Propylene resin compositions, medical components, kit formulations, pre-filled syringes, dialyzer housings, eye drop containers, food containers, and disposable syringes.

Abstract

To provide a propylene-based resin composition with excellent transparency and moldability, and a molded article made from the resin composition. [Solution] A propylene-based resin composition characterized by blending 0.02 to 0.9 parts by weight of a clearing nucleating agent (A) represented by the following chemical structural formula (1) with 100 parts by weight of a propylene-based polymer. JPEG2026104792000022.jpg45169 [In general formula (1), X 1 , X 2 and X 3 Each of the symbols represents an unsubstituted or substituted phenylene group, and *, **, and *** represent sites that bond with other atoms.

Description

[Technical Field]

[0001] The present invention relates to propylene resin compositions, medical components, kit formulations, pre-filled syringes, dialyzer housings, eye drop containers, food containers, and disposable syringes, and more particularly to propylene resin compositions and molded articles thereof that exhibit excellent transparency and moldability. [Background technology]

[0002] Propylene polymers are highly moldable, rigid, recyclable, and heat-resistant, and are widely used in various applications such as food containers, caps, medical devices, medical containers, packaging films, stationery sheets, clothing cases, daily necessities, automotive parts, and electrical components, similar to other resins like polyvinyl chloride and polystyrene. Examples of medical applications where passing pharmacopoeial tests is a mandatory requirement include kit formulations such as pre-filled syringes containing pre-pre-filled drug solutions. In these applications, superior transparency and moldability are strongly required for propylene polymers or their compositions.

[0003] Among propylene-based polymers, propylene homopolymers are preferred in terms of rigidity, heat resistance, and gas barrier properties; random copolymers of ethylene, butene, etc., and propylene are preferred in terms of transparency and impact resistance; and block copolymers of ethylene, butene, etc., and propylene are preferred in terms of heat resistance and impact resistance. They are used selectively as appropriate depending on the situation. However, block copolymers have difficulty achieving sufficient performance in terms of transparency, propylene homopolymers are inferior in transparency, though not as much as block copolymers, and have difficulty achieving sufficient performance in terms of impact resistance, and random copolymers have excellent transparency, but tend to show deterioration in moldability as the crystallization temperature decreases.

[0004] For this reason, attempts have been made not only to modify propylene polymers, but also to improve their transparency and moldability by using nucleating agents. The most commonly used nucleating agents are organophosphate-based nucleating agents (see, for example, Patent Document 1), dimethylbenzylidenesorbitol-based nucleating agents (see, for example, Patent Document 2), and nonitol-based nucleating agents (see, for example, Patent Document 3).

[0005] However, even with the use of these existing transparency-enhancing nucleating agents, the improvement in transparency is not always sufficient and does not reach the level of transparency of other resins such as polystyrene. Furthermore, although some improvement in moldability is observed, the effect is not sufficient. For this reason, there has been a strong desire to improve both transparency and moldability simultaneously using a new method. In particular, for medical and food packaging applications, in addition to the challenges of improving transparency and moldability, there were the following challenges: namely, the challenge of achieving both unprecedentedly high levels of transparency and moldability while ensuring safe use in medical applications where the material comes into direct contact with drugs and in food packaging applications where the material comes into direct contact with food. For medical applications, being safe means, for example, having low elution levels that can meet the elution test standards of the Japanese Pharmacopoeia, and for food applications, low elution and low odor are also required. Furthermore, Patent Document 4 below contains no descriptions or suggestions regarding medical or food packaging applications, and does not disclose any issues specific to this field, such as meeting the standards of the Japanese Pharmacopoeia. Patent Document 4 does not envision the use of the clearing nucleating agent disclosed in this document for medical purposes. For medical applications, for example, it is necessary to satisfy the test items described in Patent Document 5. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 5-140466 [Patent Document 2] Japanese Patent Application Publication No. 53-117044 [Patent Document 3] Japanese Patent Publication No. 2007-534827 [Patent Document 4] Japanese Patent Application Laid-Open No. 2024-117817 [Patent Document 5] Japanese Patent Application Laid-Open No. 2009-120798 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] In view of the above problems, an object of the present invention is to provide a propylene-based resin composition excellent in transparency and molding processability, and a molded product formed from the resin composition. Another object of the present invention is, in the fields of medical use and food packaging material use, not only to improve the mere transparency of the propylene-based resin composition and the molded product, but also to achieve both high safety and excellent physical properties. [Means for Solving the Problems]

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that by using a specific clarifying nucleating agent for a propylene-based polymer, a propylene-based resin composition excellent in transparency, molding processability, heat resistance, rigidity, and impact resistance can be obtained, and thus the present invention has been completed. In addition, as a result of intensive studies by the present inventors to solve the difficult problem of clearing strict regulations in the special technical fields of medical use and food packaging material use, they have found that it can be achieved for the first time in a specific configuration, and thus the present invention has been completed.

[0009] The present invention can be realized in the following forms. The inventions according to the following [1] to

[13] are also referred to as the first to thirteenth inventions. [1] A propylene-based resin composition, characterized in that 0.02 to 0.9 parts by weight of a clarifying nucleating agent (A) represented by the following chemical structural formula (1) is contained and blended with 100 parts by weight of a propylene-based polymer (B) satisfying the following condition (B-1). [Chemical Formula] [In general formula (1), X 1 , X 2 and X 3 each independently represent an unsubstituted or substituted phenylene group, and *, **, and *** represent sites for bonding to other atoms.] Condition (B-1) The propylene-based polymer (B) is at least one propylene-based polymer selected from the group consisting of a propylene homopolymer, a propylene-α-olefin random copolymer, and a propylene-α-olefin block copolymer.

[0010] [2] The propylene-based resin composition according to [1], which is for a medical member.

[0011] [3] The propylene-based resin composition according to [1] or [2], wherein the medical member is at least one selected from the group consisting of for a kit formulation, a prefilled syringe, a housing of a dialyzer, and a disposable syringe.

[0012] [4] The propylene-based resin composition according to any one of [1] to [3], wherein the propylene-based polymer (B) has a melt flow rate conforming to JIS K7210-1:2014 (230 °C, 2.16 kg load) of 0.5 to 100 g / 10 min.

[0013] [5] The propylene-based resin composition according to any one of [1] to [4], wherein the clarifying nucleating agent (A) is represented by the following chemical structural formula (2). [Chemical formula] [In general formula (2), W 1 ~W 3 each independently represent a group represented by the following general formula (3).] [Chemical formula] [In general formula (3), Ar 1 represents an unsubstituted or substituted phenyl group, R 1 represents a hydrogen atom or a monovalent substituent, L 1 and L 2 each independently represent a group represented by the following general formula (4), m represents an integer of 0 or 1 or more, and **** represents the site bonded to an oxygen atom.] [Chemical formula] [In general formula (4), X 4 and X 5 each independently represent an unsubstituted or substituted phenylene group, A 1 represents a direct bond or an alkanediyl group having 1 to 30 carbon atoms, and n represents 0 or 1.]

[0014] [6] The propylene-based resin composition according to [1] to [5], wherein the clarification nucleating agent (A) contains a compound represented by the following chemical structural formula (5). [Chemical formula]

[0015] [7] A medical member using the propylene-based resin composition according to any one of [1] to [6].

[0016] [8] A kit preparation using the propylene-based resin composition according to any one of [1] to [6].

[0017] [9] [[ID=CO]]A prefilled syringe using the propylene-based resin composition according to any one of [1] to [6].

[0018]

[10] A dialyzer housing using a propylene-based resin composition as described in any of [1] to [6].

[0019]

[11] An eye drop container using a propylene resin composition as described in any of [1] to [6].

[0020]

[12] A food container using a propylene resin composition as described in any of [1], [4], [5], or [6].

[0021]

[13] A disposable syringe using a propylene resin composition as described in any of [1] to [6]. [Effects of the Invention]

[0022] The propylene-based resin composition of the present invention is a polypropylene-based resin composition obtained by blending a novel transparency nucleating agent shown in the chemical structural formula (1) with a propylene-based polymer. By using such a novel nucleating agent, excellent transparency, moldability, heat resistance, rigidity, and impact resistance that could not be achieved with conventional propylene-based resin compositions can be obtained. Furthermore, in addition to the effects described above, the present invention can achieve excellent physical properties while ensuring safety that satisfies the test items of the Japanese Pharmacopoeia. Therefore, it is extremely suitable for medical applications where safety is of particular importance, especially kit formulations, and among them, pre-filled syringes. [Brief explanation of the drawing]

[0023] [Figure 1] This is a schematic diagram of a pre-filled syringe, an example of a kit formulation. [Figure 2] This is a conceptual diagram of hemodialysis. [Figure 3] This is a diagram illustrating the main components of a dialyzer. [Figure 4] This is a schematic diagram of an eye drop container. [Figure 5] This is a summary of the differences between eye drop containers and the Japanese Pharmacopoeia. [Figure 6]This is a schematic diagram of an example of a food container. [Figure 7] This is a schematic diagram of a disposable syringe. [Modes for carrying out the invention]

[0024] The present invention will be described in detail below. In this specification, when numerical ranges are described using "~", unless otherwise specified, both the lower limit and the upper limit are included. For example, the description "10~20" includes both the lower limit "10" and the upper limit "20". In other words, "10~20" has the same meaning as "10 or more and 20 or less". Furthermore, any combination of upper and lower limits can be used to indicate numerical ranges in this disclosure. Furthermore, "weight" and "mass," "weight%" and "mass%," and "parts of weight" and "parts of mass" are treated as synonyms.

[0025] The present invention relates to a propylene-based resin composition obtained by blending 0.02 to 0.9 parts by weight of a clearing nucleating agent (A) represented by the chemical structural formula (1) with 100 parts by weight of a propylene-based polymer (B) that satisfies the above condition (B-1), and molded articles obtained by molding the propylene-based resin composition by various methods. The components constituting the propylene-based resin composition, the method for producing the propylene-based resin composition, and the molded articles will be described in detail below. Here, molded articles include, for example, medical components, kit formulations, pre-filled syringes, dialyzer housings, eye drop containers, disposable syringes, and food containers.

[0026] [1] Components constituting the propylene resin composition (1) Propylene polymer (Condition (B-1)) The propylene polymer (B) satisfies the following condition (B-1). Condition (B-1) The propylene polymer (B) is at least one propylene polymer selected from the group consisting of propylene homopolymers, propylene-α-olefin random copolymers, and propylene-α-olefin block copolymers. While it is common for propylene-α-olefin random copolymers to use one or more α-olefins other than propylene as comonomers, they are not limited to this. Propylene-α-olefin block copolymers generally use one or more α-olefins other than propylene as comonomers, but are not limited to this. Hereinafter, in this specification, propylene-α-olefin random copolymers and propylene-α-olefin block copolymers may be simply referred to as "propylene-α-olefin copolymers." The propylene-α-olefin copolymers preferably used to exhibit excellent transparency are copolymers in which propylene and α-olefins having 2 to 8 carbon atoms other than propylene are comonomers, having a propylene content of 85 to 99.99% by weight (i.e., a comonomer content of 0.01 to 15% by weight), and more preferably random copolymers or block copolymers of propylene and α-olefins with a propylene content of 90% by weight or more. Alternatively, a mixture of different random copolymers or block copolymers of α-olefins may also be used.

[0027] Furthermore, the comonomer, which is an α-olefin with 2 to 8 carbon atoms excluding propylene, may be used alone or in combination of two or more types. Examples of propylene-α-olefin copolymers include binary copolymers such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-pentene-1 copolymer, propylene-hexene-1 copolymer, and propylene-octene-1 copolymer, and ternary copolymers such as propylene-ethylene-butene-1 copolymer and propylene-ethylene-hexene-1 copolymer, with propylene-ethylene random copolymer and propylene-ethylene-butene-1 random copolymer being preferred. The α-olefin monomer content in the propylene-α-olefin copolymer is usually about 0.01 to 30% by weight, preferably 1 to 20% by weight, and more preferably about 1 to 10% by weight.

[0028] Examples of α-olefins having 2 to 8 carbon atoms, excluding propylene, include ethylene, 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, and 1-octene.

[0029] Furthermore, from the viewpoint of moldability, the propylene polymer (B) preferably has a melting point of 100 to 170°C, and more preferably 150 to 165°C. The melting point of the propylene polymer can be appropriately controlled mainly by the type of propylene and other α-olefins used as raw materials, the copolymerization ratio, the melt flow rate (MFR), etc. In this specification, "melting point" refers to the melting peak temperature measured by a differential scanning calorimeter (DSC).

[0030] Furthermore, the propylene polymer (B) used in the present invention is preferably one with a melt flow rate (hereinafter sometimes abbreviated as "MFR") of 0.3 to 500 g / 10 min in accordance with JIS K7210 (230°C, 2.16 kg load), which allows for good moldability, the resulting physical properties of the molded article, and the transparency of the molded article, and more preferably one with a melt flow rate of 0.5 to 100 g / 10 min. That is, if the melt flow rate is significantly lower than 0.3 g / 10 min, there is a risk that the moldability and the resulting physical properties of the molded article will deteriorate. For example, in extrusion molding, the extrusion load during extrusion molding will increase, the smoothness of the surface will be impaired, and the appearance of the molded article may deteriorate. Conversely, if it is significantly higher than 500 g / 10 min, the uniform dispersion of the transparency nucleating agent in the propylene polymer will deteriorate, and transparency may not be easily achieved.

[0031] The catalyst used to obtain the propylene polymer (B) used in the present invention is not particularly limited, and known catalysts can be used. For example, known catalysts include the so-called Ziegler-Natta catalyst, which combines a titanium compound and organoaluminum, or metallocene catalysts (for example, as described in Japanese Patent Publication No. 5-295022). The polymerization process used to obtain the propylene polymer (B) used in the present invention is not particularly limited, and known polymerization processes can be used. For example, known polymerization processes include slurry polymerization, bulk polymerization, and gas-phase polymerization. Polymerization can also be performed by multi-stage polymerization using one or more of these polymerization methods. Furthermore, it can also be produced by mechanically melt-kneading two or more propylene polymers. When using two or more propylene polymers, the physical properties such as MFR are evaluated on a mixture mixed in a desired composition ratio. Furthermore, various propylene polymers are commercially available from many companies, and it is possible to obtain and use a propylene polymer with the desired physical properties from among these commercially available propylene polymers as the propylene polymer (B) used in the present invention.

[0032] (2) Clearing nucleating agent (A) The clearing nucleating agent (A) used in the propylene resin composition of the present invention is a clearing nucleating agent represented by the following chemical structural formula (1). Two or more different compounds may be used in combination as the clearing nucleating agent (A), as long as they are compounds represented by the chemical structural formula (1). [ka] [In general formula (1), X 1 , X 2 and X 3 Each of the symbols represents an unsubstituted or substituted phenylene group, and *, **, and *** represent sites that bond with other atoms.

[0033] A more preferred clearing nucleating agent (A) is shown by the following chemical structural formula (2). [ka] [In general formula (2), W 1 ~W 3 Each of these independently represents a group represented by the following general formula (3). [ka] [In general formula (3), Ar 1 R represents an unsubstituted or substituted phenyl group, 1 represents a hydrogen atom or a monovalent substituent, L 1 and L 2 Each of these independently represents a group represented by the following general formula (4), where m represents 0 or an integer greater than or equal to 1, and **** represents the site that bonds with the oxygen atom. [ka] [In general formula (4), X 4 and X 5Each of these independently represents an unsubstituted or substituted phenylene group, and A 1 [where n represents a direct bond or an alkanediyl group with 1 to 30 carbon atoms, and n represents 0 or 1.]

[0034] A more preferred clearing nucleating agent (A) is shown by the following chemical structural formula (5). When using the compound of chemical structural formula (5) as the clearing nucleating agent (A), other clearing nucleating agents may be used in combination. The other clearing nucleating agents are different from the compound of chemical structural formula (5), but compounds that satisfy the above chemical structural formula (2) are preferred. In this case, the main component of the clearing nucleating agent (A) is preferably the compound of chemical structural formula (5). The main component refers to a substance with a content (mass%) of 50% by mass or more. [ka]

[0035] The crystallization nucleating agent (A) used in the present invention can impart to the resulting molded article exceptionally high transparency, a level unattainable with conventional crystallization nucleating agents. Furthermore, because it can induce a higher crystallization temperature than conventional crystallization nucleating agents, it can also improve moldability.

[0036] The amount of the clearing nucleating agent (A) used in the propylene-based resin composition of the present invention is 0.02 to 0.9 parts by weight per 100 parts by weight of the propylene polymer, preferably 0.05 to 0.8 parts by weight, more preferably 0.06 to 0.5 parts by weight, more preferably 0.07 to 0.3 parts by weight, particularly preferably 0.08 to 0.2 parts by weight, and most preferably 0.09 to 0.15 parts by weight. By setting the content of the clearing nucleating agent (A) within this range, it is possible to obtain a propylene-based resin composition with excellent transparency. That is, if the amount is less than 0.02 parts by weight, it may be difficult to obtain a sufficient transparency effect. Also, if it exceeds 0.9 parts by weight, aggregation of the clearing nucleating agent may occur, which may reduce transparency, so this is undesirable. Furthermore, when two or more different compounds are used in combination as the clearing nucleating agent (A), the amount of clearing nucleating agent (A) refers to the total amount of the compounds used in combination.

[0037] A method for producing the clearing nucleating agent (A) used in the present invention can be described in Japanese Patent Publication No. 2024-117817, etc. Commercially available products can also be readily obtained, such as Transparex (manufactured by ADEKA Corporation).

[0038] Furthermore, in the propylene-based resin composition of the present invention, in order to further improve transparency, rigidity, moldability, etc., at least one other nucleating agent in addition to the clearing nucleating agent (A) may be used in combination to the extent that it does not significantly impede the effects of the present invention. The nucleating agent used here is not particularly limited, and known nucleating agents can be used. For example, known nucleating agents such as sorbitol-based clearing nucleating agents, nonitol-based clearing nucleating agents, organophosphate-based clearing nucleating agents, aromatic phosphate esters, and talc can be added to the extent that it does not significantly impede the effects of the present invention.

[0039] (3) Other additives In the propylene-based resin composition of the present invention, in addition to the propylene-based polymer and the clearing nucleating agent (A), various additives such as antioxidants, neutralizing agents, lubricants, ultraviolet absorbers, and light stabilizers used as stabilizers for propylene-based polymers can be incorporated to the extent that they do not significantly impair the effects of the present invention.

[0040] Specifically, examples of the antioxidant include phosphorus-based antioxidants such as bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-diphosphite, di-stearyl-pentaerythritol-diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol-diphosphite, tris(2,4-di-t-butylphenyl)phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene-diphosphonite, tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'-biphenylene-diphosphonite; phenolic antioxidants such as 2,6-di-t-butyl-p-cresol, tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate; thio-based antioxidants such as di-stearyl-ββ'-thio-dipropionate, di-myristyl-ββ'-thio-dipropionate, di-lauryl-ββ'-thio-dipropionate, and the like.

[0041] Specific examples of the neutralizing agent include metal fatty acid salts such as calcium stearate, zinc stearate, magnesium stearate; hydrotalcite (trade name: magnesium aluminum composite hydroxide salt represented by the following general formula (6) of Kyowa Chemical Industry Co., Ltd.); Mizukarak (lithium aluminum composite hydroxide salt represented by the following general formula (7)), and the like.

[0042] Mg 1-x Al x (OH)2(CO3) x / 2 ·mH2O …(6) [In the formula, x is 0 < x ≦ 0.5, and m is a number of 3 or less.] [Al2Li(OH)6]nX·mH2O …(7) [In the formula, X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less.]

[0043] Specific examples of lubricants include well-known lubricants such as oleamide, stearamide, erucamide, behenamide, and other fatty acid amides, as well as butyl stearate and silicone oil.

[0044] Examples of UV absorbers include 2-hydroxy-4-n-octoxybenzophenone, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole.

[0045] As light stabilizers, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl)ethanol condensate, poly{[6-[(1,1,3,3-tetramethylbutyl) Examples of light stabilizers include [mino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]} and N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate.

[0046] Furthermore, examples include amine-based antioxidants represented by the following chemical structural formula (8) or general formula (9), lactone-based antioxidants such as 5,7-di-t-butyl-3-(3,4-di-methylphenyl)-3H-benzofuran-2-one, and vitamin E-based antioxidants such as the following chemical structural formula (10).

[0047] [ka]

[0048] [ka] [However, in equation (9), R 1 and R 2 This refers to alkyl groups with 14 to 22 carbon atoms.

[0049] [ka]

[0050] Furthermore, other substances such as antistatic agents, dispersants like fatty acid metal salts, polyethylene, and olefin-based elastomers can be incorporated to the extent that they do not impair the objectives of the present invention.

[0051] [2] Method for producing propylene resin composition The propylene-based resin composition of the present invention can be obtained by mixing a propylene-based polymer, a clearing nucleating agent (A), and other additives as needed in a Henschel mixer, super mixer, ribbon blender, etc., and then melt-kneading it at a temperature range of 180 to 280°C in a conventional single-screw extruder, twin-screw extruder, Banbury mixer, plastic bender, roll, etc.

[0052] [3] Molded products The molded articles of the present invention are obtained by molding the above-mentioned propylene-based resin composition using various molding machines such as known injection molding machines, extrusion molding machines, film molding machines, blow molding machines, and fiber molding machines. The molded articles of the present invention include injection molded articles, extruded articles, hollow molded articles, compression molded articles, calendered articles, laminated articles, fluid immersion molded articles, blow molded articles, slush molded articles, rotational molded articles, thermoformed articles, CCM molded articles, etc. Specifically, these include food containers (pudding containers, jelly containers, yogurt containers, chawanmushi containers, instant ramen containers, chilled coffee containers, dessert containers, vending cups, iced coffee cups, bento boxes, and their respective lids), caps (PET bottle caps, one-piece caps, two-piece caps, instant coffee caps, etc.), medical devices and containers (disposable syringes and their parts, catheters and tubes, infusion bags, blood bags, vacuum blood collection tubes, surgical nonwoven fabrics, blood filters, blood circuits and other disposable devices, as well as parts for artificial organs such as artificial lungs and colostomies, dialyzers, pre-filled syringes, kit formulations, drug containers, test tubes, sutures, and poultice bases). Examples include parts for dental materials, parts for orthopedic materials, manufacturing molds and cases for contact lenses, PTP, SP / packaging, P vials, eye drop containers, drug solution containers, long-term storage containers for liquids, etc.), daily necessities (clothing cases, buckets, washbasins, writing instruments, cosmetic containers, etc.), automotive interior parts (room lamp covers, instrument panels, door trims, door pockets, consoles, etc.) and exterior parts (bumpers, grilles, light fixtures, etc.), electrical components (casings for various electrical equipment, etc.), semiconductor-related materials (semiconductor transport containers, etc.), solar cell encapsulants, sheets, fibers (monofilaments, multifilaments, spunbond nonwovens, meltblown nonwovens, etc.), extrusion lamination (single-layer, multi-layer), films (single-layer and multi-layer cast films, water-cooled inflation films, air-cooled inflation films, transversely uniaxially oriented films, longitudinally uniaxially oriented films, sequentially biaxially oriented films, simultaneously biaxially oriented films, and other films produced by known molding methods). For multilayer films, methods include co-extrusion and lamination of multiple films, and depending on the desired function, the process can be applied to the surface layer, layers other than the surface layer, or both. The film can be applied to various known uses, such as packaging films for food, pharmaceuticals, daily necessities, industrial products, clothing, etc., and decorative films for building materials, decorative film applications, etc. The film can be used as is, or it can be laminated with other substrates using methods such as dry lamination or extrusion lamination.

[0053] Suitable examples of the molded products described above include medical components. Suitable examples of medical components include kit formulations, pre-filled syringes, dialyzer housings, eye drop containers, and disposable syringes. Medical components may be subjected to known sterilization methods such as autoclave sterilization, radiation sterilization, EOG sterilization, and ultraviolet sterilization. In particular, because it can maintain excellent elution properties even after radiation sterilization, it is suitable for medical components to which radiation sterilization is applied. Other suitable examples of molded products include food containers.

[0054] [3.1] Kit formulation A kit formulation (kit product) refers to a product that combines multiple pharmaceuticals, or pharmaceuticals and medical devices, into a specific dosage system and packages them together. Typically, it combines a formulation containing the main active ingredient with a solvent or suspension for dissolution, suspension, or mixing at the time of use, or with a formulation containing other active ingredients. This configuration simplifies preparation work in the medical field, reduces the risk of bacterial contamination and foreign matter contamination, prevents drug mix-ups, and enables rapid response in emergencies. It also contributes to more efficient inventory management and the prevention of medical errors, thus having high clinical utility. Specific examples of kit products include (1) injectable drugs pre-filled into medical devices such as syringes, (2) injectable drugs and diluents set in a single container and designed to be mixed at the time of use, and (3) in which multiple pharmaceuticals are pre-dissolved or mixed and filled into a single container. These are approved as "a single pharmaceutical product" under pharmaceutical regulations, and the overall quality, efficacy, and safety of the product are evaluated.

[0055] An example of a kit formulation is a pre-filled syringe. A pre-filled syringe is a syringe-shaped preparation that is pre-filled with a drug solution or medication. There are two types: single-chamber type, which is filled with one type of liquid, and double-chamber type, which is filled with two types of medication. Most pre-filled syringes are single-chamber type, but double-chamber type preparations include liquid-powder type preparations consisting of powder and its solvent, and liquid-liquid type preparations consisting of two types of liquid. An example of a single-chamber type preparation is heparin solution. In Figure 1, reference numeral 1 indicates an example of a pre-filled syringe. Prefilled syringes must pass section 7.02 of the Test Methods for Plastic Pharmaceutical Containers in the 18th Edition of the Japanese Pharmacopoeia (hereinafter also referred to as "JP"). The prefilled syringes of this disclosure can pass at least the ashing test and the elution test (121°C).

[0056] [3.2] Dialyzer housing When kidney function declines, a device called an artificial kidney is used to remove water and waste products from the blood, while also regulating the blood to prevent it from becoming acidic. This is generally called hemodialysis. Figure 2 shows the concept, and Figure 3 shows the details of the dialyzer that cleans the blood. In Figures 2 and 3, a needle is first inserted into a blood vessel in the arm 11 of the person receiving dialysis, and blood is continuously drawn using a blood pump 13. This blood pump 13 can send blood in one direction by rotating while pressing rollers against a soft tube 12. The part that cleans the blood is a device called a dialyzer 15. To prevent air from entering the dialyzer 15, which would reduce efficiency, and to ensure the safety of the person receiving dialysis, tubes called air traps 14 are attached to the front and back of the dialyzer to prevent air from entering. The dialyzer 15 cleans the blood by removing excess water and waste products through a semipermeable membrane. At that time, a control device called a console 16 accurately sends the dialysate to the dialyzer 15, and the dialysate mixed with water and waste products inside is carried out to the outside. The console 16 is also equipped with various alarms to ensure that hemodialysis can be performed safely.

[0057] Furthermore, the dialyzer 15 consists of a cylindrical outer cylinder 22 and a header 23 that covers the outer cylinder 22. The headers 23 on both sides are connected to the hollow fiber 21, and blood flows in from the blood inlet 27 of one header 23. As the blood flows through the hollow fiber 21, water and waste products in the blood are discharged into the dialysate outside the hollow fiber 21, and then the blood flows out from the blood outlet 28 of the other header 23. The outer cylinder 22 is also provided with a dialysate inlet 29 and a dialysate outlet 30, and the dialysate is circulated within the dialyzer 15 to remove water and waste products. The outer cylinder 22 corresponds to the housing of the dialyzer in this disclosure.

[0058] The housing of the dialyzer disclosed herein meets the following criteria when measured in accordance with the quality and test method 1(2) of the Dialysis Fluid Supply Unit and Dialysis Fluid Circuit, as specified in the approval standards for dialysis-type artificial kidney devices issued by the Director of the Examination Division of the Pharmaceutical Affairs Bureau of the Ministry of Health and Welfare on June 20, 1983, as Pharmaceutical Affairs Bureau Notification No. 401 to the heads of the health departments (bureaus) of each prefecture, and when measurements are taken, the dissolution test results meet the following criteria. (i) Appearance: Colorless lamp, no foreign objects. (ii) Foaming: Disappears within 3 minutes (iii) pH: Difference from the blank is 1.5 or less (iv) Zinc: Standard solution or less (v) Potassium permanganate reducing agent: Difference in potassium permanganate consumption compared to standard solution is 1.0 ml or less. (vi) Evaporation residue: 1.0 mg or less (vii) Ultraviolet absorption spectrum: 0.1 or less

[0059] [3.3] Eye drop container Figure 4 shows an example of an eye drop container. The eye drop container 40 comprises a container body 43 (plastic container for eye drops) having a storage space for storing eye drops (liquid contents), an inner stopper 47 attached to the upper end of the mouth 45 that communicates with the storage space, and a cap 49 that is detachably attached to the mouth 45 so as to cover the inner stopper 47. The container body 43 (plastic container for eye drops) of this disclosure can meet the following standards for plastic containers for eye drops.

[0060] [3.3.1] Standards and test methods for plastic containers for eye drops The standards and test methods will be explained in accordance with Pharmaceutical Affairs Notification No. 336 dated March 28, 1996. [3.3.1.1] Outline of standards and test methods for plastic containers for eye drops (1) Transparency and appearance The container must be transparent enough to allow for the insoluble foreign body test of eye drops according to the Japanese Pharmacopoeia (JP) general rules, and must be free from streaks, scratches, bubbles, or other defects that would interfere with its use. (2) Residue after strong heating → Same as in the Japanese Pharmacopoeia (3) Heavy metals → Same as in the Japanese Pharmacopoeia (4) Eluted substances → Both the extraction method and standards differ from those of the Japanese Pharmacopoeia. The extraction process is basically performed at 70°C for 24 hours. In terms of evaluation, the appearance of the eluate will be added as an item, and the foaming criterion will be shortened from 3 minutes to 2 minutes. On the other hand, the standards for ultraviolet absorption spectra will be relaxed, and the regulations for the range above 240 nm will be eliminated.

[0061] Figure 5 summarizes the differences between the eye drop container and the Japanese Pharmacopoeia.

[0062] [3.4] Food containers Figure 6 shows an example of a food container, a dessert container 51 (pudding container).

[0063] [3.5] Disposable syringe, an example of a disposable container. Figure 7 shows an example of a disposable syringe 61. [Examples]

[0064] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these descriptions. In each example and comparative example, the physical property measurements were performed by the following methods, and the following propylene polymers (B) and clearing nucleating agents (A) were used.

[0065] Experiment A 1. Test Method (1) Melt flow rate (MFR): Measured in accordance with JIS K7210-1:2014, 230℃, 2.16kg load. (2) Flexural modulus: Measured at 23°C in accordance with JIS K7171. (3) Charpy impact strength: Measured at 23°C in accordance with JIS K7111. (4) Haze value: Measured using a 1 mm thick sheet in accordance with JIS K7105:1981. (5) Crystallization temperature: The crystallization peak temperature was measured by DSC in accordance with JIS K7121:1987. Generally, the higher this temperature, the easier injection molding, film molding, extrusion molding, etc. become, and the better the formability of the moldable material. (6) Melting point Measurements were performed using a TA Instruments Q2000 DSC. A 5.0 mg sample was taken, held at 200°C for 5 minutes, then cooled to -10°C at a rate of 10°C / min, held at -10°C for 5 minutes, and then heated to 200°C at a rate of 10°C / min. The peak top temperature of the melting curve during heating was defined as the melting point.

[0066] 2. Propylene polymer (B), clearing nucleating agent (A), and other additives (1) Propylene polymer (B) (i) Ethylene-propylene random copolymer (B1): Wintec WMG03 (manufactured by Nippon Polypropylene Co., Ltd.). Melting point: 142℃, Crystallization temperature: 109℃, MFR: 30g / 10min. (ii) Ethylene-butene-propylene random copolymer (B2): Novatec FG4A (manufactured by Nippon Polypropylene Co., Ltd.). Melting point: 136°C, crystallization temperature: 97°C, MFR: 7g / 10min.

[0067] (2) Clearing nucleating agent (A) (i)(A1) Transparex CA2302 (manufactured by ADEKA Corporation): A clearing nucleating agent corresponding to the clearing nucleating agent (A) of the present invention. (ii)(A2) Mirad NX8000J (manufactured by Milliken Japan): A clearing nucleating agent that does not fall under the category of clearing nucleating agent (A) of the present invention.

[0068] 3. Preparation and evaluation of test specimens (Examples 1-4, Comparative Examples 1-3) Propylene polymers and a clearing nucleating agent were prepared in the proportions (parts by weight) shown in Table 1. After dry blending in a super mixer, the mixture was melt-kneaded using a 35 mm diameter twin-screw extruder (Toshiba Machine Co., Ltd., model TEM-35) and extruded from the die at a die outlet temperature of 230°C to form pellets. The resulting pellets were injection-molded using an injection molding machine (Shibaura Machine Co., Ltd., model EC100) at a resin temperature of 230°C and a mold temperature of 40°C to produce test specimens. The physical properties of the obtained test specimens were measured. The results are shown in Tables 1 and 2.

[0069] [Table 1]

[0070] [Table 2]

[0071] 4. Evaluation Results As is clear from Table 1, Examples 1-3, which consist of 100 parts by weight of propylene-ethylene random copolymer with 0.05, 0.10, and 0.30 parts by weight of the clearing nucleating agent (A1), exhibit superior transparency compared to Comparative Example 1, which contained the clearing nucleating agent (A2). In particular, as shown in Example 2, the addition of 0.10 parts by weight of the clearing nucleating agent (A1) resulted in a haze value about half that of Comparative Example 1, which contained the optimal amount of a known clearing nucleating agent, demonstrating superior transparency.

[0072] Table 2 shows the results of measurements including flexural modulus when the propylene polymer was changed to B2. Comparative Example 3 did not contain a transparency nucleating agent and showed poor transparency, low flexural modulus, and low crystallization temperature. Example 4 contained 0.10 parts by weight of the transparency nucleating agent (A1) and it can be confirmed that the transparency is superior even when the propylene polymer is changed compared to Comparative Example 2, which contained the transparency nucleating agent (A2). Furthermore, compared to Comparative Example 3, Example 4 also showed improvements in flexural modulus, Charpy impact strength, and crystallization temperature, indicating not only a good balance of physical properties such as rigidity and impact resistance, but also an increased crystallization temperature and superior moldability.

[0073] Experiment B 1. Test Method (1) Melt flow rate (MFR): Measured using the same method as in Experiment A. (2) Flexural modulus: Measured using the same method as in Experiment A. (3) Charpy impact strength: Measured using the same method as in Experiment A. (4) Haze value: Measured using the same method as in Experiment A. (5) Crystallization temperature: Measured using the same method as in Experiment A. (6) Density: Measured in accordance with JIS K7112. (7) Temperature deflection under load: Measured in accordance with JIS K7191-1:2015 under a load of 0.45 MPa. (8) Tests according to the Japanese Pharmacopoeia, which is the test standard for pre-filled syringes: The elution test and ashing test, which are performed by heating at 121°C for 1 hour, were conducted as described in 7.02 Test Methods for Plastic Pharmaceutical Containers of the 18th Revised Japanese Pharmacopoeia. (9) Regarding the quality and test methods of the blood circuit in the dialysis-type artificial kidney device approval standard IV, which is a test standard for hemodialysis (dialyzer), the elution test was performed after sterilization by irradiating with gamma rays at 25 kGy. (10) An elution test was performed on the blood circuit quality and test method of the Dialysis-type Artificial Kidney Device Approval Standard IV, which is the test standard for artificial dialysis (dialyzer). (11) Tests were conducted for transparency, appearance, ignition residue, and heavy metals using the test method for plastic containers for eye drops, which is a test for eye drop containers. (12) The elution test was conducted in accordance with JIS T3210:2006, the test standard for disposable syringes. (13) As part of the testing of food cups (voluntary standard testing), an odor test was conducted. Specifically, 150g of pellets were placed in a 6L odor bag from Omi Odor Air Service Co., Ltd., left at room temperature for 24 hours, and evaluated by five monitors as follows. Judgment criteria ○: No odor is detected. ×: An odor can be detected.

[0074] 2. Propylene polymer (B), clearing nucleating agent (A), and other additives (1) Propylene polymer (B) (i) Propylene homopolymer (B3): MA3UQ (manufactured by Nippon Polypropylene Co., Ltd.). Melting point: 165°C, crystallization temperature: 115°C, MFR: 8.5g / 10min. (ii) Propylene homopolymer (B4): MA04C (manufactured by Nippon Polypropylene Co., Ltd.). Melting point: 163°C, crystallization temperature: 120°C, MFR: 40g / 10min. (ii) Propylene homopolymer (B5): EA9HD (manufactured by Nippon Polypropylene Co., Ltd.). Melting point: 163°C, crystallization temperature: 114°C, MFR: 0.4g / 10min.

[0075] (2) Clearing nucleating agent (A) (i)(A1) Transparex CA2302 (manufactured by ADEKA Corporation): A clearing nucleating agent corresponding to the clearing nucleating agent (A) of the present invention. (ii)(A3) Gelol MD (manufactured by Shin Nippon Rika Co., Ltd.): A clearing nucleating agent that does not fall under the clearing nucleating agent (A) of the present invention. (iii)(A4) Adeka Stab NA11 (manufactured by ADEKA): A clearing nucleating agent that does not fall under the category of clearing nucleating agent (A) of the present invention.

[0076] (3) Antioxidants (i) TINUVIN 622SF: TNV622SF (Manufactured by BASF Japan) (ii) IRGAFOS 168: IF168 (manufactured by BASF Japan)

[0077] (4) Peroxides Perhexa 25B: PHA25B (manufactured by Nippon Oil & Fats Co., Ltd.)

[0078] (5) Neutralizing agent DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.)

[0079] 3. Preparation and evaluation of test specimens (Examples 5-9, Comparative Examples 4-8) Propylene polymers and a clearing nucleating agent were prepared in the proportions (parts by weight) shown in Table 3. After dry blending in a super mixer, the mixture was melt-kneaded using a 35 mm diameter twin-screw extruder (Toshiba Machine Co., Ltd., model TEM-35) and extruded from the die at a die outlet temperature of 230°C to form pellets. The resulting pellets were injection-molded using an injection molding machine (Shibaura Machine Co., Ltd., model EC100) at a resin temperature of 230°C and a mold temperature of 40°C to produce test specimens. The physical properties of the obtained test specimens were measured. The results are shown in Table 3.

[0080] [Table 3]

[0081] 4. Evaluation Results As is clear from Table 3, Examples 5-9 consisted of 100 parts by weight of propylene polymer with 0.02-0.9 parts by weight of the clearing nucleating agent (A1), and exhibited superior transparency compared to Comparative Examples 4-8. Furthermore, Examples 5-9 passed the dissolution test according to the Japanese Pharmacopoeia, confirming their suitability for use in medical components. Furthermore, the results from Examples 5, 6, and 7, which contained a clearing nucleating agent equivalent to clearing nucleating agent (A), confirmed that the composition of this disclosure is suitable for use in pre-filled syringes, hemodialysis (dialyzers), eye drop containers, and disposable syringes. Furthermore, the results from Examples 5 and 7, which contained a clearing nucleating agent equivalent to clearing nucleating agent (A), confirmed that the composition of this disclosure is suitable for use in food containers. [Industrial applicability]

[0082] The propylene-based resin composition and molded articles of the present invention possess excellent transparency and moldability that could not be achieved with conventional transparency nucleating agents, making it possible to easily provide molded articles with superior transparency using known molding methods. Furthermore, the propylene-based resin composition and molded articles of the present invention also possess excellent rigidity and impact resistance, making them extremely useful for applications such as food containers, caps, medical devices, medical containers, packaging films, stationery sheets, clothing cases, daily necessities, automotive parts, and electrical components. [Explanation of Symbols]

[0083] 1… Pre-filled syringe 11…The arm of a person receiving dialysis 12... Tube 13… Blood pump 14…Air Trap 15… Dialyzer 16… Console 27…Blood inlet 28…Blood outlet 29…Dialysate inlet 30...Dialysate outlet 21… Hollow Fiber 22... Outer cylinder of the dialyzer 23... Dialyzer header 40… Eye drop container 43…Container body 45...Mouth 47...Inner stopper 49... Cap 51…Dessert container 61… Disposable syringe

Claims

1. A propylene resin composition characterized by containing 0.02 to 0.9 parts by weight of a clearing nucleating agent (A) represented by the following chemical structural formula (1) in 100 parts by weight of a propylene polymer (B) that satisfies the following condition (B-1). 【Chemistry 1】 [In general formula (1), X １ , X ２ and X ３ Each of the symbols represents an unsubstituted or substituted phenylene group, while *, **, and *** represent sites that bond with other atoms. Condition (B-1) The propylene polymer (B) is at least one propylene polymer selected from the group consisting of propylene homopolymer, propylene-α-olefin random copolymer, and propylene-α-olefin block copolymer.

2. A propylene-based resin composition according to claim 1, for use in medical components.

3. The propylene resin composition according to claim 2, wherein the medical component is at least one selected from the group consisting of kit formulations, pre-filled syringes, dialyzer housings, and disposable syringes.

4. The propylene-based polymer (B) is a propylene-based resin composition according to claim 1, wherein the propylene-based polymer (B) has a melt flow rate of 0.5 to 100 g / 10 min in accordance with JIS K7210-1:2014 (230°C, 2.16 kg load).

5. The propylene resin composition according to claim 1, wherein the clearing nucleating agent (A) is represented by the following chemical structural formula (2). 【Chemistry 2】 [In general formula (2), W １ ~W ３ Each of these independently represents a group represented by the following general formula (3). 【Transformation 3】 [In general formula (3), Ar １ represents an unsubstituted or substituted phenyl group, R １ represents a hydrogen atom or a monovalent substituent, L １ and L ２ each independently represent a group represented by the following general formula (4), m represents an integer of 0 or 1 or more, and **** represents the site bonded to the oxygen atom. ] 【Chemistry 4】 [In general formula (4), X ４ and X ５ Each of these independently represents an unsubstituted or substituted phenylene group, and A １ [where n represents a direct bond or an alkanediyl group with 1 to 30 carbon atoms, and n represents 0 or 1.]

6. The propylene resin composition according to claim 1, wherein the clearing nucleating agent (A) comprises a compound represented by the following chemical structural formula (5). 【Transformation 5】

7. A medical component using the propylene resin composition according to any one of claims 1 to 6.

8. A kit formulation using the propylene resin composition according to any one of claims 1 to 6.

9. A pre-filled syringe using the propylene resin composition according to any one of claims 1 to 6.

10. A dialyzer housing using the propylene resin composition according to any one of claims 1 to 6.

11. An eye drop container using the propylene resin composition according to any one of claims 1 to 6.

12. A food container using the propylene resin composition according to any one of claims 1, 4, 5, or 6.

13. A disposable syringe using the propylene resin composition described in any one of claims 1 to 6.

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