Resin composition for thermoforming

Abstract

The object of the present invention is to provide a thermoforming resin composition that does not emit odors during high-temperature heating such as melting and kneading of thermoplastic resins and during molding processes, and from the resin molded product. [Solution] A thermoforming resin composition comprising a thermoplastic resin (S), a hydrazine compound (B), and zeolite particles (ZL), wherein the hydrazine compound (B) is a compound represented by the following general formula (1) and / or the compound represented by the following general formula (2), and the silica / alumina ratio (SiO2 / Al2O3 molar ratio) of the zeolite particles (ZL) is 20 or less. The masterbatch composition comprising a polyolefin resin (A), a hydrazine compound (B), and zeolite particles (ZL), wherein the hydrazine compound (B) is a compound represented by the following general formula (1) and / or the compound represented by the following general formula (2), and the silica / alumina ratio (SiO2 / Al2O3 molar ratio) of the zeolite particles (ZL) is 20 or less.

Description

[Technical Field]

[0001] This invention relates to a resin composition for thermoforming. [Background technology]

[0002] Widely used resin molded products are obtained by heating and melting thermoplastic resins and then molding them. When heating and melting thermoplastic resins and molding them, they are heated to 180-220°C. Under such high-temperature conditions, the thermoplastic resin and additives undergo thermal decomposition, generating volatile components. This not only generates odors and VOCs during the molding process, but also causes odors and VOCs to be generated from residual components when the molded product is heated. In this invention, VOC (Volatile Organic Compounds) refers to chemical substances as defined by the World Health Organization (WHO). Specifically, VOC components refer to chemical substances with a boiling point range of "50-100°C" to "240-260°C" (i.e., chemical substances with a boiling point where the lower limit is in the range of 50-100°C and the upper limit is in the range of 240-260°C).

[0003] It has been proposed to add hydrazide compounds as scavenging agents for aldehydes, which are VOC components (Patent Documents 1-2). However, even the resin compositions described in Patent Documents 1-2 have residual odors, and there is a demand for resin compositions with even lower odor. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 4-345648 [Patent Document 2] Japanese Patent Publication No. 2006-182825 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a thermoforming resin composition that does not emit odors during high-temperature heating such as melting and kneading of thermoplastic resins and during molding processes, and from the resin molded product. [Means for solving the problem]

[0006] The present inventors have diligently studied to solve the above problems and have arrived at the present invention. Specifically, the present invention is a thermoforming resin composition containing a thermoplastic resin (S), a hydrazine compound (B), and zeolite particles (ZL), wherein the hydrazine compound (B) is a compound represented by the following general formula (1) and / or the following general formula (2), and the silica / alumina ratio (SiO2 / Al2O3 molar ratio) of the zeolite particles (ZL) is 20 or less. [ka] (In the formula, n represents an integer between 8 and 16.) [ka] (In the formula, m represents an integer between 8 and 16.) [Effects of the Invention]

[0007] The thermoforming resin composition (X) of the present invention does not generate odors during high-temperature heating such as melt mixing and molding processes, nor does it produce odors from the molded resin product. Furthermore, it has good mold contamination resistance. [Modes for carrying out the invention]

[0008] <Thermoplastic resin (S)> Examples of thermoplastic resins (S) in the present invention include acrylic resins, polyester resins, polyacetal resins, polyolefin resins (A), styrene resins, polyamide resins, phenolic resins, and fluororesins, and may also be recycled thermoplastic resins obtained by material recycling from collected plastic products. Furthermore, as the thermoplastic resin (S), bioplastics such as polyvinyl alcohol resin for melt molding, polylactic acid resin made from starch contained in corn, etc., and composite bioplastics which are mixtures of plant-derived starch and the aforementioned thermoplastic resin (such as rice resin which is a mixture with rice-derived starch) can also be used. Furthermore, the thermoplastic resin (S) included in the thermoforming resin composition of the present invention may be used alone or in combination of two or more types.

[0009] The thermoplastic resin (S) is preferably a polyester resin (such as polyethylene terephthalate and polybutylene succinate) or a polyolefin resin (A) (such as polyethylene, polypropylene, polybutene, and polyisobutylene). Furthermore, the aforementioned bioplastics and composite bioplastics can also be preferably used as the thermoplastic resin (S). Polypropylene includes random polypropylene, which is copolymerized with a small amount of ethylene, and block polypropylene, in which ethylene propylene rubber (EPR), a rubber component, is uniformly and finely dispersed within the polypropylene.

[0010] The melt flow rate (MFR) of the polyolefin resin (A) according to JIS K 7210-1 is preferably 35.0 g / 10 min or less, more preferably 30.0 g / 10 min or less, and most preferably 20.0 g / 10 min to 30.0 g / 10 min. For polypropylene, the measurement was performed at (230°C, load 2.16 kg), and for polyethylene, it was performed at (190°C, load 2.16 kg). If the melt flow rate of the polyolefin resin (A) is within the above range, it can be easily melt-kneaded with the hydrazine compound (B).

[0011] <Hydrazine compound (B)> The hydrazine compound (B) in the present invention is a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2). As the hydrazine compound (B), one type may be used alone, or two or more types may be used in combination.

[0012] [Chemical Formula] (In the formula, n represents an integer of 8 to 16.)

[0013] [Chemical Formula] (In the formula, m represents an integer of 8 to 16.)

[0014] Preferable examples of the compound represented by the above general formula (1) include capric acid hydrazide (n=8), lauric acid hydrazide (n=10), myristic acid hydrazide (n=12), palmitic acid hydrazide (n=14), margaric acid hydrazide (n=15) and the like.

[0015] Preferable examples of the compound represented by the above general formula (2) include sebacic acid dihydrazide (m=8), dodecanedioic acid dihydrazide and the like (m=10), octadecanedioic acid dihydrazide (m=16) and the like. From the viewpoints of compatibility with resins and odor reduction, sebacic acid dihydrazide and dodecanedioic acid dihydrazide are more preferable.

[0016] <Zeolite (ZL)> The zeolite particles (ZL) in the present invention are crystalline aluminosilicates having a three-dimensional framework structure. They may be natural products or synthetic products. Those having various known crystal structures, for example, any of A-type, X-type, LSX-type, L-type, Y-type, ferrierite, mordenite, beta-type and ZSM-5 (also referred to as MFI-type) can be used.

[0017] The zeolite particles (ZL) have regular pores in their structure. In the present invention, the pore diameter of the zeolite particles (ZL) is preferably 5 to 20 Å, and more preferably 5 to 10 Å, from the viewpoint of odor reduction. The pore diameter of the zeolite particles (ZL) is a value obtained by measuring the amount of gas adsorbed (argon gas) using a constant volume method with a fully automated gas adsorption amount measuring device.

[0018] The zeolite particles (ZL) may be spherical, rod-shaped, elliptical, or any other shape, and may be in any form such as powder, lump, or granules. However, from the viewpoint of dispersibility in industrial products when incorporated into industrial products, odor reduction effect, and moldability of industrial products, a powder form is preferred.

[0019] The average particle size of the zeolite particles (ZL) can be selected as appropriate, but a weight-average particle size of 500 μm or less is preferred, 200 μm or less is more preferred, and 2 to 100 μm is most preferred. If the average particle size of the zeolite particles (ZL) is 100 μm or more, it shall be the value obtained by the standard sieving method using a standard sieve specified in JIS Z 8801, and if it is less than 100 μm, it shall be the value obtained by the laser diffraction / scattering method in accordance with JIS Z 8825.

[0020] The zeolite particles (ZL) have a silica / alumina ratio (SiO2 / Al2O3 molar ratio) of preferably 20 or less, more preferably 2 to 10, and particularly preferably 2 to 5. The silica / alumina ratio refers to the molar ratio of silica to alumina contained in the chemical composition of the zeolite. These compounds are available commercially. Generally, zeolites tend to be more hydrophobic the higher their silica / alumina ratio (SiO2 / Al2O3 molar ratio), and more hydrophilic the lower their silica / alumina ratio. By using zeolite particles (ZL) within the aforementioned range, which are relatively hydrophilic, it is presumed that a synergistic effect of odor reduction by zeolite particles (ZL) and odor reduction by hydrazine compound (B) (chemical reaction) can be more easily obtained because the hydrazine compound (B) and the zeolite particles (ZL) have an affinity for each other.

[0021] The BET specific surface area of ​​the zeolite particles (ZL) is preferably 100 to 1000 m². 2 / g, and more preferably 200-1000m 2 The value is / g. Within the aforementioned range, odor reduction by zeolite particles (ZL) is good. The BET specific surface area can be determined by measurement in accordance with JIS Z 8830:2013.

[0022] <Thermoforming resin composition (X)> The thermoforming resin composition (X) of the present invention contains the thermoplastic resin (S), the hydrazine compound (B), and the zeolite (ZL), wherein the hydrazine compound (B) is a compound represented by the following general formula (1) and / or the following general formula (2), and the silica / alumina ratio (SiO2 / Al2O3 molar ratio) of the zeolite particles (ZL) is 20 or less.

[0023] [ka] (In the formula, n represents an integer between 8 and 16.)

[0024] [ka] (In the formula, m represents an integer between 8 and 16.)

[0025] The target odors are not particularly limited and include, for example, aldehyde-based odor substances (aldehyde compounds) such as formaldehyde, acetaldehyde, propionaldehyde, acrolein, n-butyraldehyde, isobutyraldehyde, 3-methyl-butyraldehyde, crotonaldehyde, pentanal, hexanal, heptanal, octanal, nonanal, and decanal; alcohols such as low molecular weight alkyl alcohols, glycerin derivatives, and glycol compounds; and acids such as acetic acid, propionic acid, and formic acid. In particular, it is more effective against the odors of aldehyde compounds and acids, and especially effective against the odors of formaldehyde, acetaldehyde, and acetic acid. For this reason, the thermoforming resin composition (X) can be suitably used in a variety of applications, particularly in daily necessities, electrical appliance housings, and automotive applications (preferably automotive interior parts).

[0026] In the present invention, the weight ratio of hydrazine compound (B) to zeolite particles (ZL) is preferably 0.5:99.5 to 80:20, and more preferably 0.9:99.1 to 75:25. The amount of hydrazine compound (B) is preferably 0.05 to 10% by weight, and more preferably 0.05 to 5% by weight, based on the weight of the thermoplastic resin (S). Within the above range, melt molding can be performed well and an odor reduction effect can be exhibited. The amount of zeolite particles (ZL) is preferably 0.05 to 15% by weight, and more preferably 0.1 to 10% by weight, based on the weight of the thermoplastic resin (S). Within the above range, molding is good and an odor reduction effect is also good.

[0027] In addition to the thermoplastic resin (S), hydrazine compound (B), and zeolite particles (ZL), the thermoforming resin composition (X) of the present invention may optionally contain other additives such as colorants, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, and fillers.

[0028] Examples of colorants include inorganic pigments [white pigments, cobalt compounds, iron compounds, and sulfides, etc.], organic pigments [azo pigments and polycyclic pigments, etc.], and dyes [azo, indigoid, sulfide, alizarin, acridine, thiazole, nitro, and aniline dyes, etc.].

[0029] Examples of mold release agents include lower (1-4 carbon atoms) alcohol esters of higher fatty acids (such as butyl stearate), polyvalent (2-4 or more carbon atoms) alcohol esters of fatty acids (2-18 carbon atoms) (such as hydrogenated castor oil), glycol (2-8 carbon atoms) esters of fatty acids (2-18 carbon atoms) (such as ethylene glycol monostearate), and liquid paraffin.

[0030] As antioxidants, known antioxidants can be used, and preferred antioxidants include hindered phenol-based antioxidants and phosphoric acid-based antioxidants. Examples of hindered phenol antioxidants include pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], and octadecyl-3-(3,5-di-butyl-4-hydroxyphenyl)propionate, of which pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] is preferred. Examples of phosphorus-based antioxidants include tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, and bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, of which tris(2,4-di-t-butylphenyl) phosphite is preferred.

[0031] Examples of flame retardants include halogen-containing flame retardants, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants, and phosphorus-containing flame retardants.

[0032] Examples of UV absorbers include benzotriazoles [such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole], benzophenones (such as 2-hydroxy-4-methoxybenzophenone), salicylates (such as phenyl salicylate), and acrylates (such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate).

[0033] Examples of antibacterial agents include benzoic acid, sorbic acid, halogenated phenols, organic iodine, nitriles (such as 2,4,5,6-tetrachloroisophthalonitrile), thiocyanosides (methylenebisthianocyanate), N-haloalkylthioimide, copper compounds (such as 8-oxyquinoline copper), benzimidazole, benzothiazole, trihaloallyl, triazole, organic nitrogen sulfur compounds (such as Slaoff 39), quaternary ammonium compounds, and pyridine compounds.

[0034] Examples of fillers include inorganic fillers such as kaolin, talc, silica, titanium dioxide, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fibers, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate, alumina, magnesia, wollastonite, xonotlite, whiskers, and metal powders, as well as organic fillers such as cross-linked resin particles (epoxy resin particles, etc.).

[0035] The types and amounts of other additives that the thermoforming resin composition (X) may further contain can be selected according to the application of the thermoforming resin composition and the type of thermoplastic resin (S) constituting the thermoforming resin composition. In particular, when the thermoplastic resin (S) is the bioplastic or composite bioplastic described above, it is preferable to include 0.05 to 5% by weight of antioxidants based on the total weight of the thermoforming resin composition, and more preferably 0.1 to 2% by weight of antioxidants, from the viewpoint of odor and mechanical properties of the industrial product.

[0036] The thermoforming resin composition (X) of the present invention can be produced by melt-kneading a hydrazine compound (B), zeolite particles (ZL), thermoplastic resin (S), and optionally other additives in a known manner. Specifically, this can be done by mixing pelletized or powdered raw materials in a known powder mixer (such as a Henschel mixer), and then heating and melt-mixing them in a melt-kneader (such as a twin-screw extruder) to form pellets. There are no restrictions on the order in which the raw materials are added during the melt-kneading of hydrazine compounds (B), zeolite particles (ZL), thermoplastic resins (S), and other additives.

[0037] The temperature and mixing time during melt mixing can be adjusted according to the type of thermoplastic resin (S), and the preferred mixing temperature is 130 to 230°C. The thermoforming resin composition (X) obtained by melt-kneading may be extruded in strand form from an extruder, cooled with a belt cooler or the like, and then cut and molded into pellets, or it may be pulverized into powder or granules by a known method.

[0038] The thermoforming resin composition (X) of the present invention can be molded using known molding methods such as injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, and film molding (casting method, tenter method, and inflation method, etc.), and single-layer molding, multi-layer molding, and foam molding are also possible depending on the purpose.

[0039] <Masterbatch composition (MB)> The masterbatch composition (MB) contains a polyolefin resin (A), a hydrazine compound (B), and zeolite particles (ZL), wherein the hydrazine compound (B) is a compound represented by the following general formula (1) and / or the following general formula (2), and the silica / alumina ratio (SiO2 / Al2O3 molar ratio) of the zeolite particles (ZL) is 20 or less.

[0040] [ka] (In the formula, n represents an integer between 8 and 16.)

[0041] [ka] (In the formula, m represents an integer between 8 and 16.)

[0042] In the masterbatch composition (MB), based on the total weight of the polyolefin resin (A), hydrazine compound (B), and zeolite (ZL), the weight of the hydrazine compound (B) is preferably 3 to 30% by weight, more preferably 5 to 20% by weight; the weight of the zeolite (ZL) is preferably 30 to 65% by weight, more preferably 40 to 60% by weight; and the weight of the polyolefin resin (A) is preferably 30 to 60% by weight, more preferably 35 to 50% by weight.

[0043] The masterbatch composition (MB) may further contain the other additives. The weight of the other additives is preferably 0.2 to 2% by weight, based on the weight of the masterbatch composition (MB).

[0044] The masterbatch composition (MB) can be produced, for example, by melt-kneading the polyolefin resin (A), the hydrazine compound (B), the zeolite particles (ZL), and optionally the other additives, preferably at 150°C to 220°C.

[0045] The masterbatch composition (MB) contains a hydrazine compound (B) and zeolite particles (ZL) in high concentrations, making it suitable for use in thermoforming resin compositions (X). Specifically, for example, the thermoforming resin composition (X) can be produced by melt-kneading the masterbatch composition (MB) with a thermoplastic resin (S). Furthermore, the masterbatch composition (MB) is useful as a deodorant for thermoplastic resins. From an industrial standpoint, the masterbatch composition (MB) is preferably in pellet form. [Examples]

[0046] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[0047] <Manufacturing Example 1> Biomass composite polyethylene (S-2) consisting of wood powder and polyethylene was obtained by melt-kneading 2.0 parts by weight of Umex 1010 (manufactured by Sanyo Chemical Industries, Ltd.), an acid-modified polyolefin, 58.0 parts by weight of polyethylene resin (product name: UBE Polyethylene LDPE F222NH, manufactured by Ube Maruzen Polyethylene Co., Ltd.), and 40 parts by weight of wood powder (cedar wood powder with an average particle size of 180 μm dried in a forward-flow dryer at 80°C for 2 hours) in a vented twin-screw extruder heated to 200°C at 200 rpm and with a residence time of 5 minutes.

[0048] <Manufacturing Example 2> 3.0 parts by weight of acid-modified polyolefin Yumex 1010 (manufactured by Sanyo Chemical Industries, Ltd.), 57.0 parts by weight of polybutylene succinate (product name: BioPBS FZ91, manufactured by PTT MCC Biochem), 30 parts by weight of starch (derived from wheat flour, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 10 parts by weight of D-sorbitol were melt-kneaded in a vented twin-screw extruder heated to 200°C at 200 rpm with a residence time of 5 minutes to obtain biomass-composite polybutylene succinate (S-3) consisting of starch and polybutylene succinate.

[0049] <Examples 1-3> A preliminary mixture was obtained by placing the types and amounts of hydrazine compounds (B) and zeolite particles (ZL) listed in Table 1 into a polypropylene beaker and gently stirring with a stirring blade. Next, the types and amounts of polyolefin resin (A) listed in Table 1 were added to the kneading section of a laboplast mill (a kneading and extrusion testing device from Toyo Seiki Seisakusho Co., Ltd.) that was temperature-controlled to the molding temperature listed in Table 1, and mixing for 1 minute at a stirring speed of 10 rpm. Then, the preliminary mixture was further added to the kneading section and mixed for another 10 minutes at a stirring speed of 60 rpm. The mixture was removed from the laboplast mill and molded to a thickness of 2 mm using a pressure molding machine that was temperature-controlled to the molding temperature listed in Table 1, and then cut with a pelletizer (diameter 2 mm × length 4 mm) to obtain each masterbatch composition (MB).

[0050] [Table 1]

[0051] The raw materials used in Table 1 are as follows: <Hydrazide compound (B)> • Dihydrazide sebacate (B-1) • Dodecane dioxide dihydrazide (B-2) • Hydrazide stearate (B-3) <Zeolite particles (ZL)> Zeolite (ZL-1): BET specific surface area = 850 m² 2 Synthetic zeolite powder with a silica / alumina ratio of 2.5 / g, product name: Molecular Sieve 13X Powder, manufactured by Resonaq Universal Co., Ltd. • Zeolite (ZL-2): BET specific surface area = 300 m² 2 Synthetic zeolite powder with a silica / alumina ratio of 6.1, product name: HS-500, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Zeolite (ZL-3): BET specific surface area = 400 m² 2 Synthetic zeolite powder with a silica / alumina ratio of 18 / g, product name: HS-642, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. <Polyolefin resin (A)> • (A-1): Low-density polyethylene manufactured by Ube Maruzen Polyethylene Co., Ltd., product name: J2522 • (A-2): Polypropylene injection molding block manufactured by Sun Allomer Co., Ltd., product name: Sun Allomer PM970A

[0052] <Examples 11-17, Comparative Examples 11-14> The thermoplastic resin (S) described in Table 2 was melt-kneaded at 200 rpm with a residence time of 5 minutes using a twin-screw extruder with a vent adjusted to the molding temperature described in Table 2, while adding a hydrazide compound (B) and zeolite particles (ZL) through a side feeder from the vent. Subsequently, the mixture was cut into pellets (2 mm in diameter x 4 mm in length) using a pelletizer to obtain each thermoforming resin composition (X).

[0053] <Examples 18-20> According to the formulations shown in Table 2, the thermoplastic resin (S) and the masterbatch composition (MB) were blended in a Henschel mixer for 3 minutes. The mixture was then melt-kneaded in a vented twin-screw extruder, temperature-controlled to the temperature shown in Table 2, at 200 rpm with a residence time of 5 minutes. Subsequently, it was cut into pellets (2 mm in diameter x 4 mm in length) using a pelletizer to obtain each thermoforming resin composition (X).

[0054] [Table 2]

[0055] The raw materials used in Table 2 are as follows: <Hydrazide compound (B)> • Dihydrazide sebacate (B-1) • Dodecane dioxide dihydrazide (B-2) • Hydrazide stearate (B-3) • Dihydrazide adipic acid (Ratio B-1) <Zeolite particles (B)> Zeolite (ZL-1): BET specific surface area = 850 m² 2 / g, synthetic zeolite powder with a silica / alumina ratio of 2.5, trade name: Molecular Sieve 13X Powder, manufactured by Resonac Universal Co., Ltd. ·Zeolite (ZL-2): BET specific surface area = 300 m 2 / g, synthetic zeolite powder with a silica / alumina ratio of 6.1, trade name: HS-500, manufactured by FUJIFILM Wako Pure Chemical Corporation ·Zeolite (ZL-3): BET specific surface area = 400 m 2 / g, synthetic zeolite powder with a silica / alumina ratio of 18, trade name: HS-642, manufactured by FUJIFILM Wako Pure Chemical Corporation ·Zeolite (ZL-4): BET specific surface area = 200 to 300 m 2 / g, natural zeolite powder with a silica / alumina ratio of 5, trade name: SP#600, manufactured by Nitto Funka Kogyo Co., Ltd. ·Zeolite (Comparative ZL-1): BET specific surface area = 330 m 2 / g, synthetic zeolite powder with a silica / alumina ratio of 40, trade name: HS-840, manufactured by FUJIFILM Wako Pure Chemical Corporation <Thermoplastic Resin (S)> ·(S-1): Recycled polypropylene manufactured by Teamplas Chemical, trade name: TPC-PPC 05 / 2 ·(S-2): Biomass composite polyethylene composed of wood flour and polyethylene, prepared in Production Example 1 ·(S-3): Biomass composite polybutylene succinate composed of starch and polybutylene succinate, prepared in Production Example 2

[0056] <Odor of Thermoformable Resin Composition> 50 g of the obtained pellets of each thermoformable resin composition (X) was placed in a glass Erlenmeyer flask with an internal volume of 500 mL, the flask was capped and allowed to stand in an environment at 80°C. At the point 2 hours after being left to stand, the cap was slightly opened, and the odor was sensory-evaluated according to the following criteria. <Evaluation Criteria> 0: Odorless 1: Faint odor 2: Weak odor 3: Moderate odor 4: Strong odor

[0057] <Mold Staining Resistance During Molding> For each obtained thermoformable resin composition (X), using an injection molding machine [trade name "PS40E5ASE", manufactured by Nissei Plastic Industrial Co., Ltd.], 500 shots of test specimens for evaluation (70 mm long, 70 mm wide, 2 mm thick) were injection molded at a cylinder temperature of 200°C, a mold temperature of 60°C, and a molding cycle of 30 seconds. The inner side of the mold after the molding was visually checked to confirm the state of stains, which was classified into 4 levels according to the following criteria. <Classification Criteria for Stain State> ◎: No change is observed on the mold surface. ◯: Stains (surface fogging) are slightly observed on the mold surface. △: Stains (surface fogging) and residual resin are observed on the mold surface. ×: The mold surface is extremely stained, and the appearance of the molded article is poor.

[0058] <Generation Amount of Odor-Causing Substances When Molded Article is Heated> The aforementioned evaluation test specimen was freeze-pulverized using a small refrigerated pulverizer under liquid nitrogen with a pre-cooling time of 10 minutes and a pulverization time of 20 minutes to obtain a measurement sample. 100 mg of the obtained measurement sample was placed in a 20 mL sampling tube, set in a gas chromatograph mass spectrometer (HS-GC / MS), and the odor-causing substances generated when the molded product was heated were measured under the following measurement conditions. The peak area of each odor-causing substance was divided by the weight of the measurement sample to calculate the relative value when the amount of the odor-causing substance in the thermoplastic resin (S) alone was set to 100, which was defined as the generation amount of odor-causing substances when each resin composition was heated. <GC / MS Measurement Conditions> GC Conditions ·Apparatus: GCMS-QP2020NX [manufactured by Shimadzu Corporation] ·Column: SH-WAX (Length: 60 m, Inner diameter: 0.25 mm, Film thickness: 0.25 μm) ·Split ratio: 5 ·Temperature program: After holding at 40°C for 5 minutes, the temperature is raised to 230°C, held at 230°C for 10 minutes, and the temperature rising rate is 3°C / min MS Conditions ·Ionization mode: EI ·Detection mode: Scan (m / z=33~300) • Detector voltage (relative): 0kV • Tuning voltage: 1.09kV Vial temperature: 60°C

[0059] The results in Tables 1 and 2 show that the thermoforming resin composition (X) of the present invention has reduced odor and good mold contamination properties compared to the comparative composition. [Industrial applicability]

[0060] The thermoforming resin composition (X) of the present invention, and the thermoforming resin composition (X) using the masterbatch composition (MB), do not produce odor-causing chemical substances even when heated, and odorless molded articles can be obtained. Therefore, it can be preferably used for resin molded articles used in everyday items and electrical appliances, and for resin molded articles used in enclosed spaces such as the interior of automobiles. In particular, it is useful when using bioplastics and recycled thermoplastic resins, which tend to generate odors, as the thermoplastic resin.

Claims

1. The material contains a thermoplastic resin (S), a hydrazine compound (B), and zeolite particles (ZL), wherein the hydrazine compound (B) is a compound represented by the following general formula (1) and / or the following general formula (2), and the silica / alumina ratio (SiO2) of the zeolite particles (ZL) is ２ / Al ２ O ３ A thermoforming resin composition having a molar ratio of 20 or less. 【Chemistry 1】 (In the formula, n represents an integer between 8 and 16.) 【Chemistry 2】 (In the formula, m represents an integer between 8 and 16.)

2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (S) comprises a polyolefin resin (A).

3. The material contains a polyolefin resin (A), a hydrazine compound (B), and zeolite particles (ZL), wherein the hydrazine compound (B) is a compound represented by the following general formula (1) and / or the following general formula (2), and the silica / alumina ratio (SiO2) of the zeolite particles (ZL) is ２ / Al ２ O ３ The masterbatch composition having a molar ratio of 20 or less. 【Chemistry 1】 (In the formula, n represents an integer between 8 and 16.) 【Chemistry 2】 (In the formula, m represents an integer between 8 and 16.)

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