopolymer of an α-olefin having 12 or less carbon atoms such as butene, 1-hexene and 3-methyl-1-pentene, a random or block copolymer of these α-olefins, or an α-olefin as a main component And copolymers thereof with ethylenically unsaturated monomers such as vinyl acetate, acrylic acid, methacrylic acid, alkyl acrylate and alkyl methacrylate.
Specific examples include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene elastomer, ethylene-1-butene elastomer, and ethylene-propylene-1-butene random copolymer. Polymer, ethylene-propylene block copolymer, ethylene-propylene-1-butene block copolymer, ethylene-vinyl acetate copolymer, propylene-1-butene random copolymer, ethylene-acrylic acid copolymer, ethylene -Ionomer resins which are methacrylic acid copolymers or metal salts thereof.

As the hinokitiol compound as the component (B), at least one selected from hinokitiol itself, a salt thereof, and a cyclodextrin inclusion compound containing the same is used. Hinokitiol is a seven-membered cyclic aromatic compound, and has a chemical name called β-tujaprisin, 4-isopropyltropolone, 4-isopropyl-2-hydroxy-2,4,6-cycloheptatrien-1-one, and the like.

Hinokitiol has an antibacterial and antifungal action and is used as a material for keeping freshness, medicines, cosmetics and the like, and there are natural products and synthetic products extracted from natural hinoki trees. Regarding the general properties of hinokitiol, see Dai-Okagaku Kagaku, Vol. 13, "Non-benzene-based aromatic ring compounds", Asakura Shoten (1967), Japan Food Science 1989.
April issue, p. 49-58 and ibid, September 1992, p. 41-48.

As a method for maintaining freshness using hinokitiol, a method using a synthetic resin film containing hinokitiol (for example, JP-A-3-167261,
JP-A-4-325069, JP-A-4-35902
No. 8, JP-A-4-359029), and a method using a synthetic resin film printed with a printing ink containing hinokitiol (for example, JP-A-6-16).
990, etc.).

In the above-mentioned examples of JP-A-3-167261, the carbon dioxide / oxygen gas transmission ratio of a linear low-density polyethylene film containing hinokitiol is described, and the ratio is only 3.5. And small ones.
Further, the publication discloses adjusting the thickness of the film as a method of increasing the selective transmission ratio. The hinokitiol compound as the component (B) of the present invention contains, in addition to hinokitiol itself, metal salts such as hinokitiol sodium and potassium salts and other salts (including complex salts, double salts and the like), or hinokitiol and its salts. Cyclodextrin inclusion compound, that is, α in which hinokitiol or a salt thereof is included in the hollow portion of the cyclic structure
Inclusion compounds such as-, β-, or γ-cyclodextrin.

As the inorganic filler of the component (C), carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide,
Oxides such as zinc oxide and magnesium oxide, silicates such as aluminum silicate, magnesium silicate (talc) and calcium silicate, and carbides such as silicic acid, graphite and carbon black.

Of these, silicic acid, silicates and carbonates are particularly preferred because of their excellent barrier property improving effect. Specific examples of silicic acid and silicate include silicic anhydride, hydrous silicic acid, hydrous calcium silicate, hydrous silicium aluminum and magnesium silicate. These may be natural products or synthetic products and may be used without any particular limitation. Specific examples of the carbonate include precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, and the like. Particularly, calcium carbonate is preferably used.

The polyglycerin fatty acid ester of the component (D) is an esterification product of polyglycerin obtained by polymerizing glycerin and a fatty acid, and is generally used as an antifogging agent. Specific examples of polyglycerin fatty acid esters include diglycerin laurate, diglycerin stearate, diglycerin oleate, diglycerin caprylate, diglycerin monolaurate, diglycerin monostearate, diglycerin monooleate, diglycerin laurate And diglycerin oleate. Among these, diglycerin monostearate and diglycerin monooleate are preferred.

With respect to the mixing ratio of the above components (A) to (D) of the present invention, the hinokitiol component (B), its salt, and the cyclodextrin clathrate containing them are added to 100 parts by weight of the thermoplastic resin (A). At least one hinokitiol compound selected from the group consisting of 0.1 to 1.
0 parts by weight, (C) 0.05 to 2.0 parts by weight of an inorganic filler and (D) 0.0% by weight of a polyglycerin fatty acid ester.
It is advisable to mix in the range of 5 to 1.5 parts by weight.

Preferably, 0.2 to 0.9 parts by weight of component (B), 0.07 to 1.8 parts by weight of component (C), and 0.1 to 1.0 parts by weight of component (D) based on 100 parts by weight of component (A). It is good to mix | blend in the range of 1-1.3 weight part. Particularly preferably, with respect to 100 parts by weight of the component (A), 0.3 to 0.8 parts by weight of the component (B), 0.08 to 1.6 parts by weight of the component (C), and 0.2 of the component (D). It is good to mix in the range of -1.2 parts by weight.

When the amount of the component (B) is less than 0.1 part by weight with respect to 100 parts by weight of the component (A), the effect of maintaining freshness is inferior. On the other hand, when it exceeds 1.0 part by weight, the coloring of the molded article becomes large, and the appearance of the molded article is spoiled, which is not preferable. If the amount of the component (C) is less than 0.05 part by weight, the effect of improving the selective permeability of carbon dioxide gas to oxygen gas, antibacterial properties, antifungal properties, and odor is poor. On the other hand, if it exceeds 2.0 parts by weight, transparency and impact resistance are impaired, which is not preferable.

The component (D) has no effect on the component (A) when used alone or when used in combination with the component (B). When the component (D) is used in combination with the above components (B) to (C), The selective permeation between carbon dioxide gas and oxygen gas is large, and the freshness maintaining effect is excellent. The mixing ratio of the component (D) is from 0.05 to 1. 1 part by weight based on 100 parts by weight of the component (A).
The range is 5 parts by weight. Preferably, it is added in the range of 0.1 to 1.3 parts by weight, particularly preferably in the range of 0.2 to 1.2 parts by weight. When the mixing ratio of the component (D) is 0.
When the amount is less than 05 parts by weight, the effect of improving the selective permeability between carbon dioxide gas and oxygen gas and the effect of maintaining freshness are not preferable. On the other hand, when the amount exceeds 1.5 parts by weight, bleeding is liable to occur, resulting in poor moldability and a problem of deteriorating the appearance of a molded product, which is not preferable.

The preparation of the thermoplastic resin composition of the present invention can be carried out according to a conventional method. Each component may be dry-blended at the time of molding, or the blend of each of the above-mentioned components is mixed using a mixer such as a tumbler or a mixer,
Next, a method of kneading using a mixer such as a Banbury mixer or a kneader, or an extruder is used.
Moreover, you may mix | blend with an open roll. The mixing temperature is generally between 160 ° C and 300 ° C, and between 180 ° C and 280 ° C.
C is preferred.

The melt flow rate of the thermoplastic resin composition thus prepared (measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K7210;
FR ") is required to be 0.1 to 300 (g / 10 minutes), preferably 0.2 to 250 g / 10 minutes, and particularly preferably 0.3 to 200 g / 10 minutes. If the MFR is less than 0.1 (g / 10 minutes), the moldability is poor. On the other hand, if it exceeds 300 g / 10 minutes, it tends to be difficult to increase the thickness of the product.

Further, other additives commonly used for thermoplastic resins, such as antioxidants, weathering stabilizers, antistatic agents, lubricants, antiblocking agents, are added to the thermoplastic resin composition of the present invention. , An anti-fogging agent, a dye, a pigment, an oil, a wax, and the like can be appropriately added within a range that does not impair the object of the present invention.

Specific examples of such additives include 2,5-di-t-butylhydroquinone as an antioxidant,
2,6-di-t-butyl-p-cresol, 4,4′-thiobis- (6-t-butylphenol), 2,2-methylene-bis (4-methyl-6-t-butylphenol), octadecyl 3- (3 ′, 5′-di-t-butyl-1′-hydroxyphenyl) propinate, 4,4 ′
-Thiobis- (6-butylphenol), as an ultraviolet absorber, ethyl-2-cyano-3, 3-diphenylacrylate, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxy-4- Octoxybenzophenone, dimethyl phthalate, diethyl phthalate as a plasticizer, wax, liquid paraffin, phosphate ester, as a colorant, phthalocyanine, quinacridone, indoline, azo pigments, titanium oxide, bengalara, and the like. Many polymer compounds can also be blended to such an extent that the effects of the present invention are not impaired.

The thermoplastic resin composition of the present invention obtained as described above is molded using a known T-die molding method, inflation molding method, injection molding method, hollow molding method, calender molding method and molding machine. Can be a body. In film / sheet molding, in the case of T-die film / sheet molding, the temperature of the extruder is usually from 180 ° C to 300 ° C.
° C, preferably 200 ° C to 290 ° C, particularly preferably 2 ° C.
The temperature may be in the range of 20 ° C to 280 ° C. The temperature of the cooling roll is in the range of 10 ° C to 80 ° C, preferably 20 ° C.
To 70 ° C, particularly preferably 30 ° C to 60 ° C.

On the other hand, in the case of blown film molding, the temperature of the extruder is 150 ° C. to 250 ° C., preferably 1 to 250 ° C.
60 ° C to 230 ° C, particularly preferably 170 ° C to 220 ° C
And a blow-up ratio of 1.5 to 8. In the case of injection molding, the temperature is 150 ° C to 300 ° C,
Preferably from 160 ° C. to 280 ° C., particularly preferably 170 ° C.
It is good to carry out in the range of ° C-260 ° C.

In the case of the hollow molding, the extruder temperature is set to 150.
C. to 250.degree. C., preferably 160 to 230.degree. C., particularly preferably 170 to 220.degree. The calendering method is carried out at a temperature of 150 ° C to 230 ° C, preferably 160 ° C to 210 ° C, particularly preferably 170 ° C to 200 ° C.
It is good to carry out in the range of ° C. The molded article such as the film / sheet of the present invention can be used alone or by laminating other materials by various laminating methods and various coextrusion molding methods.

[0036]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 7 and Comparative Examples 1 to 18 The following three kinds of polyolefin resins were used as the thermoplastic resin of the component (A). R-1: density 0.926 g / cm ³ , MFR 0.7 g /
Linear polyethylene 10 minutes (temperature 190 ° C., load 2.16 kg) R-2: MFR 8.8 g / 10 minutes (230 ° C., load 2.16 kg) homopolypropylene R-3: ethylene content 3.5 Wt%, MFR 6.2g
/ 10 min (temperature 230 ° C, load 2.16 kg) ethylene-propylene random copolymer

As the hinokitiol compound (B), natural hinokitiol manufactured by Takasago International Corporation was used. (C)
The following three types of compounds were used as the inorganic filler of the component. F-1: Magnesium silicate, manufactured by Takehara Chemical Co., Ltd. "Product name:
US150 "F-2: Calcium carbonate, manufactured by Shiroishi Calcium Co., Ltd." Product name: Shirahika CC "F-3: Silica, manufactured by Fuji Devison" Product name: Syloid 244 "F-4: Barium sulfate, manufactured by Nippon Chemical Company (D As the polyglycerin fatty acid ester of the component), diglycerin monooleate, manufactured by Riken Vitamin Co., Ltd. "Product name:
DO-100 "was used.

[Mixing of Polymer and Additives] The components (A) to (D) were mixed according to the formulations shown in Tables 1 and 2 and a co-axial twin-screw extruder (K) was manufactured by Kobe Steel, Ltd.
TX-37), and pelletized at a temperature of 160 to 210 ° C., and a film was formed by the following blown film molding method or cast film molding method. The following various physical properties were evaluated for each film. Table 1 shows the results.

[Inflation Film Molding] With respect to the resin composition using R-1 among the components (A), an extruder having a diameter of 50 mmφ manufactured by Yoshii Tekko Co., Ltd. was used at an extrusion temperature of 190 ° C. and a take-up speed of 35 m / min. Under the conditions, an inflation film having a folding width of 270 cm and a thickness of 20 μm was prepared. [Cast film molding] Of the above component (A), R-2
And a resin composition using R-3, using an extruder having a diameter of 40 mmφ manufactured by Yoshii Iron Works Co., Ltd.
A 0 μm cast film was prepared.

The method and apparatus for measuring various physical properties according to the present invention are described below. (1) Gas Permeation Test For the resin compositions of R-3 to R-5, the permeation amount of oxygen gas and carbon dioxide gas was measured using a mixed gas permeation tester GPM-500 manufactured by LYSSY. (2) Water Vapor Permeation Test A water vapor permeation tester PERMATRAN-W manufactured by Modern Controls was used and measured according to ASTM E96. (3) Freshness retention test Using the films molded as described above, one of the various films was heat-sealed to make a bag, cut into 450 cm lengths, and broccoli was added, and stored for 6 days. Of odor, off-flavor generation and residual chlorophyll content were evaluated.

The evaluation method was based on the following criteria. [Appearance evaluation criteria] ◎: green ○: yellowish greenish green △: yellowish green ×: yellowish green yellowish xx: yellow (completely yellowed) [Generation of mold] After storage, open the bag and generate The number of molds was measured. [Measurement of Odor] After storage, the bag was opened, and the off-flavor at the time of opening was evaluated according to the following criteria. ：: no off-flavor C: Offensive odor is slightly generated. X: A noticeable odor has been generated.

[Measurement of chlorophyll]
Cut the broccoli into small pieces, add 4 volumes of ethanol, extract by stirring with a stirrer at 10,000 rpm for 10 minutes, measure the absorbance at 665 nm, and measure the ratio of chlorophyll absorbance before storage to chlorophyll absorbance after storage. (%) Was determined. For details of this measurement method, see Horticultural Experiments and Practice (Yokendo) (1)
981).

[0043]

[Table 1]

[0044]

[Table 2]

* 1 Due to the bleed out of the component (D), the surface was sticky and the transparency was poor. The main feature of the thermoplastic resin composition of the present invention is that a hinokitiol compound (B), an inorganic filler (C) and a polyglycerin fatty acid ester (D) are added to the thermoplastic synthetic resin (A).
In that they are combined and blended. As can be seen from the data in Table 1, when only the hinokitiol compound (B) and the inorganic filler (C) were blended into the thermoplastic resin (A) (Comparative Examples 5, 10, 15), or the hinokitiol compound (B) When only polyglycerin fatty acid ester (D) was blended (Comparative Examples 4, 11, 16),
It has a low CO ₂ gas / O ₂ gas permeation ratio, is yellowish, has a poor appearance, is inferior in mold resistance, and has a bad smell.
When a hinokitiol compound (B), an inorganic filler (C) and a polyglycerin fatty acid ester (D) are combined with the thermoplastic resin (A) as in the present invention (Example 1).
7), high CO ₂ gas / O ₂ gas permeation ratio, almost green appearance, improved antifungal property, no odor, and large residual chlorophyll. Thus, the thermoplastic resin (A)
By combining and blending the three components (B), (C) and (D), the blending of the two components (B) and (C) and the blending of the two components (B) and (D) It is surprising that balanced and good properties are achieved which are not achieved at all.

In particular, in order for the thermoplastic resin composition of the present invention to exhibit the well-balanced good characteristics as described above, it is considered that the inorganic filler (C) exerts a unique action and greatly contributes. That is, an example in which only the hinokitiol compound (B) was blended into the thermoplastic resin (A) (Comparative Examples 2 and 9), and an example in which the hinokitiol compound (B) and the inorganic filler (C) were combined and blended (Comparative Example 5, Comparison with 10) shows that the addition of the inorganic filler (C) only slightly improves the antifungal property and the residual chlorophyll. In contrast, an example in which a hinokitiol compound (B) and a polyglycerin fatty acid ester (D) were blended (Comparative Examples 4 and 11), and a hinokitiol compound (B), a polyglycerin fatty acid ester (D), Comparing with the examples in which the three components of the filler (C) are combined and compounded (Examples 3 and 5), it is found that the compounding of the inorganic filler (C) significantly improves all the characteristics of the above evaluation items.

[0047]

The molded articles of the thermoplastic resin composition of the present invention, such as films and sheets, have good gas barrier properties, water vapor barrier properties, antibacterial properties, antifungal properties, etc., have no unpleasant odor, and have good appearance only. In addition, it has the proper permeability of carbon dioxide and oxygen gas, which has the effect of suppressing the respiration of fruits and vegetables, prolongs the storage period, minimizes the pre-processing steps after harvest, and simplifies the packaging work. It is possible to increase the commercial value of fruits and vegetables. Therefore, the thermoplastic resin composition of the present invention is particularly useful as a packaging material for maintaining the freshness of fruits and vegetables.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/05 C08K 5/05 5/10 5/10 C08L 5/00 C08L 5/00 23/02 23/02

Claims (3)

[Claims] 1. A hinokitiol compound of at least one selected from (B) hinokitiol and salts thereof and a cyclodextrin inclusion compound containing them, per 100 parts by weight of a thermoplastic resin. 0
Parts by weight, (C) 0.05 to 2.0 parts by weight of an inorganic filler,
(D) polyglycerin fatty acid ester 0.05 to 1.5
A thermoplastic resin composition characterized by blending parts by weight. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is a polyolefin resin. 3. The thermoplastic resin composition according to claim 1, wherein the inorganic filler is at least one selected from silicic acid and salts thereof, calcium carbonate, and talc.