Resin additive, resin composition, and method for controlling resin surface components

Abstract

To provide a resin additive and a resin composition which can continuously control effects due to the resin additive, such as an antibacterial property and the like.SOLUTION: Provided is a resin additive comprising an ester-based plasticizer and polyphenols, where the ester-based plasticizer has a main component having a molar mass of 150 or more and is formed from a monobasic acid or a polybasic acid and at least one or more alcohols selected from the group consisting of glycols, methanol, ethanol, propanol, and glycol ethers. The resin composition comprises the resin additive and a specific thermoplastic resin. An amount of the resin additive relative to 100 pts.wt of the thermoplastic resin is in a range of 0.1 pt.wt. to 100 pts.wt.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin additive, a resin composition, and a method for controlling resin surface components. [Background technology]

[0002] In recent years, hygiene awareness has increased, and antibacterial properties are also required in resin products. Conventionally, methods of imparting antibacterial properties have been considered, such as kneading an antibacterial component into a resin or applying a paint containing an antibacterial component to the surface (see, for example, Patent Document 1). However, when the kneading method is used, the antibacterial agent kneaded into the resin is not sufficiently dispersed, and properties and design properties are not sufficiently maintained. In addition, with these methods, it is difficult to maintain antibacterial properties after a long period of time has passed or when the surface is wiped off. In recent years, there has been a particular demand for sustained antibacterial properties in resin products, and product development from this perspective is being accelerated. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2019 / 208674 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention solves the above-mentioned problems, and aims to obtain a resin composition having excellent properties and designability in which polyphenols are finely dispersed in the resin by using a resin additive containing polyphenols and a specific plasticizer that has excellent affinity with polyphenols and can be used at high temperatures, and further, a resin composition in which the effects of the additive, such as antibacterial properties, can be continuously controlled. [Means for solving the problem]

[0005] In order to achieve the above object, the resin additive of the present invention comprises an ester-based plasticizer and a polyphenol, The ester-based plasticizer has a molar mass of a main component of 150 or more, a monobasic or polybasic acid, and at least one alcohol selected from the group consisting of glycol, methanol, ethanol, propanol, and glycol ether. It is characterized by:

[0006] In the resin additive of the present invention, the polybasic acid is preferably succinic acid or adipic acid.

[0007] In the resin additive of the present invention, the glycol ether is preferably an ethylene glycol monoalkyl ether.

[0008] In the resin additive of the present invention, the glycol ether is preferably a diethylene glycol monoalkyl ether.

[0009] In the resin additive of the present invention, the polyphenols are preferably catechins.

[0010] In the resin additive of the present invention, the amount of the polyphenols relative to 100 parts by weight of the ester plasticizer is preferably within the range of 1 part by weight to 100 parts by weight.

[0011] The resin composition of the present invention is a resin composition comprising the resin additive of the present invention and at least one thermoplastic resin selected from resins of resin group A and resins of resin group B, The amount of the resin additive relative to 100 parts by weight of the thermoplastic resin is in the range of 0.1 parts by weight to 100 parts by weight. Resin group A: Polyolefin resin Resin group B: vinyl acetate copolymer olefin resins and polyvinyl acetates, their complete or partial saponification products, and polyvinyl acetals obtained by reacting these with aldehydes, etc. Vinyl acetate copolymer olefin resin, polyvinyl acetate resin, polyester resin, polyamide resin, acrylic resin, polyurethane resin, polycarbonate resin, polyvinyl chloride resin, acetyl cellulose resin, styrene rubber, nitrile rubber, and chloroprene rubber

[0012] In the resin composition of the present invention, the thermoplastic resin preferably contains at least one selected from the group consisting of polyvinyl acetate and ethylene-vinyl acetate copolymer.

[0013] In the resin composition of the present invention, it is preferable that the thermoplastic resin contains a polyester-based resin, and that the polyester-based resin is at least one selected from the group consisting of aliphatic polyesters and aliphatic aromatic polyesters.

[0014] In the resin composition of the present invention, it is preferable that the thermoplastic resin contains a polyester-based resin, and that the polyester-based resin is polylactic acid.

[0015] In the resin composition of the present invention, the amount of the resin of the resin group B relative to 100 parts by weight of the resin of the resin group A is preferably within the range of 2 parts by weight or more and 20 parts by weight or less.

[0016] The method for controlling resin surface components of the present invention includes the steps of: preparing a resin composition containing the resin additive of the present invention and at least one thermoplastic resin selected from the resins of Resin Group A and Resin Group B; The amount of the resin additive present on the surface of the resin composition is controlled by changing the weight ratio between the content of the resin in the resin group A and the content of the resin in the resin group B. [Effects of the Invention]

[0017] According to the present invention, by using a resin additive containing polyphenols and a specific plasticizer that has excellent affinity with polyphenols and can be used at high temperatures, it is possible to obtain a resin composition in which polyphenols are finely dispersed in the resin, which has excellent properties and design, and which further allows for sustained control of the antibacterial and other effects of the additive. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 1 is a photograph of a microscope image of the surface of the resin composition of Example 17. [Figure 2] FIG. 2 is a microscopic photograph of the surface of the resin composition of the reference example. DETAILED DESCRIPTION OF THE INVENTION

[0019] Preferred embodiments of the present invention are described in detail below. The resin additive of the present invention includes an ester-based plasticizer and polyphenols. The inventors discovered that ester-based plasticizers, which have a molar mass of 150 or more as the main component and are composed of a monobasic acid or polybasic acid and at least one alcohol selected from the group consisting of glycol, methanol, ethanol, propanol, and glycol ether, have excellent affinity with polyphenols. By using the ester-based plasticizer and polyphenols, they obtained a resin additive that can be uniformly mixed with polyphenols even at high concentrations.

[0020] Examples of ester-based plasticizers that can be used include bis(2-(2-butoxyethoxy)ethyl) adipate, bis(2-methoxyethyl) phthalate, bis(2-methoxyethyl) adipate, bis(2-butoxyethyl) adipate, triethylene glycol bis(2-ethylhexanoate), and benzylmethyl diglycol adipate. The polybasic acid constituting the ester-based plasticizer is preferably succinic acid or adipic acid. The glycol ether constituting the ester-based plasticizer is preferably ethylene glycol monoalkyl ether or diethylene glycol monoalkyl ether, and more preferably ethylene glycol monopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monoethyl ether, or diethylene glycol monomethyl ether. One type of ester-based plasticizer may be blended alone, or two or more types of the ester-based plasticizers may be blended in combination. Alternatively, a mixed ester consisting of the polybasic acid and two or more of the alcohols may be used.

[0021] The molar mass of the main component of the ester-based plasticizer is 150 or more. Plasticizers are resin additives and must be used at high temperatures of 100°C or higher, and in some cases, even higher than 150°C. If the molar mass of the main component is less than 150, the ester-based plasticizer may volatilize during kneading with the resin, which may worsen the working environment and handling. The molar mass is preferably 200 or more, and more preferably 300 or more.

[0022] Examples of polyphenols that can be used include (-) epicatechin, (-) epigallocatechin, (-) epigallocatechin gallate, (-) epicatechin gallate, anthocyanins, isoflavones, ellagic acid, oleuropein, curcumin, chlorogenic acid, lignans, catechin mixtures derived from green tea, tea catechin powder, and tannins such as persimmon tannin, with catechins being preferred. One type of polyphenol may be used alone, or two or more types of polyphenols may be used in combination.

[0023] Considering the durability of antibacterial and other effects, the amount of polyphenols ultimately contained in the resin composition is preferably several to several tens of parts by weight per 100 parts by weight of thermoplastic resin. If the amount of polyphenols in the resin additive is too small, the amount of resin additive added to the thermoplastic resin to achieve the desired amount of polyphenols will be too large, which is inefficient. Furthermore, if the amount of polyphenols in the resin additive is too large, the viscosity of the resin additive will be too high, resulting in reduced production and operating efficiency. Therefore, in the resin additive of the present invention, the amount of polyphenols per 100 parts by weight of the ester-based plasticizer is preferably in the range of 1 part by weight to 100 parts by weight, more preferably 10 parts by weight to 60 parts by weight.

[0024] Because the antibacterial performance of resin products is believed to be due to the presence of antibacterial components on the resin surface, maintaining antibacterial properties becomes difficult over long periods of time or when the surface is wiped. Therefore, to maintain the antibacterial properties of resin products, a resin composition that continuously supplies the antibacterial component to the surface, i.e., a resin composition in which the amount of antibacterial component present on the resin surface can be controlled, has been sought. The resin additive of the present invention is a mixture of an ester-based plasticizer and a polyphenol. The ester-based plasticizer and the polyphenol behave as a single entity, and the polyphenols bleed to the surface as the ester-based plasticizer bleeds to the surface. However, when the resin additive is mixed with a low-polarity thermoplastic resin, the low affinity between the low-polarity resin and the ester-based plasticizer increases the amount of ester-based plasticizer that bleeds to the resin surface, resulting in significant stickiness on the resin surface and making it difficult to use in products. In this case, the bleeding of the ester-based plasticizer results in the supply of more polyphenols to the surface than necessary. Therefore, it was necessary to find a resin composition in which the amount of ester-based plasticizer bleeding was controlled, and thus a resin composition in which the amount of polyphenols supplied to the surface was controlled. The present invention was developed in consideration of these circumstances. As a result of studies, the present inventors have discovered a resin composition in which the amount of ester-based plasticizer bleeding and, therefore, the amount of polyphenols supplied to the surface can be controlled by mixing a low-polarity resin (resin group A) with a polar resin (resin group B) as needed to adjust the polarity of the entire resin. That is, the resin composition of the present invention includes the resin additive and at least one thermoplastic resin selected from the resins of resin group A and resin group B below. The amount of the resin additive per 100 parts by weight of the thermoplastic resin is in the range of 0.1 parts by weight to 100 parts by weight, thereby enabling a resin composition in which the antibacterial and other effects of the additive can be sustainably controlled.

[0025] Resin group A: Polyolefin resin

[0026] Resin group B: vinyl acetate copolymer olefin resins and polyvinyl acetates, their complete or partial saponification products, and polyvinyl acetals obtained by reacting these with aldehydes, etc. Vinyl acetate copolymer olefin resin, polyvinyl acetate resin, polyester resin, polyamide resin, acrylic resin, polyurethane resin, polycarbonate resin, polyvinyl chloride resin, acetyl cellulose resin, styrene rubber, nitrile rubber, and chloroprene rubber

[0027] The thermoplastic resin preferably includes at least one selected from the group consisting of polyethylene, polypropylene, and copolymers thereof, ethylene-propylene-diene copolymer, polymethylpentene, and cycloolefin copolymer as resin group A. Furthermore, resin group A is more preferably polyethylene or polypropylene.

[0028] The thermoplastic resin preferably includes at least one selected from the group consisting of polyvinyl acetate and ethylene-vinyl acetate copolymer as resin group B. The thermoplastic resin also preferably includes a polyester-based resin as resin group B, and the polyester-based resin is preferably at least one selected from the group consisting of aliphatic polyesters and aliphatic-aromatic polyesters. The polyester-based resin is also preferably polylactic acid.

[0029] The resin composition of the present invention may contain a resin selected from either Resin Group A or Resin Group B, or may contain resins selected from both groups. When resins selected from both groups are contained, i.e., when at least one resin from Resin Group A and at least one resin from Resin Group B are contained, it is preferable that the amount of resin from Resin Group B per 100 parts by weight of resin from Resin Group A is in the range of 2 to 20 parts by weight, since this allows for sustained control of the antibacterial and other effects of the additive. The amount of Resin Group B is more preferably in the range of 3 to 10 parts by weight.

[0030] The resin composition of the present invention may further contain, as optional components, general additives such as inorganic fillers, organic fillers, pigments, dyes, radical initiators, flame retardants, antioxidants, antibacterial agents, bacteriostatic agents, and disinfectants, within a range that does not impair the effects of the present invention. As the radical initiator, a peroxidizer or the like can be suitably used.

[0031] The resin composition of the present invention can be produced, for example, by kneading the materials in a kneader and then extruding them in an extruder. If necessary, the resulting resin composition may be pelletized or processed into a sheet or film.

[0032] The resin surface component control method of the present invention is a method for controlling the amount of ester-based plasticizer bleed and thus the amount of polyphenols supplied to the surface by mixing a resin with low polarity (resin group A) and a resin with polarity (resin group B) in a predetermined ratio as needed and adjusting the polarity of the entire resin, and is characterized in that when preparing a resin composition containing the resin additive of the present invention and at least one thermoplastic resin selected from the resins of resin group A and resins of resin group B, the amount of the resin additive present on the surface of the resin composition is controlled by changing the weight ratio between the content of the resin of resin group A and the content of the resin of resin group B. [Example]

[0033] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0034] (Resin additives) [Example 1] The plasticizer used was bis(2-(2-butoxyethoxy)ethyl) adipate (BXA-N, manufactured by Daihachi Chemical Industry Co., Ltd., molar mass 435), an ester-based plasticizer. This ester-based plasticizer is composed of adipic acid as a polybasic acid and diethylene glycol monobutyl ether as a glycol ether. In addition, (-)-epicatechin (manufactured by Nagara Science Co., Ltd.) was used as a polyphenol. The resin additive of this example was prepared by blending 100 parts by weight of the ester-based plasticizer with 1 part by weight of the polyphenol.

[0035] [Example 2] A resin additive was prepared in the same manner as in Example 1, except that (-) epigallocatechin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the polyphenol.

[0036] [Example 3] A resin additive was prepared in the same manner as in Example 1, except that (-) epigallocatechin gallate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the polyphenol.

[0037] [Example 4] A resin additive was prepared in the same manner as in Example 1, except that a catechin mixture (derived from green tea) (manufactured by Nagara Science Co., Ltd.) was used as the polyphenol.

[0038] [Example 5] A resin additive was prepared in the same manner as in Example 1, except that Qualselect tea catechin powder (manufactured by Global Fort LLC) was used as the polyphenol.

[0039] [Example 6] A resin additive was prepared in the same manner as in Example 1, except that Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as the polyphenol and 66.7 parts by weight of polyphenols were blended with 100 parts by weight of the ester-based plasticizer.

[0040] [Example 7] A resin additive was prepared in the same manner as in Example 1, except that Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as the polyphenol and 100 parts by weight of polyphenols was blended with 100 parts by weight of ester-based plasticizer.

[0041] [Example 8] A resin additive was prepared in the same manner as in Example 1, except that Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as the polyphenol and 150 parts by weight of polyphenols were blended with 100 parts by weight of the ester-based plasticizer.

[0042] [Example 9] A resin additive was prepared in the same manner as in Example 1, except that persimmon tannin (manufactured by Iwamoto Kametaro Honten Co., Ltd.) was used as the polyphenol and 0.1 parts by weight of polyphenols was blended with 100 parts by weight of the ester-based plasticizer.

[0043] [Example 10] The plasticizer used was bis(2-methoxyethyl)phthalate (manufactured by Tokyo Chemical Industry Co., Ltd., molar mass 282), an ester-based plasticizer. This ester-based plasticizer is composed of phthalic acid as a polybasic acid and ethylene glycol monomethyl ether as a glycol ether. Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as a polyphenol. The resin additive of this example was prepared by blending 1 part by weight of polyphenols with 100 parts by weight of the ester-based plasticizer.

[0044] [Example 11] The plasticizer used was bis(2-methoxyethyl) adipate (manufactured by Tokyo Chemical Industry Co., Ltd., molar mass 262), an ester-based plasticizer. This ester-based plasticizer is composed of adipic acid as a polybasic acid and ethylene glycol monomethyl ether as a glycol ether. Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as the polyphenol. The resin additive of this example was prepared by blending 1 part by weight of polyphenols with 100 parts by weight of the ester-based plasticizer.

[0045] [Example 12] The plasticizer used was bis(2-butoxyethyl) adipate (manufactured by Tokyo Chemical Industry Co., Ltd., molar mass 346), an ester-based plasticizer. This ester-based plasticizer is composed of adipic acid as a polybasic acid and ethylene glycol monobutyl ether as a glycol ether. Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as the polyphenol. The resin additive of this example was prepared by blending 1 part by weight of polyphenols with 100 parts by weight of the ester-based plasticizer.

[0046] [Example 13] The plasticizer used was an ester-based plasticizer, triethylene glycol di-2-ethylhexanoate (G-260, manufactured by Sekisui Chemical Co., Ltd., molar mass 402). This ester-based plasticizer is composed of 2-ethylhexanoic acid as a monobasic acid and triethylene glycol as a glycol ether. Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as a polyphenol. The resin additive of this example was prepared by blending 1 part by weight of polyphenols with 100 parts by weight of the ester-based plasticizer.

[0047] [Example 14] The plasticizer used was an ester-based plasticizer, benzyl methyl diglycol adipate (DAIFATTY-101, manufactured by Daihachi Chemical Industry Co., Ltd., molar mass 338). This ester-based plasticizer is composed of adipic acid as a polybasic acid and a mixture of diethylene glycol monomethyl ether and diethylene glycol monobenzyl ether as a glycol ether. Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as a polyphenol. The resin additive of this example was prepared by blending 1 part by weight of polyphenols with 100 parts by weight of the ester-based plasticizer.

[0048] [Example 15] A resin additive was prepared in the same manner as in Example 14, except that Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as the polyphenol and 50 parts by weight of polyphenols were blended with 100 parts by weight of the ester-based plasticizer.

[0049] [Example 16] A resin additive was prepared in the same manner as in Example 14, except that Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as the polyphenol and 100 parts by weight of polyphenols was blended with 100 parts by weight of ester-based plasticizer.

[0050] [Comparative Example 1] The plasticizer used was an ester-based plasticizer, dibutyl adipate (DBA, manufactured by Daihachi Chemical Industry Co., Ltd., molar mass 258). This ester-based plasticizer is composed of adipic acid as a polybasic acid and butanol as an alcohol. In addition, (-)-epicatechin (manufactured by Nagara Science Co., Ltd.) was used as a polyphenol. The resin additive of this comparative example was prepared by blending 1 part by weight of polyphenols with 100 parts by weight of the ester-based plasticizer.

[0051] Comparative Example 2 A resin additive was prepared in the same manner as in Comparative Example 1, except that (-) epigallocatechin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the polyphenol.

[0052] Comparative Example 3 A resin additive was prepared in the same manner as in Comparative Example 1, except that (-) epigallocatechin gallate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the polyphenol.

[0053] Comparative Example 4 A resin additive was prepared in the same manner as in Comparative Example 1, except that Qualselect tea catechin powder (manufactured by Global Fort LLC) was used as the polyphenol.

[0054] Comparative Example 5 A resin additive was prepared in the same manner as in Comparative Example 1, except that persimmon tannin (manufactured by Iwamoto Kametaro Honten Co., Ltd.) was used as the polyphenol and 0.1 parts by weight of polyphenols was blended with 100 parts by weight of the ester-based plasticizer.

[0055] Comparative Example 6 The plasticizer used was an ester-based plasticizer, bis(2-ethylhexyl) adipate (manufactured by Tokyo Chemical Industry Co., Ltd., molar mass 370). This ester-based plasticizer is composed of adipic acid as a polybasic acid and 2-ethylhexanol as an alcohol. Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as a polyphenol. The resin additive of this comparative example was prepared by blending 100 parts by weight of the ester-based plasticizer with 1 part by weight of the polyphenol.

[0056] Comparative Example 7 Polyethylene glycol 400 (manufactured by Nacalai Tesque, Inc., molar mass approximately 400) was used as the plasticizer. Qualselect tea catechin powder (manufactured by Globalfort LLC) was used as the polyphenol. The resin additive of this comparative example was prepared by blending 1 part by weight of polyphenols with 100 parts by weight of plasticizer.

[0057] [Comparative Example 8] The resin additive of this comparative example was prepared by blending 1 part by weight of polyphenols with 100 parts by weight of ethyl acetate (manufactured by Nacalai Tesque, Inc., molar mass 88) and Qualselect tea catechin powder (manufactured by Globalfort LLC) as a polyphenol.

[0058] (Solubility test) For the resin additives of Examples 1 to 16 and Comparative Examples 1 to 8, polyphenols and plasticizers were mixed in a sample bottle and gently stirred with a metal spatula. The mixture was then left at room temperature overnight, and the solubility was visually evaluated according to the following criteria. The results are shown in Tables 1 and 2. S: Dissolves within a few hours after mixing A: Dissolve after standing for a day and night. B: Almost completely dissolved, but some undissolved matter remains C: Clearly undissolved matter remains (NG)

[0059] [Table 1]

[0060] [Table 2]

[0061] Examples 1 to 8 dissolved within a few hours after mixing. Example 8 became a paste. Examples 11 and 14 to 16 dissolved after standing overnight. Examples 9, 10, 12, and 13 were almost completely dissolved, although some undissolved matter remained even after standing overnight. Comparative Examples 1 to 6 clearly had undissolved matter remaining even after standing overnight. Comparative Example 7 dissolved within a few hours after mixing, but foamed due to water evaporation when added to a thermoplastic resin, and was therefore not suitable for melt-kneading as a resin additive. Comparative Example 8 dissolved within a few hours after mixing, but this resin additive was highly volatile and not suitable for melt-kneading.

[0062] (Resin composition) [Example 17] (1) Batch mixing A mixture of 10 parts by weight of bis(2-(2-butoxyethoxy)ethyl) adipate (BXA-N, manufactured by Daihachi Chemical Industry Co., Ltd.) as a resin additive and 3 parts by weight of Qualselect tea catechin powder (manufactured by Globalfort LLC) as a polyphenol was used. Low-density polyethylene (LDPE, "Novatec LD" LC525, manufactured by Japan Polyethylene Corporation, corresponding to Resin Group A) was used as a polyolefin resin. 100 parts by weight of the low-density polyethylene and 13 parts by weight of the resin additive were placed in a batch kneader (10S100, manufactured by Toyo Seiki Seisakusho Co., Ltd.) set at 140°C and kneaded for 10 minutes at 12.5 rpm to obtain a kneaded sample.

[0063] (2) Sheet molding (heat press method) Approximately 2.5 g of the obtained kneaded sample was weighed out and placed in a 10 cm × 10 cm × 0.3 mm spacer, and then heated and pressed using a tabletop press (small press G-12, manufactured by Techno Supply Co., Ltd.) set to 140 ° C., and then immediately sandwiched between metal plates with tap water running through them to cool, thereby obtaining a sheet-like test piece. The thickness of the obtained sheet-like test piece was approximately 0.3 mm.

[0064] [Example 18] A mixture of 10 parts by weight of bis(2-(2-butoxyethoxy)ethyl) adipate (BXA-N, manufactured by Daihachi Chemical Industry Co., Ltd.) as a resin additive and 3 parts by weight of Qualselect tea catechin powder (manufactured by Globalfort LLC) as a polyphenol was used. Low-density polyethylene (LDPE, "Novatec LD" LC525, manufactured by Japan Polyethylene Corporation, corresponding to Resin Group A) was used as a polyolefin resin, and ethylene-vinyl acetate copolymer (EVA, "Ultrasene" injection grade 633, manufactured by Tosoh Corporation, corresponding to Resin Group B) was used as a copolymerized olefin resin. 100 parts by weight of the low-density polyethylene, 5 parts by weight of the ethylene-vinyl acetate copolymer, and 13 parts by weight of the resin additive were placed in a batch kneader (10S100, manufactured by Toyo Seiki Seisakusho Co., Ltd.) set at 140 °C and kneaded for 10 minutes at 12.5 rpm to obtain a kneaded sample. Using the obtained kneaded sample, a sheet-like test piece was obtained in the same manner as in Example 17.

[0065] [Example 19] A mixture of 10 parts by weight of benzyl methyl diglycol adipate (DAIFATTY-101, manufactured by Daihachi Chemical Industry Co., Ltd.) as a resin additive and 3 parts by weight of Qualselect tea catechin powder (manufactured by Globalfort LLC) as a polyphenol was used. Polylactic acid (PLA, "REVODE" 101L, manufactured by Zhejiang Haizheng Biomaterials, corresponding to Resin Group B) was used as a polyester-based resin. 100 parts by weight of the polylactic acid and 13 parts by weight of the resin additive were placed in a batch kneader (10S100, manufactured by Toyo Seiki Seisakusho Co., Ltd.) set at 140°C and kneaded for 10 minutes at a rotation speed of 12.5 rpm to obtain a kneaded sample. Using the obtained kneaded sample, a sheet-like test piece was obtained in the same manner as in Example 17.

[0066] [Example 20] The resin additive used was a mixture of 10 parts by weight of benzyl methyl diglycol adipate (DAIFATTY-101, manufactured by Daihachi Chemical Industry Co., Ltd.), 3 parts by weight of Qualselect tea catechin powder (manufactured by Globalfort LLC) as a polyphenol, polylactic acid (PLA, "REVODE" 101, manufactured by Zhejiang Haizheng Biomaterials, corresponding to resin group B) as a polyester resin, and polyvinyl acetal with a molecular weight of 1.15 × 10 5 The PVB ("S-LEC B·K" BH-A, manufactured by Sekisui Chemical Co., Ltd.) was blended with triethylene glycol di-2-ethylhexanoate (G-260, manufactured by Sekisui Chemical Co., Ltd.) as a PVB plasticizer at a weight ratio of PVB:PVB plasticizer = 3:1 (corresponding to Resin Group B). 75 parts by weight of the polylactic acid, 25 parts by weight of the polyvinyl acetal, and 13 parts by weight of the resin additive were placed in a batch kneader (10S100, manufactured by Toyo Seiki Seisakusho Co., Ltd.) set to 180°C and kneaded for 10 minutes at a rotation speed of 12.5 rpm to obtain a kneaded sample. Sheet-shaped test pieces were obtained from the kneaded sample in the same manner as in Example 17, except that the temperature of the tabletop press was set to 180°C.

[0067] [Reference example] 100 parts by weight of low-density polyethylene (LDPE, "Novatec LD" LC525, manufactured by Japan Polyethylene Corporation, corresponding to resin group A) and 3 parts by weight of Qualselect tea catechin powder (manufactured by Globalfort LLC) were placed in a batch kneader (10S100, manufactured by Toyo Seiki Seisakusho Co., Ltd.) set to 140°C, and kneaded at a rotation speed of 12.5 rpm for 10 minutes to obtain a kneaded sample. Using the obtained kneaded sample, a sheet-like test piece was obtained in the same manner as in Example 17.

[0068] (Microscopic observation) The sheet-like test pieces obtained in Example 17 and the Reference Example were observed through a stereomicroscope (HDMI digital microscope: STZ-171-TLED-1080, manufactured by Shimadzu Corporation) set at 50x magnification. Figure 1 is a photograph of a microscopic image of the surface of a sheet-like test piece obtained from the resin composition of Example 17. Figure 2 is a photograph of a microscopic image of the surface of a sheet-like test piece obtained from the resin composition of the Reference Example. Figure 2 shows that catechin is coarsely dispersed, whereas Figure 1 shows that it is finely dispersed. Similarly to Figure 1, catechin was also finely dispersed in the sheet-like test pieces obtained in Examples 19 and 20. Thus, it was demonstrated that by using the resin additive of the present invention in which polyphenols are dissolved in a specific plasticizer, polyphenols are finely dispersed in the resin, resulting in a resin composition with excellent properties and design.

[0069] (Surface catechin amount measurement) The amount of catechins on the surface of the sheet-like test piece was measured using a high performance liquid chromatograph analyzer (HPLC EXTREMA, manufactured by JASCO Corporation) under the following method and conditions. <Surface component extraction method> A 35 mm x 55 mm strip sample (approximately 1 g) was cut from the sheet-like test piece. 1.5 mL of 10% aqueous methanol solution was prepared in a petri dish, and the front and back of the strip sample were contacted with the aqueous methanol solution at room temperature. The contact time was 1 second for each side, and the contact was repeated 30 times (total contact time 60 seconds). The aqueous methanol solution in the petri dish was then filtered through a 0.5 μm filter, and the resulting filtrate was used as a sample for high-performance liquid chromatography. <High-performance liquid chromatography conditions> Column: Inertsil ODSC8-3 (GL Sciences, Inc., reversed-phase column with silica gel particle diameter of 5 μm, inner diameter of 4.6 μm, and length of 150 mm) Temperature: 40℃ Injection volume: 10μL Elution method: Gradient elution using a mixed solution of water (A) and methanol (B) (elution conditions: A / B concentration changed from 90 / 10 to 60 / 40 over 20 minutes) Flow rate: 1.0mL / min <Quantitative method> The peak observed at 12.4 minutes obtained by measuring a (-) epigallocatechin gallate (EGCg) standard sample (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was defined as the catechin-derived peak, and the amount of catechin per 1 g of sample was calculated from the peak area of ​​the same part of each sample, which was used as an index of the amount of surface catechin.

[0070] The amount of catechins on the surface of the sheet-like test pieces obtained in Example 17 and Reference Example was measured. The amount of catechins on the surface was measured at the following three stages. First step: After preparing the sheet-shaped test piece, measure it as is without any special treatment. Second step: Wipe the front and back of the sheet test piece with a cloth soaked in ethanol, then measure immediately. Third step: The sheet specimen after the second step was left at room temperature for one month and then measured.

[0071] In the sheet-like test piece obtained in Example 17, approximately 110 μg of catechins were present on the surface per gram of sample at the first stage. However, when both surfaces were wiped with ethanol, the amount of catechins present on the surface decreased to approximately 20% (stage 2). Furthermore, after leaving the sample for one month, the amount increased to approximately 40% of the amount before wiping, confirming that catechins bleed to the surface over time (stage 3). This indicates that the effects of catechins can be sustained even after wiping.

[0072] In the sheet-shaped test piece obtained in the Reference Example, approximately 80 μg of catechins per 1 g of sample was present on the surface at the first stage. However, when both sides were wiped with ethanol, the amount of catechins present on the surface decreased to approximately 10% (stage 2). However, this amount did not increase even after being left for one month (stage 3). This indicates that the effect of catechins may be limited once the surface is wiped.

[0073] The sheet-like test piece obtained in Example 18 had reduced surface stickiness and a good feel compared to Example 17. This indicates that it is possible to achieve both good surface properties (reduced stickiness) and sustained effects of catechin. Thus, by combining Resin Group A and Resin Group B, bleeding of the ester-based plasticizer was reduced, resulting in reduced amounts of resin additives present on the surface. This result indicates that the amount of resin additives present on the surface can be controlled by changing the weight ratio of the resin content of Resin Group A to the resin content of Resin Group B.

[0074] The above-described embodiments are merely examples for carrying out the present invention. Therefore, the present invention is not limited to the above-described embodiments, and the above-described embodiments can be appropriately modified and carried out without departing from the spirit of the present invention. [Industrial Applicability]

[0075] According to the present invention, in a resin containing polyphenols as additives, the polyphenols can be finely dispersed in the resin to provide a resin composition with excellent properties and design, and further, effects such as antibacterial properties can be continuously controlled. Furthermore, by using a specific plasticizer with excellent affinity for polyphenols, even if the amount of polyphenols added is increased, the polyphenols can be contained in the resin with good dispersibility, thereby enhancing the effects attributable to polyphenols, such as antibacterial properties. Because a resin composition can be obtained in which the effects can be continuously controlled, for example, the replacement (replacement) cycle can be extended, which not only has the effect of reducing the environmental burden caused by waste, but is also thought to be a significant contribution to industrial use.

Claims

1. A resin composition comprising a resin additive and at least one thermoplastic resin selected from resins of resin group A and resins of resin group B, the resin additive contains an ester-based plasticizer and a polyphenol; The ester-based plasticizer has a molar mass of a main component of 150 or more, a monobasic or polybasic acid, and at least one alcohol selected from the group consisting of glycol, methanol, ethanol, propanol, and glycol ethers; A resin composition characterized in that the amount of the resin additive relative to 100 parts by weight of the thermoplastic resin is in the range of 0.1 parts by weight to 100 parts by weight. Resin group A: Polyolefin resin Resin group B: vinyl acetate copolymerized olefin resins and polyvinyl acetates, their complete or partial saponification products, and polyvinyl acetals obtained by reacting these with aldehydes, etc. Vinyl acetate copolymer olefin resin, polyvinyl acetate resin, polyester resin, polyamide resin, acrylic resin, polyurethane resin, polycarbonate resin, polyvinyl chloride resin, acetyl cellulose resin, styrene rubber, nitrile rubber, and chloroprene rubber

2. A resin composition as described in claim 1, wherein the polybasic acid is succinic acid or adipic acid.

3. A resin composition according to claim 1 or 2, wherein the glycol ether is an ethylene glycol monoalkyl ether or a diethylene glycol monoalkyl ether.

4. A resin composition described in any one of claims 1 to 3, wherein the polyphenols are catechins.

5. A resin composition described in any one of claims 1 to 4, wherein the amount of polyphenols per 100 parts by weight of the ester-based plasticizer is in the range of 1 part by weight or more and 100 parts by weight or less.

6. The resin composition according to claim 1 , wherein the thermoplastic resin comprises at least one selected from the group consisting of polyvinyl acetate and ethylene-vinyl acetate copolymer.

7. The resin composition according to claim 1 , wherein the amount of the resin of the resin group B relative to 100 parts by weight of the resin of the resin group A is in the range of 2 parts by weight or more and 20 parts by weight or less.

8. During preparation of a resin composition containing a resin additive and at least one thermoplastic resin selected from resins of resin group A and resins of resin group B, the resin additive contains an ester-based plasticizer and a polyphenol; The ester-based plasticizer has a molar mass of a main component of 150 or more, a monobasic or polybasic acid, and at least one alcohol selected from the group consisting of glycol, methanol, ethanol, propanol, and glycol ethers; A method for controlling resin surface components, characterized in that the amount of the resin additive present on the surface of the resin composition is controlled by changing the weight ratio of the content of the resin in resin group A to the content of the resin in resin group B. Resin group A: Polyolefin resin Resin group B: vinyl acetate copolymerized olefin resins and polyvinyl acetates, their complete or partial saponification products, and polyvinyl acetals obtained by reacting these with aldehydes, etc. Vinyl acetate copolymer olefin resin, polyvinyl acetate resin, polyester resin, polyamide resin, acrylic resin, polyurethane resin, polycarbonate resin, polyvinyl chloride resin, acetyl cellulose resin, styrene rubber, nitrile rubber, and chloroprene rubber

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