Thermoplastic resin composition and molded article made from the same

Abstract

To provide a thermoplastic resin composition excellent in transparency, impact resistance, moldability and oil resistance, and a molding.SOLUTION: A thermoplastic resin composition contains cyclic polyolefin (A) and a tackifier resin (B). The cyclic polyolefin (A) is composed of a hydrogenated block copolymer that is a hydrogenated material of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit. The hydrogenated block copolymer has a hydrogenated aromatic vinyl polymer block unit that is a hydrogenated body of a polymer block composed of an aromatic vinyl monomer unit, and a hydrogenated conjugated diene polymer block unit that is a hydrogenated body of a polymer block composed of a conjugated diene monomer unit. The hydrogenated block copolymer has at least the two hydrogenated aromatic vinyl polymer block units, and at least one hydrogenated conjugated diene polymer block unit.SELECTED DRAWING: None

Description

[Technical Field]

[0001] An object of the present invention is to provide a thermoplastic resin composition having excellent transparency, impact resistance, moldability and oil resistance, and a molded article made from the same. [Background technology]

[0002] Cyclic polyolefins having hydrogenated aromatic vinyl polymer block units, which are hydrogenated products of polymer blocks comprising at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit, and hydrogenated conjugated diene polymer block units, which are hydrogenated products of polymer blocks comprising the conjugated diene monomer units, are hydrogenated products of block copolymers comprising at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit, have excellent transparency and impact resistance, and are therefore expected to be used in medical molded articles (see Patent Document 1), optical components, electrical and electronic components, and food containers such as food bottles and Tupperware. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2018-023771 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the study of cyclic polyolefins by the present inventors, it was found that the application of cyclic polyolefins to food containers is difficult due to their poor oil resistance. Furthermore, it was found that when applied to food containers such as food bottles and Tupperware, it is necessary to improve moldability and oil resistance while maintaining transparency and impact resistance. The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a thermoplastic resin composition and a molded article thereof that are excellent in transparency, impact resistance, moldability, and oil resistance. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have discovered that the use of a specific cyclic polyolefin and a specific tackifying resin provides excellent transparency, impact resistance, moldability, and oil resistance, and that the material can be suitably used as a material for food containers such as food bottles and Tupperware, thereby arriving at the present invention. That is, the present invention has the following features.

[0006] [1] A thermoplastic resin composition comprising a cyclic polyolefin (A) and a tackifier resin (B), wherein the cyclic polyolefin (A) comprises a hydrogenated block copolymer which is a hydrogenated product of a block copolymer comprising at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit, and the hydrogenated block copolymer has hydrogenated aromatic vinyl polymer block units which are hydrogenated products of polymer blocks comprising the aromatic vinyl monomer units, and hydrogenated conjugated diene polymer block units which are hydrogenated products of polymer blocks comprising the conjugated diene monomer units, and the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit, and the content of the hydrogenated aromatic vinyl polymer block units in the cyclic polyolefin (A) is 30 to 80 mol % and the content of the hydrogenated conjugated diene polymer block units is 20 to 70 mol %.

[0007] [2] The thermoplastic resin composition according to [1], which contains 5 to 90 parts by mass of a tackifier resin (B) relative to 100 parts by mass of the cyclic polyolefin (A). [3] The thermoplastic resin composition according to [1] or [2], wherein the hydrogenated aromatic vinyl polymer block units have a hydrogenation level of 90% or more, and the hydrogenated conjugated diene polymer block units have a hydrogenation level of 95% or more. [4] The thermoplastic resin composition according to any one of [1] to [3], wherein the hydrogenated aromatic vinyl polymer block units are units composed of hydrogenated polystyrene, and the hydrogenated conjugated diene polymer block units are units composed of hydrogenated polybutadiene.

[0008] [5] The thermoplastic resin composition according to any one of [1] to [4], wherein the tackifier resin (B) is at least one selected from the group consisting of hydrogenated terpene resins, hydrogenated rosin and hydrogenated rosin ester resins, disproportionated rosin and disproportionated rosin ester resins, and hydrogenated petroleum resins. [6] The thermoplastic resin composition according to any one of [1] to [4], wherein the tackifier resin (B) is a hydrogenated petroleum resin. [7] The thermoplastic resin composition according to any one of [1] to [6], wherein the tackifier resin (B) has a softening point of 100 to 180°C.

[0009] [8] The thermoplastic resin composition according to any one of [1] to [7], further comprising a styrene-based elastomer (C). [9] The thermoplastic resin composition according to [8], wherein the styrene-based elastomer (C) is a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit.

[10] The thermoplastic resin composition according to [9], wherein the block copolymer is a hydrogenated block copolymer.

[0010]

[11] The thermoplastic resin composition according to

[10] , wherein the hydrogenated block copolymer has an aromatic vinyl polymer block unit composed of the aromatic vinyl monomer unit and a hydrogenated conjugated diene polymer block unit that is a hydrogenated product of a polymer block composed of the conjugated diene monomer unit.

[12] The thermoplastic resin composition according to

[11] , wherein the content of aromatic vinyl polymer block units in the styrene-based elastomer (C) is 15 to 50 mass %.

[13] The thermoplastic resin composition according to any one of [8] to

[12] , wherein the styrene-based elastomer (C) has a weight average molecular weight of 10,000 to 200,000.

[0011]

[14] A molded article made of the thermoplastic resin composition according to any one of [1] to

[13] .

[15] The molded article according to

[14] , which is a food container, a medical molded article, an optical part, or an electric / electronic part.

[16] The molded article according to

[15] , wherein the food container is a food bottle or a Tupperware.

[17] The medical molded article according to

[15] , which is a plastic slide glass, an eye dropper, a medicine bottle ampoule, a vial, a cap used therefor, a test tube, a blood collection tube, a specimen container, a pre-filled syringe, or a syringe. [Effects of the Invention]

[0012] The thermoplastic resin composition and molded article containing the specific cyclic polyolefin and tackifier resin according to the present invention have excellent transparency, impact resistance, moldability, and oil resistance, and can therefore be suitably used as materials for food containers such as food bottles and Tupperware, as well as medical molded articles, optical components, and electrical and electronic components. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not go beyond the gist of the present invention. The present invention can be implemented by modifying it as desired within the scope of the gist of the present invention. In the following, when "~" is used to express a numerical value or physical property value, the values ​​before and after it will be used as including the values ​​before and after it.

[0014] The present invention relates to a thermoplastic resin composition containing a cyclic polyolefin (A) and a tackifier resin (B).

[0015] <Cyclic polyolefin (A)> The cyclic polyolefin (A) of the present invention (hereinafter sometimes referred to as "component (A)") comprises a hydrogenated block copolymer, which is a hydrogenated product of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit. The hydrogenated block copolymer has hydrogenated aromatic vinyl polymer block units, which are hydrogenated products of polymer blocks composed of the aromatic vinyl monomer units, and hydrogenated conjugated diene polymer block units, which are hydrogenated products of polymer blocks composed of the conjugated diene monomer units. The hydrogenated block copolymer has at least two of the hydrogenated aromatic vinyl polymer block units and at least one of the hydrogenated conjugated diene polymer block units.

[0016] From the viewpoints of transparency and weather resistance, the cyclic polyolefin (A) of the present invention preferably comprises the hydrogenated block copolymer. As used herein, the term "block" refers to a copolymeric polymeric segment that exhibits microphase separation from structurally or compositionally distinct polymeric segments of the copolymer, as described below. Thus, for example, "having at least two block units" refers to the presence of at least two copolymeric polymeric segments that exhibit microphase separation from structurally or compositionally distinct polymeric segments in the hydrogenated block copolymer.

[0017] The aromatic vinyl monomer that is the raw material for the aromatic vinyl monomer unit is a monomer represented by the general formula (1).

[0018] [ka]

[0019] Here, R is hydrogen or an alkyl group, and Ar is a phenyl group, a halophenyl group, an alkylphenyl group, an alkylhalophenyl group, a naphthyl group, a pyridinyl group, or an anthracenyl group.

[0020] The alkyl group may be a mono- or poly-substituted alkyl group with a functional group such as a halo group, a nitro group, an amino group, a hydroxy group, a cyano group, a carbonyl group, or a carboxyl group, and the number of carbon atoms of the alkyl group is preferably 1 to 6. Furthermore, the aforementioned Ar is preferably a phenyl group or an alkylphenyl group, and more preferably a phenyl group.

[0021] Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene (including all isomers, particularly p-vinyltoluene), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, vinylanthracene (all isomers), and mixtures thereof.

[0022] The conjugated diene monomer that is the raw material for the conjugated diene monomer unit is not particularly limited as long as it is a monomer having two conjugated double bonds. Conjugated diene monomers include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3 pentadiene and the like, and mixtures thereof.

[0023] The polybutadiene, a polymer of 1,3-butadiene, can contain either the 1,2 configuration, which upon hydrogenation gives the equivalent of a 1-butene repeat unit, or the 1,4 configuration, which upon hydrogenation gives the equivalent of an ethylene repeat unit.

[0024] The hydrogenated polymerizable block composed of the aromatic vinyl monomer or the conjugated diene monomer including 1,3-butadiene is included in the hydrogenated block copolymer used in the present invention. Preferably, the hydrogenated block copolymer is a block copolymer without functional groups. The term "no functional groups" means that the block copolymer does not contain any functional groups, i.e., groups containing elements other than carbon and hydrogen.

[0025] A preferred example of the hydrogenated aromatic vinyl polymer block unit is a unit made of hydrogenated polystyrene, and a preferred example of the hydrogenated conjugated diene polymer block unit is a unit made of hydrogenated polybutadiene. A preferred embodiment of the hydrogenated block copolymer is a hydrogenated triblock or pentablock copolymer of styrene and butadiene, which preferably does not contain any other functional group or structural modifier. A "block" is defined as a polymeric segment of a copolymer that exhibits microphase separation from structurally or compositionally distinct polymeric segments of the copolymer. Microphase separation results from the immiscibility of polymeric segments in a block copolymer. Microphase separation and block copolymers are extensively discussed in "Block Copolymers - Designer Soft Materials," February 1999 issue of PHYSICS TODAY, pp. 32-38.

[0026] The content of the hydrogenated aromatic vinyl polymer block unit is 30 to 80 mol %, preferably 40 to 75 mol %, based on the cyclic polyolefin (A). If the ratio of hydrogenated aromatic vinyl polymer block units is equal to or greater than the above lower limit, the rigidity will not decrease, and if it is equal to or less than the above upper limit, the impact resistance will improve and the brittleness will not worsen.

[0027] The content of the hydrogenated conjugated diene polymer block unit is 20 to 70 mol %, preferably 25 to 60 mol %, based on the cyclic polyolefin (A). If the ratio of the hydrogenated conjugated diene polymer block units is equal to or greater than the above lower limit, the impact resistance is improved and the brittleness is not deteriorated, and if it is equal to or less than the above upper limit, the rigidity is not reduced.

[0028] As described above, the polyolefin according to the present invention is a "cyclic polyolefin," and the term "cyclic" here refers to an alicyclic structure formed by hydrogenation of the aromatic ring contained in the hydrogenated aromatic vinyl polymer block unit.

[0029] The hydrogenated block copolymers of the present invention are prepared by hydrogenation of block copolymers, including triblock, multiblock, tapered block, and star block copolymers, such as SBS, SBSBS, SIS, SISIS, and SISBS (where S is polystyrene, B is polybutadiene, and I is polyisoprene).

[0030] The hydrogenated block copolymer of the present invention contains an aromatic vinyl polymer segment at each end, resulting in at least two hydrogenated aromatic vinyl polymer block units, and at least one hydrogenated conjugated diene polymer block unit between the two hydrogenated aromatic vinyl polymer block units.

[0031] The block copolymers that make up the hydrogenated block copolymers before hydrogenation may contain additional blocks, which may be attached at any position along the triblock polymer backbone. Thus, linear blocks include, for example, SBS, SBSB, SBSBS, and SBSBSB. The copolymers may also be branched, with the polymer chains attached at any position along the copolymer backbone.

[0032] The lower limit of the weight average molecular weight (Mw) of the hydrogenated block copolymer is preferably 30,000 or more, more preferably 40,000 or more, even more preferably 45,000 or more, and particularly preferably 50,000 or more.The upper limit of Mw is preferably 120,000 or less, more preferably 100,000 or less, even more preferably 95,000 or less, particularly preferably 90,000 or less, most preferably 85,000 or less, and most preferably 80,000 or less. If Mw is equal to or greater than the lower limit, the mechanical strength will not decrease, and if it is equal to or less than the upper limit, the moldability will not deteriorate. Mw herein is determined using gel permeation chromatography (GPC).

[0033] The hydrogenation levels of the hydrogenated block copolymer are preferably 90% or more hydrogenated aromatic vinyl polymer block units and 95% or more hydrogenated conjugated diene polymer block units; more preferably 95% or more hydrogenated aromatic vinyl polymer block units and 99% or more hydrogenated conjugated diene polymer block units; even more preferably 98% or more hydrogenated aromatic vinyl polymer block units and 99.5% or more hydrogenated conjugated diene polymer block units; and particularly preferably 99.5% or more hydrogenated aromatic vinyl polymer block units and 99.5% or more hydrogenated conjugated diene polymer block units. The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit refers to the proportion of the aromatic vinyl polymer block unit saturated by hydrogenation, and the hydrogenation level of the hydrogenated conjugated diene polymer block unit refers to the proportion of the conjugated diene polymer block unit saturated by hydrogenation. Such a high level of hydrogenation is preferred for heat resistance and transparency.

[0034] The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit and the hydrogenated conjugated diene polymer block unit are determined using proton NMR.

[0035] The melt flow rate (MFR) of the cyclic polyolefin (A) of the present invention is not particularly limited, but is 0.1 g / 10 min or more, preferably 0.2 g / 10 min or more from the viewpoint of molding method and appearance of molded articles, and 200 g / 10 min or less, preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less from the viewpoint of material strength. The MFR was measured in accordance with ISO R1133 at a measurement temperature of 230°C and a measurement load of 2.16 kg.

[0036] The cyclic polyolefin (A) may be used alone or in combination of two or more different types having different monomer unit compositions, physical properties, etc. As the cyclic polyolefin (A) of the present invention, commercially available products can be used, specifically, XELAS (registered trademark) manufactured by Mitsubishi Chemical Corporation.

[0037] <Tackifying resin (B)> The tackifier resin (B) of the present invention (hereinafter, sometimes referred to as "component (B)") refers to a resin that can impart oil resistance, and examples thereof include hydrogenated terpene resins, hydrogenated rosin and hydrogenated rosin ester resins, disproportionated rosin and disproportionated rosin ester resins, and hydrogenated petroleum resins, and one or more selected from these may be used. When a tackifier resin (B) having good compatibility with component (A) is used, it can be compatible with component (A) in the thermoplastic resin composition, and transparency can be maintained.

[0038] The hydrogenated terpene resin is a hydrogenated thermoplastic resin whose main component is monoterpene (C10) or the like. Examples of hydrogenated terpene resins include terpene resins obtained by cationic polymerization of monomers mainly composed of α-pinene, β-pinene, dipentene, etc., and aromatic terpene resins copolymerized with phenols or aromatic monomers, and hydrogenated resins thereof.

[0039] Commercially available hydrogenated terpene resins include, for example, Clearon (registered trademark) P, M, and K series manufactured by Yasuhara Chemical Co., Ltd.

[0040] The hydrogenated rosin and hydrogenated rosin ester resin are natural resins obtained from pine trees and hydrogenated resins of their esters. Examples of the hydrogenated rosin and hydrogenated rosin ester resin include hydrogenated resins of rosin containing abietic acid and a mixture of its isomers as the main component and its ester resin.

[0041] Commercially available hydrogenated rosin and hydrogenated rosin ester resins include, for example, Foral (registered trademark) AX-E and Foral 105-E manufactured by Eastman Chemical Company; and Pencel (registered trademark) A, Estergum (registered trademark) H, and Superester (registered trademark) A series manufactured by Arakawa Chemical Industries, Ltd.

[0042] The disproportionated rosin and disproportionated rosin ester resin are those obtained by disproportionating rosin or rosin ester resin. Examples of the disproportionated rosin and disproportionated rosin ester resin include those obtained by adding a catalyst to rosin or a rosin ester resin, heating and melting the resin, and transferring hydrogen between resin acid molecules to convert abietic acid to dehydroabietic acid, dihydroabietic acid, or tetrahydroabietic acid.

[0043] Commercially available products of the disproportionated rosin and disproportionated rosin ester resin include, for example, the Pine Crystal (registered trademark) series manufactured by Arakawa Chemical Industries, Ltd.

[0044] The hydrogenated petroleum resin is a resin obtained by hydrogenating a petroleum resin solidified by an acid catalyst without isolating unsaturated hydrocarbons from mainly the C5 fraction and the C9 fraction, which are the remaining fractions obtained after the necessary fractions are extracted by thermal cracking of petroleum naphtha. Examples of the hydrogenated petroleum resins include hydrogenated dicyclopentadiene resins and partially hydrogenated aromatic-modified dicyclopentadiene resins, which are hydrogenated resins of C5 petroleum resins obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, and 1,3-pentadiene produced by the thermal decomposition of petroleum naphtha; C9 hydrogenated petroleum resins obtained by copolymerizing C9 fractions such as indene, vinyltoluene, and α- or β-methylstyrene produced by the thermal decomposition of petroleum naphtha; and hydrogenated petroleum resins copolymerized with the C5 fraction and the C9 fraction.

[0045] Examples of commercially available hydrogenated dicyclopentadiene resins include Escolez (registered trademark) 5300 and 5400 series manufactured by Donex Co., Ltd. and Eastotac (registered trademark) H series manufactured by Eastman Chemical Japan Co., Ltd. Commercially available products of the partially hydrogenated aromatic modified dicyclopentadiene resin include, for example, Escolez (registered trademark) 5600 series manufactured by Tonex Corporation.

[0046] Examples of commercially available C9 hydrogenated petroleum resins include Alcon (registered trademark) P and M series manufactured by Arakawa Chemical Industries, Ltd., and Polystolyn manufactured by Eastman Chemical Company. Examples of copolymerized hydrogenated petroleum resins of C5 fraction and C9 fraction include the Imarv (registered trademark) series manufactured by Idemitsu Kosan Co., Ltd.

[0047] Among the above, hydrogenated petroleum resins are preferred as the tackifier resin (B) from the viewpoint of color. The tackifier resin (B) may be used alone or in combination of two or more kinds.

[0048] The softening point of the tackifier resin (B), as measured by JIS K6823 (ring and ball method), is preferably 100° C. or higher, more preferably 115° C. or higher, and even more preferably 125° C. or higher. Also, it is preferably 180° C. or lower, more preferably 175° C. or lower, even more preferably 170° C. or lower, and particularly preferably 165° C. or lower. If the softening point is equal to or higher than the lower limit, the high-temperature adhesive strength and moldability will be good, and if it is equal to or lower than the upper limit, the moldability will be good.

[0049] <Styrene-based elastomer (C)> The thermoplastic resin composition according to the present invention may contain a styrene-based elastomer (C) in addition to the cyclic polyolefin (A) and tackifier resin (B). This styrene elastomer (C) is effective in improving the impact resistance while maintaining the transparency, moldability and oil resistance of the thermoplastic composition of the present invention.

[0050] The styrene elastomer (C) of the present invention is a copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit, and among these copolymers, a block copolymer containing both of these units and a hydrogenated block copolymer of this block copolymer are preferred. This block copolymer is a styrene-based block copolymer having an aromatic vinyl polymer block unit composed of at least one aromatic vinyl monomer unit and a conjugated diene polymer block unit composed of at least one conjugated diene monomer unit. The hydrogenated block copolymer is a hydrogenated styrene-based block copolymer (hereinafter, sometimes simply referred to as "hydrogenated block copolymer") having an aromatic vinyl polymer block unit composed of the aromatic vinyl monomer unit and a hydrogenated conjugated diene polymer block unit, which is a hydrogenated product of a polymer block composed of the conjugated diene monomer unit.

[0051] The relationship between the two block units of the styrene-based block copolymer or hydrogenated styrene-based block copolymer can be expressed by the following formula (2) or formula (3). S-(DS)m …(2) (SD)n …(3) (In the formula, S represents a polymer block composed of aromatic vinyl monomer units, D represents a polymer block composed of conjugated diene monomer units or a hydrogenated product thereof, and m and n represent integers of 1 to 5.)

[0052] As the styrene elastomer (C), the above-mentioned hydrogenated styrene block copolymer is particularly preferred. The styrene-based block copolymer and the hydrogenated styrene-based block copolymer may be linear, branched, and / or radial.

[0053] The aromatic vinyl monomer used as a raw material for the styrene-based block copolymer is preferably styrene or a styrene derivative such as α-methylstyrene, and the conjugated diene monomer used as a raw material for the styrene-based block copolymer is preferably butadiene and / or isoprene, more preferably butadiene.

[0054] The styrene-based block copolymer is particularly preferably a styrene-butadiene copolymer rubber or a styrene-isoprene copolymer rubber, and the hydrogenated styrene-based block copolymer is particularly preferably a styrene-butadiene copolymer rubber or a styrene-isoprene copolymer rubber in which the polybutadiene block unit or the polyisoprene block unit has been hydrogenated (hydrogenated). Specific examples of such hydrogenated styrene-based block copolymers include hydrogenated products of styrene-butadiene-styrene block copolymers and hydrogenated products of styrene-isoprene-styrene block copolymers, and hydrogenated products of styrene-butadiene-styrene block copolymers are particularly preferred.

[0055] When the block copolymer represented by the formula (2) and / or the formula (3) is a hydrogenated block copolymer and the polymer block D is composed only of a hydrogenated polybutadiene block unit, it is preferable that the 1,2-addition structure in the microstructure of the D block is 20 to 70 mass % in order to maintain the properties of the elastomer after hydrogenation.

[0056] The above m and n are preferably large in terms of lowering the order-disorder transition temperature, but are preferably small in terms of ease of production and cost. As the styrene-based block copolymer, a block copolymer represented by formula (2) or a hydrogenated block copolymer is preferred because of its excellent rubber elasticity, a block copolymer represented by formula (2) or a hydrogenated block copolymer in which m is 3 or less is more preferred, and a block copolymer represented by formula (2) or a hydrogenated block copolymer in which m is 2 or less is even more preferred.

[0057] The proportion of the "polymer block S" in the block copolymer or hydrogenated block copolymer represented by the formula (2) and / or formula (3) is preferably high from the viewpoint of the rigidity of the styrene-based elastomer, and is preferably low from the viewpoint of impact resistance. The proportion of the "polymer block S" in the block copolymer or hydrogenated block copolymer of formula (2) is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. From the viewpoint of the transparency of the thermoplastic resin composition of the present invention, the content of the "polymer block of S" (aromatic vinyl polymer block unit) in the styrene elastomer (C) is particularly preferably 25 to 35 mass %.

[0058] The weight average molecular weight (Mw) of the styrene elastomer (C) is preferably large in terms of impact resistance and mechanical strength, but is preferably small in terms of transparency, molded appearance and flowability. The weight average molecular weight (Mw) of the styrene elastomer (C) is preferably 10,000 or more, more preferably 30,000 or more, and is preferably 200,000 or less, more preferably 180,000 or less, and even more preferably 150,000 or less.

[0059] The weight average molecular weight (Mw) is a polystyrene-equivalent value measured using GPC under the following conditions. Equipment: 150CALC / GPC manufactured by Nihon Millipore Co., Ltd. Column: Showa Denko "AD80M / S" (3 columns) Detector: FOXBORO infrared spectrophotometer "MIRANIA" ·Wavelength: 3.42μm Solvent: o-dichlorobenzene ·Temperature: 140℃ ·Flow velocity: 1cm 3 / min ·Injection volume: 200μL ·Concentration: 2mg / cm 3 0.2% by mass of 2,6-di-t-butyl-p-phenol is added as an antioxidant. The hydrogenation rate of the conjugated diene block of the styrene elastomer (C) is preferably as high as possible in terms of compatibility with the component (A) and durability. The hydrogenation rate of the conjugated diene block of the styrene-based elastomer (C) is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more.

[0060] The styrene elastomer (C) may be produced by any method as long as the above-mentioned structure and physical properties are obtained, and known production methods can be used.

[0061] Commercially available hydrogenated block copolymers include "Tipole (registered trademark)" manufactured by TSRC, "Kraton (registered trademark) G" manufactured by Kraton Polymers, "Septon (registered trademark)" manufactured by Kuraray Co., Ltd., and "Tuftec (registered trademark)" manufactured by Asahi Kasei Corporation.

[0062] The styrene-based elastomer (C) may be used alone or in combination of two or more kinds.

[0063] <Thermoplastic resin composition> The thermoplastic resin composition of the present invention is a composition containing the above-mentioned cyclic polyolefin (A) and tackifier resin (B), and by further containing a styrene-based elastomer (C), the impact resistance can be further improved. The thermoplastic resin composition preferably contains 5 to 90 parts by mass of a tackifier resin (B) and 0 to 50 parts by mass of a styrene-based elastomer (C) relative to 100 parts by mass of the cyclic polyolefin (A).

[0064] The content of the tackifier resin (B) is more preferably 7 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the component (A), and more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less. When the content of the tackifier resin (B) is within the above range, the transparency, impact resistance, moldability and oil resistance are good.

[0065] The content of the styrene-based elastomer (C) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, per 100 parts by mass of the component (A). When the content of the styrene-based elastomer (C) is within the above range, the transparency, impact resistance, moldability and oil resistance are good.

[0066] The haze of the thermoplastic resin composition is preferably 20% or less, more preferably 10% or less, even more preferably 5% or less, and particularly preferably 3% or less. The MFR of the thermoplastic resin composition is preferably 1 g / 10 min or more, more preferably 2 g / 10 min or more, and is preferably 100 g / 10 min or less, more preferably 70 g / 10 min or less.

[0067] The Charpy impact strength of the thermoplastic resin composition is 10 kJ / m 2 More than 20kJ / m is preferable. 2 More preferably, 30 kJ / m or more 2 The above is more preferable. Furthermore, the thermoplastic resin composition preferably has oil resistance such that deformation is small, and more preferably no deformation occurs.

[0068] <Other ingredients> The thermoplastic resin composition of the present invention may contain, as other components, compounding agents that are commonly used in resin compositions, to the extent that the effects of the present invention are not impaired. Examples of such additives include heat stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, crystal nucleating agents, rust inhibitors, inorganic fillers, foaming agents, and pigments. Among these, it is preferable to add an antioxidant, particularly a phenol-based, sulfur-based, or phosphorus-based antioxidant, in an amount of 0.01 to 2 parts by mass per 100 parts by mass of the thermoplastic resin composition.

[0069] Furthermore, resin components and elastomer components other than component (A) and component (B) may be contained within the range that does not impair the effects of the present invention. Examples of such resin components include polyethylene resins, polypropylene resins, ethylene-α-olefin copolymer resins, propylene-α-olefin copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene-acrylic acid ester copolymer resins, ethylene-(meth)acrylic acid copolymer resins, polystyrene-based resins, polyvinyl chloride-based resins, polyester-based resins, polyamide-based resins, ethylene-vinyl alcohol copolymers, acrylic resins, and styrene-conjugated diene block copolymer resins.

[0070] Examples of the elastomer component include olefin elastomers, styrene elastomers, polyester elastomers, urethane elastomers, acrylic elastomers, and nylon elastomers.

[0071] The other components may be added to component (A) and component (B) by a kneading method commonly used for melt-kneading thermoplastic resins, or may be dissolved in an organic solvent together with component (A) and mixed. The content of other resin components is preferably 50% by mass or less, more preferably 30% by mass or less, of all components.

[0072] <Method of producing thermoplastic resin composition> The thermoplastic resin composition of the present invention can be produced by kneading component (A), component (B), and, if necessary, component (C) and other components in a conventional manner using a conventional extruder, Banbury mixer, roll, Brabender Plastograph, kneader-Brabender, or the like. Among these production methods, it is preferable to use an extruder, particularly a twin-screw extruder. When the thermoplastic resin composition of the present invention is produced by kneading it in an extruder or the like, it is usually melt-kneaded in a heated state at 180 to 300°C, preferably 220 to 280°C.

[0073] <Molded body and its manufacturing method> The thermoplastic resin composition of the present invention can be molded to obtain various molded articles. As a molding method, various molded articles can be produced by molding methods such as injection molding (insert molding, two-color molding, sandwich molding, gas injection molding, injection blow molding, etc.), extrusion molding, inflation molding, T-die film molding, lamination molding, blow molding, hollow molding, compression molding, and calendar molding. The thermoplastic resin composition of the present invention is preferably injection molded into a molded article, and the molding conditions for injection molding are as follows. The molding temperature is 200 to 300°C, and preferably 220 to 280°C. The injection pressure is 5 to 100 MPa, preferably 10 to 80 MPa. The mold temperature is 0 to 100°C, preferably 30 to 95°C.

[0074] <Application> The thermoplastic resin composition and molded article of the present invention are excellent in transparency, impact resistance, moldability, and oil resistance, and can therefore be suitably used as food containers, medical molded articles, optical parts, or electrical / electronic parts.

[0075] Examples of the food container include food bottles and Tupperware. Examples of the medical molded article include plastic slides; pharmaceutical containers such as eye drop containers, medicine bottle ampoules, vials, and caps used therefor; sampling containers such as test tubes, blood collection tubes, and specimen containers; and syringes such as prefilled syringes and injector syringes.

[0076] Examples of the optical component include a case, an optical lens, a light guide plate, a prism sheet, a Fresnel lens, a lenticular lens, an optical disk, an optical disk substrate, an optical disk for a blue laser, an optical disk substrate for a blue laser, a magneto-optical disk, a magneto-optical disk substrate, an optical card substrate, an optical waveguide, a diffusion sheet, a light-collecting sheet, and a light guide plate. Examples of the electric and electronic parts include connectors, relays, capacitors, sensors, antennas, IC trays, chassis, coil seals, motor cases, and power supply boxes. [Example]

[0077] The present invention will be explained in more detail below using examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. The values ​​of various production conditions and evaluation results in the following examples are meant as preferred upper or lower limit values ​​in the embodiments of the present invention, and a preferred range may be defined by a combination of the above-mentioned upper or lower limit value and the values ​​of the following examples or values ​​of the examples themselves. In the following description, "parts" refers to "parts by mass".

[0078] [Physical Properties] <Polymer block ratio> [Carbon NMR measurements] Equipment: Bruker AVANCE400 spectrometer Solvent: o-dichlorobenzene-H4 / p-dichlorobenzene-D4 mixed solvent ·Concentration: 0.3g / 2.5mL ·measurement: 13 C-NMR ·Resonance frequency: 400MHz Accumulation count: 1536 Flip angle: 45 degrees Data acquisition time: 1.5 seconds Pulse repetition time: 15 seconds ·Measurement temperature: 100℃ · 1 H irradiation: fully decoupled

[0079] <Hydrogenation level of hydrogenated aromatic vinyl polymer block unit and hydrogenated conjugated diene polymer block unit> [Proton NMR measurements] Equipment: JASCO Corporation "400YH Spectrometer" Solvent: deuterated chloroform ·Concentration: 0.045g / 1.0mL ·measurement: 1 H-NMR ·Resonance frequency: 400MHz Number of times accumulated: 8 ·Measurement temperature: 18.5℃ Hydrogenation level of hydrogenated aromatic vinyl polymer block unit: Integrated value reduction rate of 6.8 to 7.5 ppm Hydrogenation level of hydrogenated conjugated diene polymer block unit: Integrated value reduction rate of 5.7 to 6.4 ppm

[0080] <Melt flow rate (MFR)> In accordance with ISO R1133, the MFR, which is an index of moldability, was measured under the following conditions. Equipment: "Melt Indexer" manufactured by Toyo Seiki Seisakusho Co., Ltd. ·Temperature: 230℃ Orifice diameter: 2mm Load capacity: 2.16kg

[0081] <Haze> Using the obtained thermoplastic resin composition, a test piece having a thickness of 2 mm, a width of 50 mm, and a length of 50 mm was molded using an inline screw type injection molding machine ("SE18D" manufactured by Sumitomo Heavy Industries, Ltd.) at an injection pressure of 50 MPa, a cylinder temperature of 250°C, and a mold temperature of 50°C. The haze, which is an index of transparency, was measured in accordance with ISO 14782.

[0082] <Charpy impact strength> Using the obtained thermoplastic resin composition, a test piece for Charpy impact strength (a test piece having a thickness of 4 mm, a width of 10 mm, and a length of 80 mm) was molded using an in-line screw type injection molding machine (SE18D manufactured by Sumitomo Heavy Industries, Ltd.) at an injection pressure of 50 MPa, a cylinder temperature of 250°C, and a mold temperature of 50°C. Using this test piece, the Charpy impact strength, which is an index of impact resistance, was measured at 23°C without a notch in accordance with ISO179.

[0083] <Oil resistance> Using the obtained thermoplastic resin composition, a test piece having a thickness of 2 mm, a width of 50 mm, and a length of 50 mm was molded using an inline screw type injection molding machine (SE18D manufactured by Sumitomo Heavy Industries, Ltd.) at an injection pressure of 50 MPa, a cylinder temperature of 250°C, and a mold temperature of 50°C. A drop of paraffin oil was dropped onto this test piece using a dropper, and the test piece was placed in a Gyre oven adjusted to 80°C for 24 hours, and deformation was visually confirmed. Large deformations were marked with an X, and small deformations were marked with an ◯.

[0084] [Raw materials] <Cyclic polyolefin (A-1)> Mitsubishi Chemical Corporation Zelas (registered trademark) MC930 ·Density (ASTM D792): 0.94g / cm 3 ·MFR (230℃, 2.16kg): 1g / 10 minutes Hydrogenated aromatic vinyl polymer block unit: Hydrogenated polystyrene with a content of 65 mol% and a hydrogenation level of 99.5% or more Hydrogenated conjugated diene polymer block units: Hydrogenated polybutadiene with a content of 35 mol% and a hydrogenation level of 99.5% or higher Block structure: Pentablock structure, Total hydrogenation level: 99.5% or more

[0085] <Cyclic polyolefin (A-2)> Mitsubishi Chemical Corporation Zelas (registered trademark) MC932 ·Density (ASTM D792): 0.94g / cm 3 ·MFR (230℃, 2.16kg): 0.5g / 10 minutes Hydrogenated aromatic vinyl polymer block unit: Hydrogenated polystyrene with a content of 50 mol% and a hydrogenation level of 98.7% Hydrogenated conjugated diene polymer block unit: Hydrogenated polybutadiene with a content of 50 mol% and a hydrogenation level of 99.5% or more Block structure: Pentablock structure, Total hydrogenation level: 99.2%

[0086] <Cyclic polyolefin (A-3)> Mitsubishi Chemical Corporation Zelas (registered trademark) MC933 ·Density (ASTM D792): 0.94g / cm 3 ·MFR (230℃, 2.16kg): 1.1g / 10 minutes Hydrogenated aromatic vinyl polymer block unit: Hydrogenated polystyrene with a content of 50 mol% and a hydrogenation level of 99.9% Hydrogenated conjugated diene polymer block unit: Hydrogenated polybutadiene with a content of 50 mol% and a hydrogenation level of 99.8% or higher Block structure: Pentablock structure, Total hydrogenation level: 99.8%

[0087] <Tackifying resin (B-1)> Arakawa Chemical Industries, Ltd. Alcon (registered trademark) P-115 ·Density (ASTM D792): 1.00g / cm 3 Hydrogenated petroleum resin ·Softening temperature: 115℃

[0088] <Tackifying resin (B-2)> Arakawa Chemical Industries, Ltd. Alcon (registered trademark) P-140 Hydrogenated petroleum resin ·Density (ASTM D792): 1.00g / cm 3 ·Softening temperature: 140℃

[0089] <Tackifying resin (B-3)> Idemitsu Kosan Co., Ltd. Imarv (registered trademark) P-140 Hydrogenated petroleum resin ·Density (ASTM D792): 1.03g / cm 3 ·Softening temperature: 140℃

[0090] <Tackifying resin (B-4)> Eastman Chemical Company Plastolyn® R1140 ·Density (ASTM D792): 0.98g / cm 3 Hydrogenated petroleum resin ·Softening temperature: 140℃

[0091] <Styrene-based elastomer (C-1)> Kraton® G1650MU manufactured by Kraton Polymers [Hydrogenated styrene-butadiene-styrene block copolymer, aromatic vinyl polymer block unit: 30% by mass, butadiene hydrogenation rate: 99% or more, Mw: 90,000]

[0092] <Cyclic Polyolefin (D-1)> Cyclic polyolefin (A-1) 25 parts, hydrogenated polystyrene (density: 0.94 g / cm 3 75 parts of a cyclic polyolefin (H2O3, MFR 0.3 g / 10 min, hydrogenation level 99.5% or higher) and 0.05 parts of Irgafos 168 manufactured by BASF as an antioxidant were added, and the mixture was melt-kneaded for 1 minute at a temperature of 270°C and a screw rotation speed of 100 rpm using a plunger-type injection molding machine (an injection molding machine attached to a small kneader Xplore MC15 manufactured by Xplore Instruments) to obtain a cyclic polyolefin (D-1). ·Density (ASTM D792): 0.94g / cm 3 ·MFR (230℃, 2.16kg): 0.5g / 10 minutes Hydrogenated aromatic vinyl polymer block units: Hydrogenated polystyrene with a content of 91 mol% and a hydrogenation level of 99.5% or higher Hydrogenated conjugated diene polymer block units: Hydrogenated polybutadiene with a content of 9 mol% and a hydrogenation level of 99.5% or higher Block structure: Pentablock structure, Total hydrogenation level: 99.5% or more

[0093] < Reference example 1 > 100 parts of cyclic polyolefin (A-1), 11 parts of tackifier resin (B-1), and 0.05 parts of BASF Irgafos 168 as an antioxidant were added and fed into a co-rotating twin-screw extruder (Technovel KZW15-45MG Φ15, L / D=45) at a rate of 2 kg / h, heated to a temperature of 240°C, and melt-kneaded to obtain pellets of a thermoplastic resin composition. The obtained pellets were used to evaluate various physical properties, and the results are shown in Table 1.

[0094] < Reference Examples 2 to 9, Examples 1 to 2 , Comparative Examples 1-2> According to the formulation shown in Table 1, Reference example 1 In the same manner as above, pellets of a thermoplastic resin composition were obtained. Reference example 1 The various physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0095] <Comparative Example 3> 100 parts of cyclic polyolefin (D-1), 11 parts of tackifier resin (B-1), and 0.05 parts of BASF Irgafos 168 as an antioxidant were added, and the mixture was melt-mixed for 1 minute using a plunger-type injection molding machine (Xplore Instruments, Xplore MC15 compact kneader attached injection molding machine) at 270 ° C. and 100 rpm. The injection pressure was 3.5 bar, the cylinder temperature was 270 ° C., and the mold temperature was 70 ° C. Test pieces measuring 2 mm thick x 30 mm wide x 80 mm long and 4 mm thick x 10 mm wide x 80 mm long were molded, and various physical properties were evaluated. The results are shown in Table 1.

[0096] <Comparative Example 4> According to the formulation shown in Table 1, melt-kneading and molding were carried out in the same manner as in Comparative Example 3 to obtain test specimens. Various physical properties were evaluated in the same manner, and the results are shown in Table 1.

[0097] [Table 1]

[0098] From Table 1, the present invention is applicable Reference Examples 1 to 9, Examples 1 to 2It was found that the resin had excellent transparency, impact resistance, moldability and oil resistance. In contrast, it was found that Comparative Examples 1 and 2, which did not contain the tackifier resin (B), had poor oil resistance. Furthermore, Comparative Example 2 had a low MFR and poor moldability.

[0099] It was found that Comparative Examples 3 and 4, in which the cyclic polyolefin (D) having a low content of hydrogenated conjugated diene polymer block units was used instead of the cyclic polyolefin (A), were inferior in impact resistance. [Industrial Applicability]

[0100] The thermoplastic resin composition and molded article of the present invention can be suitably used for food containers such as food bottles and Tupperware, medical molded articles such as plastic slides, drug storage containers, sampling containers and syringes, optical parts such as lenses and covers, or electric / electronic parts, etc.

Claims

1. A thermoplastic resin composition containing a cyclic polyolefin (A), a tackifier resin (B), and a styrene-based elastomer (C), the cyclic polyolefin (A) comprises a hydrogenated block copolymer which is a hydrogenated product of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit; the hydrogenated block copolymer comprises a hydrogenated aromatic vinyl polymer block unit which is a hydrogenated product of a polymer block composed of the aromatic vinyl monomer unit, and a hydrogenated conjugated diene polymer block unit which is a hydrogenated product of a polymer block composed of the conjugated diene monomer unit, the hydrogenated block copolymer has at least two of the hydrogenated aromatic vinyl polymer block units and at least one of the hydrogenated conjugated diene polymer block units; the hydrogenated aromatic vinyl polymer block units have a hydrogenation level of 90% or greater, and the hydrogenated conjugated diene polymer block units have a hydrogenation level of 95% or greater; the styrene-based elastomer (C) is a styrene-butadiene copolymer rubber or a styrene-isoprene copolymer rubber, and the polybutadiene block unit or the polyisoprene block unit is hydrogenated; the content of the hydrogenated aromatic vinyl polymer block unit in the cyclic polyolefin (A) is 30 to 80 mol % and the content of the hydrogenated conjugated diene polymer block unit is 20 to 70 mol %, A thermoplastic resin composition for food containers or medical molded articles, comprising 5 to 90 parts by mass of a tackifier resin (B) and 1 to 50 parts by mass of a styrene-based elastomer (C) relative to 100 parts by mass of the cyclic polyolefin (A).

2. 2. The thermoplastic resin composition for food containers or medical molded articles according to claim 1, wherein the hydrogenated aromatic vinyl polymer block units are units consisting of hydrogenated polystyrene, and the hydrogenated conjugated diene polymer block units are units consisting of hydrogenated polybutadiene.

3. 3. The thermoplastic resin composition for food containers or medical molded articles according to claim 1 or 2, wherein the tackifier resin (B) is at least one selected from the group consisting of hydrogenated terpene resins, hydrogenated rosin and hydrogenated rosin ester resins, disproportionated rosin and disproportionated rosin ester resins, and hydrogenated petroleum resins.

4. 3. The thermoplastic resin composition for food containers or medical molded articles according to claim 1, wherein the tackifier resin (B) is a hydrogenated petroleum resin.

5. The thermoplastic resin composition for food containers or medical molded articles according to any one of claims 1 to 4, wherein the softening point of the tackifier resin (B) is 100 to 180°C.

6. The thermoplastic resin composition for food containers or medical molded articles according to any one of claims 1 to 5, wherein the styrene-based elastomer (C) has a weight average molecular weight of 10,000 to 200,000.

7. A molded article made of the thermoplastic resin composition for food containers or medical molded articles according to any one of claims 1 to 6.

8. 8. The molded article according to claim 7, which is a food container or a medical molded article.

9. The molded article according to claim 8, wherein the food container is a food bottle or a Tupperware.

10. The medical molded article according to claim 8, which is a plastic slide glass, an eye dropper, a medicine bottle ampoule, a vial, a cap used therefor, a test tube, a blood collection tube, a specimen container, a prefilled syringe, or a syringe syringe.

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